CN114242983A - V-shaped groove3S4@ C composite material and preparation method and application thereof - Google Patents
V-shaped groove3S4@ C composite material and preparation method and application thereof Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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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
- H01M4/58—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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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Abstract
The invention discloses a V3S4The @ C composite material and the preparation method and the application thereof. The composite material comprises a carbon matrix with a one-dimensional rod-shaped structure and V grown on the surface of the carbon matrix in situ3S4A nanoplatelet of component (a). The preparation method comprises the following steps: (1) will contain V2And (3) carrying out hydrothermal reaction on the solution of the C MXene material and the terephthalic acid, separating a solid product in a reaction liquid, and drying for later use. (2) And (2) annealing the solid product obtained in the step (1) to obtain a precursor MIL-47 as. (3) Carrying out gas phase vulcanization treatment on the precursor MIL-47as obtained in the step (2) to obtain V3S4@ C composite material. When the V is3S4When the @ C composite material is used as a positive electrode material of a lithium-sulfur battery, the material may beAs a sulfur conductive matrix, the method can also accelerate the conversion of long-chain lithium polysulfide to Li2S2With Li2And the transformation of S effectively inhibits the shuttle effect and improves the cycle performance of the battery.
Description
Technical Field
The invention relates to the technical field of preparation of lithium-sulfur battery cathode materials, in particular to a lithium-sulfur battery cathode materialAnd a V3S4The @ C composite material and the preparation method and the application thereof.
Background
The information in this background section is disclosed to enhance understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms part of the prior art already known to a person of ordinary skill in the art.
The lithium-sulfur battery is a next-generation secondary battery candidate system with great potential due to the advantages of high theoretical energy density, low raw material and lining, environmental protection, abundant reserves and the like. However, due to its serious shuttling effect, the battery has the disadvantages of low utilization rate of active substances, poor cycle stability and the like. To solve the above problems, it was first thought that the dissolution of lithium polysulfide was suppressed to some extent by designing a reasonably designed carbon material having a nanostructure, such as graphene, carbon nanofibers, carbon nanotubes, and the like. However, although this class of non-polar materials has good electrical conductivity, there is limited adsorption and conversion to polysulfides.
More and more experiments prove that the polar material, particularly the two-dimensional transition metal sulfide, has extremely strong chemical adsorption and catalytic action on lithium polysulfide. For example, Ruihu Wang et al (Zhuibin Cheng, Zhubibg Xiao, Hui Pan, et al, Elastic Sandwich-Type rGO-VS2(S compositions with High Tap sensitivity: Structural and Chemical Cooperation engineering Lithium-sulfurer Batteries with High Energy sensitivity, Advanced Energy Materials, 2017.8.1702337. doi: 10.1002/aenm.201702337) reports a sandwich structure rGO-VS2Composite material due to VS2The polar adsorption and the catalytic action of the catalyst are that under the current density of 0.2C, the capacity loss of each circle is only 0.11-0.27%. V3S4NiAs type structure possessing unique twist, usually from VS2The monolayer member and the additional V atoms connect the two adjacent layers, which will provide a multidimensional channel for the electron/ion charge carriers and at the same time improve their diffusion rate. In addition, V having a unique crystal structure3S4Also has strong adsorption and catalysis effects on lithium polysulfide. 2020 toTianyu Tang et al (Tianyu Tang, Teng Zhang, Lina Zhao, et al. Multifunctional V)3S4Nanowire/graphene compositions for high performance Li-S batteries, Science China Materials, 2020.63.1910 doi:10.1007/S40843-020-3S4Of a nanocomposite V3S4G, which has excellent electrochemical performance as a positive electrode material of a lithium-sulfur battery, however, the preparation method of the precursor is too complicated to facilitate subsequent large-scale production, and in addition, the existing V has the defects of low cost and low cost3S4The electrochemical properties of the composite material formed with the carbon material are yet to be further improved.
Disclosure of Invention
In order to solve the above difficult problems, the present invention provides a V3S4The @ C composite material can effectively inhibit shuttle effect when being used as a positive electrode material of a lithium-sulfur battery, improves the cycle performance of the battery, and the V provided by the invention3S4The preparation method of the @ C composite material is simpler and more efficient. In order to achieve the purpose, the invention discloses the following technical scheme.
