WO2022032745A1 - Vo2/mxene composite material, preparation method therefor and use thereof - Google Patents

Vo2/mxene composite material, preparation method therefor and use thereof Download PDF

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WO2022032745A1
WO2022032745A1 PCT/CN2020/112566 CN2020112566W WO2022032745A1 WO 2022032745 A1 WO2022032745 A1 WO 2022032745A1 CN 2020112566 W CN2020112566 W CN 2020112566W WO 2022032745 A1 WO2022032745 A1 WO 2022032745A1
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composite material
mxene
preparation
mxene composite
material according
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French (fr)
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张业龙
徐晓丹
周健文
孙宏阳
陈俞程
郭月
彭章泉
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五邑大学
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • 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

Definitions

  • the invention belongs to the technical field of nanomaterials, and in particular relates to a VO 2 /MXene composite material and a preparation method thereof.
  • potassium ion batteries At present, with the continuous development of economy, lithium-ion batteries have been widely used in people's daily life. At the same time, the large consumption of metal lithium has caused people's concerns. Therefore, the development of new secondary alkali metal batteries has become the current research focus. It has been found that potassium ions are abundant on earth, more than 1,000 times that of lithium ions. Due to their relatively low cost, long cycle life, and high energy density, potassium ion batteries can meet the needs of the energy storage field. , is a new type of secondary alkali metal battery with great potential. Based on the above advantages, potassium ion battery is considered to be a promising large-scale electrochemical energy storage technology in the future, which is of great value to the development of new energy storage fields.
  • the radius of potassium ions is larger than that of lithium ions, and the graphite anode materials that have been commercially used in lithium ion batteries cannot meet the rapid deintercalation of potassium ions due to their small interlayer spacing (0.335 nm).
  • Anode materials for potassium-ion batteries with excellent cycle performance have become a research hotspot in this field.
  • MXene is a new type of two-dimensional transition metal carbide or nitride, which stands out because of its unique physicochemical properties.
  • this new material can be obtained by selective chemical etching, using HF to etch the A layer in the MAX phase to obtain an "accordion-like" MXene material with hydroxyl, oxygen, and fluorine functional groups on its surface, rich in chemical composition and abundant
  • the functional groups of MXene give MXene a hydrophilic surface, excellent chemical properties, and good mechanical properties. However, its interlayer spacing is small, and the surface functional groups have certain adsorption properties, so the ideal rapid ion migration effect cannot be achieved when used alone.
  • transition metal compounds have been widely studied due to their high reversible specific capacity.
  • pure transition metal compounds generate huge volume expansion during the repeated de-intercalation process of potassium ions, resulting in the crushing and shedding of electrode materials and easy agglomeration. resulting in poor electrochemical performance.
  • one of the objectives of the present invention is to provide a VO 2 /MXene composite material.
  • Another object of the present invention is to provide a preparation method of the VO 2 /MXene composite material.
  • the present invention provides an application of a VO 2 /MXene composite material, and the VO 2 /MXene composite material is applied to a negative electrode of a potassium ion battery.
  • the present invention adopts following technical scheme:
  • a preparation method of VO 2 /MXene composite material comprising the following steps:
  • step (1) The vanadium source and the reducing agent are added to the dispersion liquid obtained in step (1) according to the molar ratio of 1:2-6, preferably 1:2-4, and more preferably 1:4-6, and stir 6-20h, such as 6h, 12h, 16h, 20h, to obtain a mixed solution;
  • step (3) Transfer the mixed solution described in step (2) to the reaction kettle, put it in an oven, heat up to 110-240°C, such as 120°C, 150°C, 180°C, 220°C, and react for 10-30h, such as 10h , 15h, 20h, 24h, 28h, and then naturally cooled to room temperature to obtain a suspension;
  • step (3) the suspension described in step (3) is centrifuged, and the filter residue is thoroughly cleaned with a cleaning agent to obtain a precipitate;
  • step (4) the sediment described in step (4) is placed in a vacuum drying oven and dried to obtain a crude product
  • step (6) the crude product described in step (5) is placed in a quartz boat, the quartz boat is placed in a tube furnace, a protective gas is introduced, and heated to 400-1100 DEG C at a heating rate of 5-8 DEG C/min, For example, at 400°C, 600°C, 800°C, and 1100°C, keep the temperature for 2-12h, such as 2h, 6h, 10h, 12h, and then naturally cool to room temperature to obtain VO 2 /MXene composite material.