In a first aspect of the invention, a V is disclosed3S4The @ C composite material comprises a carbon matrix with a one-dimensional rod-like structure and V grown in situ on the surface of the carbon matrix3S4A nanoplatelet of component (a).
Further, some of the V3S4The nano sheet is inserted on the carbon substrate. The composite material disclosed by the invention not only has excellent electronic conductivity, but also has a good catalytic sulfur fixation effect, and can effectively inhibit a shuttle effect when being used as a positive electrode material of a lithium-sulfur battery, so that the cycle performance of the battery is improved.
Further, the diameter of the carbon substrate is 1 μm or less.
In a second aspect of the invention, a V is disclosed3S4The preparation method of the @ C composite material comprises the following steps:
(1) will contain V2And (3) carrying out hydrothermal reaction on the solution of the C MXene material and terephthalic acid (BDC), separating a solid product in a reaction liquid, and drying for later use.
(2) Annealing the solid product of step (1) to obtain a vanadium-based Metal Organic Framework (MOF): v (OH) (BDC.)x(H2BDC), as precursor MIL-47 as.
(3) Carrying out gas phase vulcanization treatment on the precursor MIL-47as obtained in the step (2) to obtain V3S4@ C composite material.
Further, in the step (1), the V2The mass ratio of the C MXene material to the terephthalic acid is controlled to be 1: (5-10) preferably. In the present invention, said V2C MXene is used as a vanadium source, and terephthalic acid is used as an organic ligand.
Further, in the step (1), the temperature of the hydrothermal reaction is controlled to be 150-220 ℃ and the time is controlled to be 8-14 hours. In this step, V2C MXene can release vanadium ions with different valence states in the solution, and at high temperature, trivalent vanadium ions can be used as central ions to react with terephthalic acid to generate a precursor MIL-47 as.
Further, in the step (1), a solid product in the reaction liquid is centrifugally separated, and then dried for 10-24 hours at 50-80 ℃ to obtain a dried solid product, so that annealing treatment is conveniently carried out.
Further, in the step (2), the temperature of the annealing treatment is controlled to be 260-300 ℃, and the time is preferably controlled to be 20-26 hours. In this step, the excessive terephthalic acid is removed at a high temperature, and the MIL-47as is more crystalline.
Further, in the step (3), the temperature of the gas phase vulcanization treatment is controlled to be 600-700 ℃, and the time is preferably controlled to be 1-3 hours. In the step, the central vanadium ion of the precursor MIL-47as can generate a two-dimensional sheet V at high temperature in situ3S4The corresponding organic ligand terephthalic acid is then derivatized to carbon.
Further, in the step (3), the sulfur source used in the gas-phase vulcanization treatment comprises: thioacetamide, sulfur powder, etc.
Further, in the step (3), the gas-phase vulcanization treatment method comprises: and placing the precursor MIL-47as into a heating furnace, arranging a sulfur source at the upstream of the precursor MIL-47as, and heating under the flowing nitrogen or inert atmosphere condition to enable the sulfur source to form gas-phase sulfur and flow through the precursor MIL-47 as.
Further, the mass ratio of the precursor MIL-47as to the sulfur source is controlled to be 1: (5-10) preferably.
In a third aspect of the invention, said V is disclosed3S4The application of the @ C composite material in an energy storage device and an energy storage material is preferably used as a positive electrode material of a lithium-sulfur battery, so that the shuttle effect of the lithium-sulfur battery can be effectively inhibited, and the cycle performance of the battery is improved.
Compared with the prior art, the invention has the following beneficial and unique effects:
(1) compared with the existing V3S4And a carbon material, since the present invention is represented by V2C MXene is a vanadium source, and is subjected to simple hydrothermal reaction with terephthalic acid and subsequent high-temperature treatment to generate a one-dimensional rod-shaped precursor MIL-47as, wherein the surface of the one-dimensional rod-shaped precursor can be V3S4The in-situ generation of the nano-sheet provides a wide foundation, after gas phase vulcanization treatment, the one-dimensional rod-shaped precursor is converted into a one-dimensional rod-shaped carbon matrix, and a large number of V grows on the matrix in situ3S4Nanosheets, forming V3S4@ C composite material, wherein part V3S4The nano sheet is inserted on the carbon substrate. These two dimensions V3S4Nanosheets, in particular V intercalated on the carbon substrate3S4The nano-sheet can extend a large amount of specific surface area from the surface of one-dimensional rod-shaped carbon substrate for fixing sulfur, and V3S4@ C has excellent electron conductivity, when V is the one of the present invention3S4When the @ C composite material is used as a positive electrode material of a lithium-sulfur battery, the @ C composite material can be used as a conductive matrix of sulfur on the one handOn the other hand, the conversion of long-chain lithium polysulfides to Li can be accelerated2S2With Li2And the transformation of S effectively inhibits the shuttle effect and improves the cycle performance of the battery.
(2) Compared with the prior preparation V3S4And the method for preparing the carbon material has the characteristics of simplicity and high efficiency, simple and convenient operation, low cost, less pollution and high purity of the obtained product, so that the preparation process is more suitable for large-scale production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
fig. 1 is an SEM picture of the precursor MIL-47as prepared in the first embodiment of the present invention.
Fig. 2 is an XRD pattern of the precursor MIL-47as prepared in the first example of the present invention.
FIG. 3 is a bar V prepared by a first embodiment of the present invention3S4SEM pictures of @ C composite.
FIG. 4 is a bar V prepared by the first embodiment of the present invention3S4TEM and HRTEM pictures of @ C composite.
FIG. 5 is a bar-like V prepared by the first embodiment of the present invention3S4The XRD pattern of the @ C composite material.
FIG. 6 is a bar-like V prepared by the first embodiment of the present invention3S4A current density of 2C as a lithium sulfur battery cathode material of the @ C composite material.
Fig. 7 is an XRD pattern of a product prepared according to the seventh embodiment of the present invention.
Fig. 8 is a graph of cycle data for a current density of 2C for a positive electrode material for a lithium sulfur battery prepared according to a seventh embodiment of the present invention.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The reagents or starting materials used in the present invention can be purchased from conventional sources, and unless otherwise specified, the reagents or starting materials used in the present invention can be used in a conventional manner in the art or in accordance with the product specifications. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred methods and materials described in this invention are exemplary only.
As described above, although V3S4Has strong adsorption and catalysis effects on lithium polysulfide, has excellent electrochemical performance when being used as a positive electrode material of a lithium-sulfur battery, but the conventional synthesized V3S4The process of the carbon material is complicated, and the electrochemical performance of the formed composite material is still to be further improved. Therefore, the present invention proposes V3S4The invention is further illustrated by the accompanying drawings and the detailed description of the specification.
First embodiment
V-shaped groove3S4The preparation method of the @ C composite material comprises the following steps:
(1) 40mL of deionized water was placed in a 50mL reactor liner, to which was then added 0.08g of V2C MXene, stirred with a magnetic stirrer to the stated V2And C MXene is completely dissolved in deionized water, then 0.8g of terephthalic acid is added, and stirring is continued for 0.5 hour to obtain a precursor solution for later use.
(2) And (3) putting the liner filled with the precursor solution into a reaction kettle, heating to 180 ℃, preserving heat for 12 hours, naturally cooling, centrifugally washing the obtained reaction liquid by using deionized water, putting the obtained solid product into a dryer, and drying at 60 ℃ for 24 hours to obtain a yellow-green powdery precursor for later use.
(3) And putting the precursor into a porcelain boat, putting the porcelain boat into a muffle furnace, annealing at 280 ℃ for 24 hours, and naturally cooling to obtain yellow powder MIL-47as for later use.
(4) Taking 0.05g of MIL-47as and placing the MIL-47as in a porcelain boat (marked as porcelain boat 1), then taking 0.5g of thioacetamide and placing the thioacetamide in the porcelain boat (marked as porcelain boat 2), placing the porcelain boat 2 in the upstream of the airflow of the protective gas in the tube furnace, and placing the porcelain boat 1 in the downstream of the airflow of the protective gas in the tube furnace, wherein the protective gas is flowing nitrogen. After the completion, the temperature is raised to 700 ℃ at the speed of 3 ℃/min and kept for 3 hours. Naturally cooling after the heat preservation is finished to obtain a target product V3S4@C。
Second embodiment
V-shaped groove3S4The preparation method of the @ C composite material comprises the following steps:
(1) 40mL of deionized water was placed in a 50mL reactor liner, to which was then added 0.05g of V2C MXene, stirred with a magnetic stirrer to the stated V2And C MXene is completely dissolved in deionized water, then 0.4g of terephthalic acid is added, and stirring is continued for 1 hour to obtain a precursor solution for later use.