  • a protective gas is introduced, and heated to 400-1100 DEG C at a heating rate of 5-8 DEG C/min, For example, at 400°C, 600°C, 800°C, and 1100°C, keep the temperature for 2-12h, such as 2h, 6h, 10h, 12h, and then naturally cool to room temperature to obtain VO 2 /MXene composite material.
  • the vanadium source is at least one of NH 4 VO 3 and NaVO 3 .
  • the MXene is at least one of Ti 3 C 2 T x , V 3 C 2 T x , and Mo 3 N 2 T x , preferably Ti 3 N 2 T x , V 3 C 2 T x , Tx is a surface functional group -O, -F or -OH.
  • the reducing agent is at least one of oxalic acid and ascorbic acid.
  • the dispersant is at least one of N,N-dimethylformamide, ethanol, and ethylene glycol.
  • step (3) the dispersion liquid is transferred to the reaction kettle, put into an oven, heated to 110-240°C, preferably 150-200°C, such as 130°C, 150°C, 180°C, and reacted for 10-30h , preferably 15-24h, such as 10, 14, 18, 20, 30h.
  • the protective gas is Ar or N 2
  • the gas flow rate is 150-300ml/min, such as 170ml/min, 190ml/min, 200ml/min, 220ml/min, 240ml/min, 260ml/min, 280ml/min , 300ml/min.
  • the cleaning agent is at least one of water and ethanol, preferably, the suspension obtained in step (3) is thoroughly cleaned with deionized water and absolute ethanol, and deionized water and absolute ethanol can be used for alternate cleaning 3-10 times, preferably 4-7 times.
  • the rotational speed used for centrifugation in step (4) is 4000-8000r/min, preferably 6000r/min, and the centrifugation time is 4-8min, preferably 6min.
  • the temperature of vacuum drying in step (5) is 50-70°C, preferably 60°C, and the drying time is 5-12h, preferably 10h, such as 6h, 8h, 10h, 12h.
  • the degree of vacuum does not exceed 131Pa, preferably 130Pa, 125Pa, 100Pa, 90Pa.
  • the loading amount of VO 2 in the VO 2 /MXene composite material is 40-180wt%, preferably 40-100wt%, 80-130wt%, 100-180wt%.
  • a potassium ion battery negative electrode comprising the VO 2 /MXene composite material prepared by the above preparation method.
  • a potassium ion battery comprising the above-mentioned battery negative electrode.
  • the VO 2 /MXene composite material of the present invention can effectively suppress the volume expansion of the electrode material during the cycle, prevent the VO 2 material from falling off and agglomeration, improve the cycle stability, increase the Reversible specific capacity; compared with pure MXene material, VO 2 material can grow crystals between MXene layers, which is beneficial to the increase of interlayer spacing and the expansion of specific surface area. It can be seen that VO 2 material and MXene material have a synergistic effect.
  • the VO 2 /MXene composite material of the present invention exhibits good electrical conductivity, high reversible specific capacity, and excellent cycle stability.
  • the composite material of the present invention has low cost of raw materials, high production efficiency and simple preparation method, and has great practical significance for the large-scale development and application of potassium ion batteries.
  • Fig. 1 is the scanning electron microscope image of VO 2 /MXene composite material in embodiment 3;
  • Fig. 2 is the cycle performance diagram measured under the current density of 100mA/g of potassium ion battery assembled with VO 2 /Mxene composite material in Example 3;
  • Figure 3 is a graph of the cycle performance measured at a current density of 100 mA/g for a potassium-ion battery assembled with a pure VO 2 material in Comparative Example 1;
  • Figure 4 is a graph of the cycle performance of the potassium-ion battery assembled with pure MXene material in Comparative Example 2 at a current density of 100 mA/g.