(2) And (3) putting the liner filled with the precursor solution into a reaction kettle, heating to 200 ℃, preserving heat for 10 hours, naturally cooling, centrifugally washing the obtained reaction liquid by using deionized water, putting the obtained solid product into a dryer, and drying at 50 ℃ for 12 hours to obtain a yellow-green powdery precursor for later use.
(3) And putting the precursor into a porcelain boat, putting the porcelain boat into a muffle furnace, annealing for 20 hours at 300 ℃, and naturally cooling to obtain yellow powder MIL-47as for later use.
(4) Taking 0.05g of MIL-47as and placing the MIL-47as in a porcelain boat (marked as porcelain boat 1), then taking 0.5g of thioacetamide and placing the thioacetamide in the porcelain boat (marked as porcelain boat 2), placing the porcelain boat 2 in the upstream of the airflow of the protective gas in the tube furnace, placing the porcelain boat 1 in the downstream of the airflow of the protective gas in the tube furnace, wherein the protective gasIs flowing nitrogen. After completion, the temperature is raised to 600 ℃ at the rate of 1 ℃/min and kept for 1 hour. Naturally cooling after the heat preservation is finished to obtain a target product V3S4@C。
Third embodiment
V-shaped groove3S4The preparation method of the @ C composite material comprises the following steps:
(1) 40mL of deionized water was placed in a 50mL reactor liner, to which was then added 0.12g of V2C MXene, stirred with a magnetic stirrer to the stated V2And C MXene is completely dissolved in deionized water, then 0.6g of terephthalic acid is added, and stirring is continued for 1 hour to obtain a precursor solution for later use.
(2) And (3) putting the liner filled with the precursor solution into a reaction kettle, heating to 150 ℃, preserving heat for 14 hours, naturally cooling, centrifugally washing the obtained reaction liquid by using deionized water, putting the obtained solid product into a dryer, and drying at 80 ℃ for 12 hours to obtain a yellow-green powdery precursor for later use.
(3) And putting the precursor into a porcelain boat, putting the porcelain boat into a muffle furnace, annealing for 22 hours at 290 ℃, and naturally cooling to obtain yellow powder MIL-47as for later use.
(4) Taking 0.05g of MIL-47as and placing the MIL-47as in a porcelain boat (marked as porcelain boat 1), then taking 0.25g of thioacetamide and placing the thioacetamide in the porcelain boat (marked as porcelain boat 2), placing the porcelain boat 2 in the upstream of the airflow of the protective gas in the tube furnace, and placing the porcelain boat 1 in the downstream of the airflow of the protective gas in the tube furnace, wherein the protective gas is flowing nitrogen. After completion, the temperature was raised to 650 ℃ at a rate of 2 ℃/min and held for 2 hours. Naturally cooling after the heat preservation is finished to obtain a target product V3S4@C。
Fourth embodiment
V-shaped groove3S4The preparation method of the @ C composite material comprises the following steps:
(1) 40mL of deionized water was placed in a 50mL reactor liner, to which was then added 0.2g of V2C MXene, stirred with a magnetic stirrer to the stated V2C MXene, completely dissolving in deionized water, then adding 1.2g of terephthalic acid, and continuously stirring for 1 hour to obtain a precursor solution for later use.
(2) And (3) putting the liner filled with the precursor solution into a reaction kettle, heating to 220 ℃, preserving heat for 8 hours, naturally cooling, centrifugally washing the obtained reaction liquid by using deionized water, putting the obtained solid product into a dryer, and drying at 50 ℃ for 12 hours to obtain a yellow-green powdery precursor for later use.
(3) And putting the precursor into a porcelain boat, putting the porcelain boat into a muffle furnace, annealing for 26 hours at 260 ℃, and naturally cooling to obtain yellow powder MIL-47as for later use.
(4) Taking 0.05g of MIL-47as and placing the MIL-47as in a porcelain boat (marked as porcelain boat 1), then taking 0.3g of thioacetamide and placing the thioacetamide in the porcelain boat (marked as porcelain boat 2), placing the porcelain boat 2 in the upstream of the airflow of the protective gas in the tube furnace, and placing the porcelain boat 1 in the downstream of the airflow of the protective gas in the tube furnace, wherein the protective gas is flowing nitrogen. After completion, the temperature is raised to 600 ℃ at the rate of 1 ℃/min and kept for 1 hour. Naturally cooling after the heat preservation is finished to obtain a target product V3S4@C。
Fifth embodiment
V-shaped groove3S4The preparation method of the @ C composite material comprises the following steps:
(1) 40mL of deionized water was placed in a 50mL reactor liner, to which was then added 0.08g of V2C MXene, stirred with a magnetic stirrer to the stated V2And C MXene is completely dissolved in deionized water, then 0.4g of terephthalic acid is added, and stirring is continued for 1 hour to obtain a precursor solution for later use.