  • the Ti 3 C 2 T x nanoparticles were purchased from Beijing Beike New Material Technology Co., Ltd., number BK2020011814, size: 1-5 ⁇ m, purity: 99%, product application fields: energy storage, catalysis, analytical chemistry, etc.
  • a preparation method of VO 2 /MXene composite material comprising the following steps:
  • step (1) (2) adding 0.3 mol NH 4 VO 3 and 0.6 mol oxalic acid to the dispersion described in step (1), and stirring for 6 hours to obtain a mixed solution;
  • step (3) transferring the mixed solution of step (2) into a reaction kettle with a capacity of 50ml and sealing, placing it in an oven, heating to 110°C, keeping the temperature for 12h, and then cooling to room temperature to obtain a suspension;
  • step (3) the suspension described in step (3) was centrifuged for 4 minutes under the condition of 4000r/min, and the filter residue was washed 3 times with deionized water and absolute ethanol alternately, and the precipitate was collected;
  • step (4) drying the precipitate obtained in step (4) in a vacuum drying oven at a drying temperature of 60° C. and a drying time of 6 hours to obtain a crude product;
  • step (6) the crude product obtained in step (5) is placed in a quartz boat, the quartz boat is placed in a tube furnace, high-purity Ar is introduced, and the flow rate is 150ml/min, and heated to 400 °C with a heating rate of 5°C/min °C, kept for 3h, and then naturally cooled to room temperature to obtain VO 2 /MXene composites.
  • the electrochemical test of the VO 2 /MXene composite prepared in this example shows that at a current density of 100 mA/g, after 100 cycles, the reversible specific capacity is 338 mAh/g, which is a pure VO 2 (103.6 mAh/g ) is 3.26 times that of undoped MXene (61.1 mA h/g), and 5.5 times that of undoped MXene (61.1 mA h/g), and the VO 2 /MXene composite in this example exhibits excellent potassium storage performance.
  • a preparation method of VO 2 /MXene composite material comprising the following steps:
  • step (2) adding 0.5mol NH 4 VO 3 and 2mol oxalic acid to the dispersion described in step (1), and stirring for 14 hours to obtain a mixed solution;
  • step (3) transfer the mixed solution obtained in step (2) into a reaction kettle with a capacity of 50ml and seal it, place it in an oven, heat to 180°C, keep the temperature for 20h, and then cool to room temperature to obtain a suspension;
  • step (3) the suspension obtained in step (3) is centrifuged for 6 minutes under the condition of 6000 r/min, and after alternately washing the filter residue 3 times with deionized water and absolute ethanol, the precipitate is collected;
  • step (4) drying the precipitate obtained in step (4) in a vacuum drying oven at a drying temperature of 60° C. and a drying time of 9 hours to obtain a crude product;
  • step (6) place the crude product obtained in step (5) in a quartz boat, place the quartz boat in a tube furnace, feed high-purity Ar, flow rate is 220ml/min, heat to 800 with a heating rate of 7°C/min °C, kept for 8 h, and then naturally cooled to room temperature to obtain VO 2 /MXene composites.
  • the electrochemical test of the VO 2 /MXene composite prepared in this example shows that at a current density of 100 mA/g and 100 cycles, the reversible specific capacity is 466 mAh/g, which is a pure VO 2 (103.6 mAh/g ) is 4.50 times that of undoped MXene (61.1 mA h/g), and 7.6 times that of undoped MXene (61.1 mA h/g), and the VO 2 /MXene composite in this example exhibits excellent potassium storage performance.