(2) And (3) putting the liner filled with the precursor solution into a reaction kettle, heating to 160 ℃, preserving heat for 13 hours, naturally cooling, centrifugally washing the obtained reaction liquid by using deionized water, putting the obtained solid product into a dryer, and drying at 50 ℃ for 12 hours to obtain a yellow-green powdery precursor for later use.
(3) And putting the precursor into a porcelain boat, putting the porcelain boat into a muffle furnace, annealing for 22 hours at 275 ℃, and naturally cooling to obtain yellow powder MIL-47as for later use.
(4) Taking 0.05g of MIL-47as and placing the MIL-47as in a porcelain boat (marked as porcelain boat 1), then taking 0.4g of thioacetamide and placing the thioacetamide in the porcelain boat (marked as porcelain boat 2), placing the porcelain boat 2 in the upstream of the airflow of the protective gas in the tube furnace, and placing the porcelain boat 1 in the downstream of the airflow of the protective gas in the tube furnace, wherein the protective gas is flowing nitrogen. After completion, the temperature is raised to 680 ℃ at the rate of 3 ℃/min and kept for 1 hour. Naturally cooling after the heat preservation is finished to obtain a target product V3S4@C。
Sixth embodiment
V-shaped groove3S4The preparation method of the @ C composite material comprises the following steps:
(1) 40mL of deionized water was placed in a 50mL reactor liner, to which was then added 0.12g of V2C MXene, stirred with a magnetic stirrer to the stated V2And C MXene is completely dissolved in deionized water, then 1.2g of terephthalic acid is added, and stirring is continued for 1 hour to obtain a precursor solution for later use.
(2) And (3) putting the liner filled with the precursor solution into a reaction kettle, heating to 180 ℃, preserving heat for 12 hours, naturally cooling, centrifugally washing the obtained reaction liquid by using deionized water, putting the obtained solid product into a dryer, and drying at 80 ℃ for 24 hours to obtain a yellow-green powdery precursor for later use.
(3) And putting the precursor into a porcelain boat, putting the porcelain boat into a muffle furnace, annealing at 280 ℃ for 24 hours, and naturally cooling to obtain yellow powder MIL-47as for later use.
(4) Taking 0.05g of MIL-47as and placing the MIL-47as in a porcelain boat (marked as porcelain boat 1), then taking 0.5g of thioacetamide and placing the thioacetamide in the porcelain boat (marked as porcelain boat 2), placing the porcelain boat 2 in the upstream of the airflow of the protective gas in the tube furnace, and placing the porcelain boat 1 in the downstream of the airflow of the protective gas in the tube furnace, wherein the protective gas is flowing nitrogen. After the completion, the temperature is raised to 700 ℃ at the speed of 3 ℃/min and kept for 3 hours. Naturally cooling after the heat preservation is finished to obtain a target product V3S4@C。
Seventh embodiment
(1) 40mL of deionized water was placed in a 50mL reactor liner, to which was then added 0.12g of V2C MXene, stirred with a magnetic stirrer to the stated V2And C MXene is completely dissolved in deionized water, then 1.2g of terephthalic acid is added, and stirring is continued for 1 hour to obtain a precursor solution for later use.
(2) And (3) putting the liner filled with the precursor solution into a reaction kettle, heating to 180 ℃, preserving heat for 12 hours, naturally cooling, centrifugally washing the obtained reaction liquid by using deionized water, putting the obtained solid product into a dryer, and drying at 80 ℃ for 24 hours to obtain a yellow-green powdery precursor for later use.
(3) And putting the precursor into a porcelain boat, putting the porcelain boat into a muffle furnace, annealing at 280 ℃ for 24 hours, and naturally cooling to obtain yellow powder MIL-47as for later use.
(4) Taking 0.05g of MIL-47as and placing the MIL-47as in a porcelain boat (marked as porcelain boat 1), then taking 0.5g of thioacetamide and placing the thioacetamide in the porcelain boat (marked as porcelain boat 2), placing the porcelain boat 2 in the upstream of the airflow of the protective gas in the tube furnace, and placing the porcelain boat 1 in the downstream of the airflow of the protective gas in the tube furnace, wherein the protective gas is flowing nitrogen. After completion, the temperature is raised to 500 ℃ at the rate of 3 ℃/min and kept for 3 hours. And naturally cooling after heat preservation is finished to obtain the target product.
Performance testing
Fig. 1 is an SEM picture of the precursor MIL-47as prepared in step (3) of the first example, and it can be seen that this precursor has a distinct one-dimensional rod-like structure with a diameter below 1 μm.
Fig. 2 is an XRD pattern of the precursor MIL-47as prepared in step (3) of the first example, which can be seen to have better crystallinity and purity, and the precursor component is v (oh) ((bdc)).x(H2BDC), small amounts of organic ligands (terephthalic acid) remain in the vanadium-based MOF formed.
FIG. 3 shows V prepared in step (4) of the first embodiment3S4Structure of @ CThe morphology of the composite material can be seen to comprise a structure of a one-dimensional rod-shaped structure and two-dimensional nanosheets grown in situ on the surface of the structure, and the structure enables the surface of the one-dimensional rod-shaped structure to extend out of a large specific surface area, so that more active sites are exposed.
FIG. 4 is V prepared in step (4) of the first embodiment3S4In TEM picture (a picture) and HRTEM picture (b picture and C picture) of @ C composite material, it can be seen that the component of the two-dimensional nanosheet is V3S4。
FIG. 5 shows V prepared in step (4) of the first embodiment3S4XRD picture of @ C composite material proves that V is successfully synthesized in the first embodiment3S4The @ C nanocomposite material has the one-dimensional rod-shaped structure which is a carbon substrate and retains the one-dimensional rod-shaped structural characteristics of the precursor MIL-47 as.
FIG. 6 shows V prepared in step (4) of the first embodiment3S4The discharge curve and coulombic efficiency of the @ C composite material at 2C current density (electrolyte is 1M lithium bis (trifluoromethane) sulfonamide (LiTFSI) dissolved in a mixed solvent of DOL and DME with a volume ratio of 1: 1, and contains 1.0% LiNO3(ii) a The voltage interval is 1.7-2.8V; the surface loading amount is 1.21mg cm-2). It can be seen that: v3S4When the @ C composite material is used as a positive electrode material of a lithium-sulfur battery, the first-circle discharge capacity is up to 547.1mAhg at a high current density of 2C-1And after 500 cycles, the capacity can still be maintained by 70%, and excellent electrochemical performance is shown. This is due to the in situ growth of a large number of V's on a one-dimensional rod-like carbon substrate3S4Nanosheet to form V3S4@ C composite material. These two dimensions V3S4The nano-sheet can extend a large amount of specific surface area from the surface of one-dimensional rod-shaped carbon substrate for fixing sulfur, and V3S4@ C has excellent electron conductivity, when V is the one of the present invention3S4When the @ C composite material is used as a positive electrode material of a lithium-sulfur battery, the material can serve as a conductive matrix of sulfur on the one hand, and can accelerate the conversion of long-chain lithium polysulfide into long-chain lithium polysulfide on the other handLi2S2With Li2And the transformation of S effectively inhibits the shuttle effect and improves the cycle performance of the battery.
FIG. 7 is an XRD picture of the product prepared in step (4) of the seventh example, which shows that the precursor MIL-47as can not be successfully converted into V under the condition that the annealing temperature in step (3) is not reached3S4@C。
FIG. 8 is a graph showing the discharge curve and coulombic efficiency at 2C current density of the material prepared in step (4) of the seventh example (electrolyte is 1M lithium bis (trifluoromethane) sulfonamide (LiTFSI) dissolved in a mixed solvent of DOL and DME at a volume ratio of 1: 1, and contains 1.0% LiNO)3(ii) a The voltage interval is 1.7-2.8V; the surface loading amount is 1.18 mg cm-2). It can be seen that: when the unsulfurized material is adopted as the positive electrode material of the lithium-sulfur battery, the discharge capacity of the first circle is only 473 mAh g at the high current density of 2C-1And can only maintain 45% of the capacity after 500 cycles, and the long-cycle performance under high current is poor.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. V-shaped groove3S4A @ C composite material, characterized in that the composite material comprises a carbon matrix of one-dimensional rod-like structure and V grown in situ on the surface of the carbon matrix3S4A nanoplatelet of component (a).