  • a preparation method of VO 2 /MXene composite material comprising the following steps:
  • step (2) adding 0.5mol NH 4 VO 3 and 3mol oxalic acid to the dispersion described in step (1), and stirring for 20 hours to obtain a mixed solution;
  • step (3) transferring the mixed solution obtained in step (2) into a reaction kettle with a capacity of 50ml and sealing, placing it in an oven, heating to 240° C., keeping the temperature for 24h, and then cooling to room temperature to obtain a suspension;
  • step (3) the suspension obtained in step (3) was centrifuged for 8 minutes under the condition of 8000 r/min, and after alternately washing the filter residue 3 times with deionized water and absolute ethanol, the precipitate was collected;
  • step (4) drying the precipitate obtained in step (4) in a vacuum drying oven at a drying temperature of 60° C. and a drying time of 12 hours to obtain a crude product;
  • step (6) place the crude product obtained in step (5) in a quartz boat, place the quartz boat in a tube furnace, feed high-purity Ar, flow rate is 300ml/min, heat to 1000 with a heating rate of 8°C/min °C, kept for 10 h, and then naturally cooled to room temperature to obtain VO 2 /MXene composites.
  • the electrochemical test of the VO 2 /MXene composite prepared in this example shows that the reversible specific capacity is 421mAh/g after 100 cycles at a current density of 100mA/g, which is a pure VO 2 (103.6mAh/g) ) is 4.06 times that of undoped MXene (61.1 mA h/g), and the VO 2 /MXene composite in this example exhibits excellent potassium storage performance.
  • the preparation method of pure VO material includes the following steps:
  • step (2) The dispersion liquid obtained in step (1) is transferred into a reaction kettle with a capacity of 50ml, sealed and placed in an oven, heated to 240° C., maintained for 24h, and then cooled to room temperature;
  • step (3) the product obtained in step (2) was washed 3 times with deionized water and dehydrated alcohol alternately, and centrifuged for 8 minutes under the condition of 8000 r/min with a centrifuge;
  • step (3) Drying the centrifuged product obtained in step (3) in a vacuum drying oven at a drying temperature of 60° C. and a drying time of 12 hours.
  • step (4) placing the product obtained in step (4) in a quartz boat, placing the quartz boat in a tube furnace, feeding high-purity Ar, the flow rate of 300ml/min, and heating to 1000°C with a temperature increase rate of 8°C/min , kept for 10h, and then naturally cooled to room temperature to obtain the VO 2 composite material.
  • the electrochemical test of the VO 2 material prepared in this comparative example shows that the reversible specific capacity is 103.6mAh/g after 100 cycles at a current density of 100mA/g.
  • Figure 1 is the scanning electron microscope image of the VO 2 /MXene composite material in Example 3. It can be seen from Figure 1 that the VO 2 nanomaterial in the VO 2 /MXene composite material is uniformly distributed on the surface of the MXene material sheet, and the VO 2 nanomaterial is 20nm. Around, the VO2 nanomaterials are well combined with the matrix, which can expand the distance between the lamellae without agglomeration, indicating that the layered structure of the VO2/ MXene composite was successfully prepared and effectively increased the interlayer spacing and specific surface area.
  • Figures 2-4 are graphs of the cycle performances of the potassium ion batteries of Example 3, Comparative Example 1, and Comparative Example 2 measured at a current density of 100 mA/g, respectively.
  • the VO2/ MXene composites show high battery capacity and good cycling performance compared to the pure VO2 material.
  • the potassium-ion battery assembled with MXene material exhibits good cycling stability during charge-discharge at a current density of 100 mA/g, but has a small specific capacity.
  • the layered structure of the VO 2 /MXene material contributes to the specific surface area and the active sites for ion attachment in the electrolyte, there is van der Waals force between the VO 2 material and MXene, and the surface functional groups can form chemical bonds with the material; compared with pure MXene materials , VO2 material can grow crystals between MXene layers, which is beneficial to the increase of interlayer spacing, enlarges the specific surface area, prevents agglomeration by interaction, still maintains stable capacity after 200 cycles, and larger transfer and ion adsorption area, double
  • the electric layer capacitance has good performance, which improves the ability to store potassium ions and significantly increases the specific capacity of the material. It can be seen that the VO2 material has a synergistic effect with the MXene material.
  • test methods are:
  • the specific surface area was measured by the BET specific surface area test method, and the VO2 load was analyzed by X-ray energy dispersive spectroscopy (EDS).
  • the performance test results of each group are shown in Table 1.

Abstract

A VO2/MXene composite material and a preparation method therefor. The preparation method comprises the following steps: (1) adding a MXene material into a dispersant to formulate a dispersion solution having a concentration of 10-100 mg/mL, and then stirring same for 1-6 h; (2) adding a vanadium source and a reductant into the dispersion solution of step (1) according to a molar ratio of 1: 2-6, and stirring same for 6-20 h to obtain a mixed solution; (3) reacting the mixed solution of step (2) at 110-240 °C for 10-30 h, and cooling to obtain a suspension; (4) washing the suspension of step (3) by means of a detergent, centrifuging same at 4000-8000 r/min for 4-8 min, and collecting the precipitate; (5) drying the precipitate of step (4) to obtain a crude product; and (6) heating the crude product of step (5) to 400-1100 °C at a heating rate of 5-8 °C/min in a protective atmosphere, holding the temperature for 2-12 min, and cooling same, so as to obtain the VO2/MXene composite material. Said composite has excellent rate performance, higher reversible specific capacity and good cycling stability.

Description

一种VO 2/MXene复合材料及其制备方法与应用 a VO 2/MXene composite material and its preparation method and application 技术领域technical field
本发明属于纳米材料技术领域，具体涉及一种VO 2/MXene复合材料及其制备方法。 The invention belongs to the technical field of nanomaterials, and in particular relates to a VO 2 /MXene composite material and a preparation method thereof.
背景技术Background technique
随着当今世界人口的急剧增长以及工业技术的快速发展，煤、石油、天然气等能源资源的消耗急剧增加，在传统能源日渐耗竭的同时，伴随着生态环境的日趋恶化，这也是目前人类面临的两大问题。因此，研究开发新型的可再生清洁能源以及相应的能量存储和转换装置，以提高能源的利用率，是本世纪重要的研究课题之一。With the rapid growth of the world's population and the rapid development of industrial technology, the consumption of coal, oil, natural gas and other energy resources has increased sharply. While traditional energy sources are increasingly depleted, accompanied by the deterioration of the ecological environment, this is also the current human beings are facing. Two big questions. Therefore, research and development of new types of renewable clean energy and corresponding energy storage and conversion devices to improve the utilization rate of energy is one of the important research topics in this century.
目前，随着经济的不断发展，锂离子电池已经广泛应用到人们的日常生活当中，同时，金属锂的大量消耗引起人们的担忧，为此，开发新型二次碱金属电池成为目前的研究重点。人们发现钾离子在地球上储量丰富，是锂离子的1000多倍，钾离子电池因其具有相对较低的成本，长的循环使用寿命，高的能量密度等优势，可满足储能领域的需求，是一种极具潜力的新型二次碱金属电池，基于以上优点，钾离子电池被认为是未来极具前景的大规模电化学储能技术，对新型储能领域的发展具有重要价值。At present, with the continuous development of economy, lithium-ion batteries have been widely used in people's daily life. At the same time, the large consumption of metal lithium has caused people's concerns. Therefore, the development of new secondary alkali metal batteries has become the current research focus. It has been found that potassium ions are abundant on earth, more than 1,000 times that of lithium ions. Due to their relatively low cost, long cycle life, and high energy density, potassium ion batteries can meet the needs of the energy storage field. , is a new type of secondary alkali metal battery with great potential. Based on the above advantages, potassium ion battery is considered to be a promising large-scale electrochemical energy storage technology in the future, which is of great value to the development of new energy storage fields.
但是，钾离子的半径比锂离子大，在锂离子电池中已经商业应用的石墨负极材料因其层间距(0.335nm)较小，无法满足钾离子的快速脱嵌，为此，研究高容量且循环性能优异的钾离子电池负极材料成为该领域的研究热点。However, the radius of potassium ions is larger than that of lithium ions, and the graphite anode materials that have been commercially used in lithium ion batteries cannot meet the rapid deintercalation of potassium ions due to their small interlayer spacing (0.335 nm). Anode materials for potassium-ion batteries with excellent cycle performance have become a research hotspot in this field.