2. V according to claim 13S4@ C composite material, wherein a part of said V3S4The nano sheet is inserted on the carbon substrate; preferably, theThe diameter of the carbon substrate is less than 1 μm.
3. V-shaped groove3S4The preparation method of the @ C composite material is characterized by comprising the following steps of:
(1) will contain V2Carrying out hydrothermal reaction on the solution of the C MXene material and the terephthalic acid, separating a solid product in a reaction liquid, and drying for later use;
(2) annealing the solid product obtained in the step (1) to obtain a vanadium-based Metal Organic Framework (MOF): v (OH) (BDC.)x(H2BDC), as precursor MIL-47 as;
(3) carrying out gas phase vulcanization treatment on the MIL-47as obtained in the step (2) to obtain V3S4@ C composite material.
4. V according to claim 33S4A process for the preparation of @ C composite materials, characterized in that in step (1), said V is2The mass ratio of the C MXene material to the terephthalic acid is 1: (5-10).
5. V according to claim 33S4The preparation method of the @ C composite material is characterized in that in the step (1), the temperature of the hydrothermal reaction is 150-220 ℃, and the time is 8-14 hours;
preferably, in the step (1), a solid product in the reaction solution is centrifugally separated, and then dried at 50-80 ℃ for 10-24 hours, so as to obtain a dried solid product.
6. V according to claim 33S4The preparation method of the @ C composite material is characterized in that in the step (2), the annealing treatment temperature is 260-300 ℃ and the annealing treatment time is 20-26 hours.
7. V according to claim 33S4The preparation method of the @ C composite material is characterized in that in the step (3), the temperature of the gas-phase vulcanization treatment is 600-7 DEG CThe temperature is 00 ℃ and the time is 1-3 hours;
preferably, in the step (3), the gas-phase vulcanization treatment method includes: and placing the precursor MIL-47as into a heating furnace, arranging a sulfur source at the upstream of the precursor MIL-47as, and heating under the flowing nitrogen or inert atmosphere condition to enable the sulfur source to form gas-phase sulfur and flow through the precursor MIL-47 as.
8. V according to claim 73S4The preparation method of the @ C composite material is characterized in that in the step (3), the sulfur source adopted in the gas-phase vulcanization treatment comprises the following steps: thioacetamide or sulfur powder.
9. V according to any one of claims 3 to 83S4The preparation method of the @ C composite material is characterized in that the mass ratio of the precursor MIL-47as to the sulfur source is 1: (5-10).
10. V according to claim 1 or 23S4@ C composite or V prepared by the method of any one of claims 3-83S4Application of @ C composite material in energy storage device and energy storage material, preferably, V is applied3S4The @ C composite material is used as a positive electrode material of the lithium-sulfur battery.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114843476A (en) * | 2022-05-20 | 2022-08-02 | 重庆大学 | V-shaped groove 3 S 4 Preparation method and application of @ C/G composite electrode material |
| CN115410835A (en) * | 2022-08-29 | 2022-11-29 | 西北工业大学宁波研究院 | Multifunctional vanadium metal organic framework-based carbon nanotube fiber and preparation method and application thereof |
| CN115490213A (en) * | 2022-08-30 | 2022-12-20 | 华东师范大学 | Metal organic framework derived VSe 2 Material, preparation method and application thereof |
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2021
- 2021-12-20 CN CN202111563122.8A patent/CN114242983A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114843476A (en) * | 2022-05-20 | 2022-08-02 | 重庆大学 | V-shaped groove 3 S 4 Preparation method and application of @ C/G composite electrode material |
| CN115410835A (en) * | 2022-08-29 | 2022-11-29 | 西北工业大学宁波研究院 | Multifunctional vanadium metal organic framework-based carbon nanotube fiber and preparation method and application thereof |
| CN115490213A (en) * | 2022-08-30 | 2022-12-20 | 华东师范大学 | Metal organic framework derived VSe 2 Material, preparation method and application thereof |
| CN115490213B (en) * | 2022-08-30 | 2023-08-18 | 华东师范大学 | VSe derived from metal-organic frameworks 2 Material, preparation method and application thereof |
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