近年来，一种新型的二维材料MXene，为二维材料家族增添了新成员，MXene是一种新型的二维过渡金属碳化物或氮化物，因其具有独特的物化性质脱颖而出。通常，这种新型材料可以通过选择性化学蚀刻获得，使用HF将MAX相中的A层蚀刻，得到“手风琴状”MXene材料，该材料表面含有羟基、氧、氟官能团，丰富的化学成分和丰富的官能团使MXene具有亲水表面，优异的化学性质以及良好的机械性能。但是其层间距较小，并且表面官能团具有一定的吸附性，因此单独使用并不能取得理想的离子快速迁移效果。In recent years, a new type of two-dimensional material, MXene, has added a new member to the two-dimensional material family. MXene is a new type of two-dimensional transition metal carbide or nitride, which stands out because of its unique physicochemical properties. Typically, this new material can be obtained by selective chemical etching, using HF to etch the A layer in the MAX phase to obtain an "accordion-like" MXene material with hydroxyl, oxygen, and fluorine functional groups on its surface, rich in chemical composition and abundant The functional groups of MXene give MXene a hydrophilic surface, excellent chemical properties, and good mechanical properties. However, its interlayer spacing is small, and the surface functional groups have certain adsorption properties, so the ideal rapid ion migration effect cannot be achieved when used alone.
目前，过渡金属化合物因其具有高的可逆比容量已被广泛研究，然而，单纯的过渡金属化合物在钾离子重复脱嵌过程中产生巨大的体积膨胀，造成电极材料粉碎与脱落，易团聚，从而导致较差的电化学性能。At present, transition metal compounds have been widely studied due to their high reversible specific capacity. However, pure transition metal compounds generate huge volume expansion during the repeated de-intercalation process of potassium ions, resulting in the crushing and shedding of electrode materials and easy agglomeration. resulting in poor electrochemical performance.
发明内容SUMMARY OF THE INVENTION
针对现有技术存在的问题，本发明的目的之一在于提供一种VO 2/MXene复合材料。本发明的另一目的在于提供所述VO 2/MXene复合材料的制备方法。进一步的，本发明提供一种 VO 2/MXene复合材料的应用，将所述VO 2/MXene复合材料应用于钾离子电池负极。 In view of the problems existing in the prior art, one of the objectives of the present invention is to provide a VO 2 /MXene composite material. Another object of the present invention is to provide a preparation method of the VO 2 /MXene composite material. Further, the present invention provides an application of a VO 2 /MXene composite material, and the VO 2 /MXene composite material is applied to a negative electrode of a potassium ion battery.
本发明采用以下技术方案：The present invention adopts following technical scheme:
一种VO 2/MXene复合材料的制备方法，包括以下步骤： A preparation method of VO 2 /MXene composite material, comprising the following steps:
(1)将MXene材料加入分散剂中，配制成浓度为10-100mg/ml的分散液，优选的为10-90mg/ml，进一步优选的为30-80mg/ml，例如40-70mg/ml，然后搅拌1-6h，优选的为2h、4h、6h；(1) Add the MXene material to the dispersing agent, and prepare a dispersion liquid with a concentration of 10-100 mg/ml, preferably 10-90 mg/ml, more preferably 30-80 mg/ml, such as 40-70 mg/ml, Then stir for 1-6h, preferably 2h, 4h, 6h;
(2)将钒源与还原剂按照1：2-6的摩尔比，优选的为1：2-4，进一步优选的为1：4-6，加入到步骤(1)所得分散液中，搅拌6-20h，例如6h、12h、16h、20h，得到混合液；(2) The vanadium source and the reducing agent are added to the dispersion liquid obtained in step (1) according to the molar ratio of 1:2-6, preferably 1:2-4, and more preferably 1:4-6, and stir 6-20h, such as 6h, 12h, 16h, 20h, to obtain a mixed solution;
(3)将步骤(2)所述混合液转移至反应釜中，放入烘箱中，升温至110-240℃，例如120℃、150℃、180℃、220℃，反应10-30h，例如10h、15h、20h、24h、28h，然后自然冷却至室温，得到悬浊液；(3) Transfer the mixed solution described in step (2) to the reaction kettle, put it in an oven, heat up to 110-240°C, such as 120°C, 150°C, 180°C, 220°C, and react for 10-30h, such as 10h , 15h, 20h, 24h, 28h, and then naturally cooled to room temperature to obtain a suspension;
(4)将步骤(3)所述悬浊液，离心，用清洗剂彻底清洗滤渣，获得沉淀物；(4) the suspension described in step (3) is centrifuged, and the filter residue is thoroughly cleaned with a cleaning agent to obtain a precipitate;
(5)将步骤(4)所述沉淀物置于真空干燥箱中进行干燥，得到粗产物；(5) the sediment described in step (4) is placed in a vacuum drying oven and dried to obtain a crude product;
(6)将步骤(5)所述粗产物放置于石英舟中，将石英舟放于管式炉中，通入保护气体，以5～8℃/min的升温速率加热至400-1100℃，例如400℃、600℃、800℃、1100℃，保温2-12h，例如2h、6h、10h、12h，然后自然冷却到室温，得到VO 2/MXene复合材料。 (6) the crude product described in step (5) is placed in a quartz boat, the quartz boat is placed in a tube furnace, a protective gas is introduced, and heated to 400-1100 DEG C at a heating rate of 5-8 DEG C/min, For example, at 400°C, 600°C, 800°C, and 1100°C, keep the temperature for 2-12h, such as 2h, 6h, 10h, 12h, and then naturally cool to room temperature to obtain VO 2 /MXene composite material.
进一步地，所述钒源为NH 4VO 3、NaVO 3中的至少一种。 Further, the vanadium source is at least one of NH 4 VO 3 and NaVO 3 .
进一步地，所述MXene为Ti 3C 2T x、V 3C 2T x、Mo 3N 2T x中的至少一种，优选的为Ti 3N 2T x，V 3C 2T x，T x为表面官能团-O、-F或-OH。 Further, the MXene is at least one of Ti 3 C 2 T x , V 3 C 2 T x , and Mo 3 N 2 T x , preferably Ti 3 N 2 T x , V 3 C 2 T x , Tx is a surface functional group -O, -F or -OH.
进一步地，所述还原剂为草酸、抗坏血酸中的至少一种。Further, the reducing agent is at least one of oxalic acid and ascorbic acid.
进一步地，所述分散剂为N，N-二甲基甲酰胺、乙醇、乙二醇中的至少一种。Further, the dispersant is at least one of N,N-dimethylformamide, ethanol, and ethylene glycol.
进一步地，步骤(3)中所述分散液转移至反应釜中，放入烘箱中，升温至110-240℃，优选150-200℃，例如130℃、150℃、180℃，反应10-30h，优选的为15-24h，例如10、14、18、20、30h。Further, in step (3), the dispersion liquid is transferred to the reaction kettle, put into an oven, heated to 110-240°C, preferably 150-200°C, such as 130°C, 150°C, 180°C, and reacted for 10-30h , preferably 15-24h, such as 10, 14, 18, 20, 30h.
进一步地，所述保护气体为Ar或N 2，气体流速为150-300ml/min，例如170ml/min、190ml/min、200ml/min、220ml/min、240ml/min、260ml/min、280ml/min、300ml/min。 Further, the protective gas is Ar or N 2 , and the gas flow rate is 150-300ml/min, such as 170ml/min, 190ml/min, 200ml/min, 220ml/min, 240ml/min, 260ml/min, 280ml/min , 300ml/min.
进一步地，所述清洗剂为水、乙醇中的至少一种，优选地，用去离子水和无水乙醇彻底清洗步骤(3)所得悬浊液，可以用去离子水和无水乙醇交替清洗3-10次，优选的为4-7次。Further, the cleaning agent is at least one of water and ethanol, preferably, the suspension obtained in step (3) is thoroughly cleaned with deionized water and absolute ethanol, and deionized water and absolute ethanol can be used for alternate cleaning 3-10 times, preferably 4-7 times.
进一步地，步骤(4)中所述离心使用的转速为4000-8000r/min，优选的为6000r/min，离心时间为4-8min，优选的为6min。Further, the rotational speed used for centrifugation in step (4) is 4000-8000r/min, preferably 6000r/min, and the centrifugation time is 4-8min, preferably 6min.
进一步地，步骤(5)中真空干燥的温度为50-70℃，优选的为60℃，干燥时间5-12h，优选的为10h，例如6h、8h、10h、12h。真空度不超过131Pa，优选的为130Pa、125Pa、 100Pa、90Pa。Further, the temperature of vacuum drying in step (5) is 50-70°C, preferably 60°C, and the drying time is 5-12h, preferably 10h, such as 6h, 8h, 10h, 12h. The degree of vacuum does not exceed 131Pa, preferably 130Pa, 125Pa, 100Pa, 90Pa.
进一步地，所述VO 2/MXene复合材料中VO 2负载量为40-180wt％，优选的为40-100wt％，80-130wt％，100-180wt％。 Further, the loading amount of VO 2 in the VO 2 /MXene composite material is 40-180wt%, preferably 40-100wt%, 80-130wt%, 100-180wt%.
一种钾离子电池负极，其包括利用上述制备方法制备得到的VO 2/MXene复合材料。 A potassium ion battery negative electrode, comprising the VO 2 /MXene composite material prepared by the above preparation method.
一种钾离子电池，其包括上述电池负极。A potassium ion battery, comprising the above-mentioned battery negative electrode.
本发明的有益效果：Beneficial effects of the present invention:
(1)与单纯的VO 2材料相比，本发明的VO 2/MXene复合材料可有效抑制电极材料在循环过程中的体积膨胀，防止VO 2材料的脱落和团聚，提高循环稳定性，增大可逆比容量；与单纯的MXene材料相比，VO 2材料可以在MXene层间生长结晶，有利于层间距的增加，扩大比表面积，可见VO 2材料与MXene材料具有协同增效作用。 (1) Compared with the pure VO 2 material, the VO 2 /MXene composite material of the present invention can effectively suppress the volume expansion of the electrode material during the cycle, prevent the VO 2 material from falling off and agglomeration, improve the cycle stability, increase the Reversible specific capacity; compared with pure MXene material, VO 2 material can grow crystals between MXene layers, which is beneficial to the increase of interlayer spacing and the expansion of specific surface area. It can be seen that VO 2 material and MXene material have a synergistic effect.
(2)本发明的VO 2/MXene复合材料，表现出良好的导电性，较高的可逆比容量，以及优异的循环稳定性能。 (2) The VO 2 /MXene composite material of the present invention exhibits good electrical conductivity, high reversible specific capacity, and excellent cycle stability.
(3)本发明的复合材料原料成本低廉，生产效率高，制备方法简单，对于钾离子电池的大规模开发与应用具有重大的现实意义。(3) The composite material of the present invention has low cost of raw materials, high production efficiency and simple preparation method, and has great practical significance for the large-scale development and application of potassium ion batteries.
附图说明Description of drawings
图1是实施例3中VO 2/MXene复合材料的扫描电镜图； Fig. 1 is the scanning electron microscope image of VO 2 /MXene composite material in embodiment 3;
图2是实施例3中VO 2/Mxene复合材料组装钾离子电池在100mA/g的电流密度下所测的循环性能图； Fig. 2 is the cycle performance diagram measured under the current density of 100mA/g of potassium ion battery assembled with VO 2 /Mxene composite material in Example 3;
图3是对比例1中单纯的VO 2材料组装钾离子电池在100mA/g的电流密度下所测的循环性能图； Figure 3 is a graph of the cycle performance measured at a current density of 100 mA/g for a potassium-ion battery assembled with a pure VO 2 material in Comparative Example 1;
图4是对比例2中单纯的MXene材料组装钾离子电池在100mA/g的电流密度下所测的循环性能图。Figure 4 is a graph of the cycle performance of the potassium-ion battery assembled with pure MXene material in Comparative Example 2 at a current density of 100 mA/g.
具体实施方式detailed description
为了更好的解释本发明，现结合以下具体实施例作进一步说明，但是本发明不限于具体实施例。In order to better explain the present invention, further description will now be made in conjunction with the following specific embodiments, but the present invention is not limited to the specific embodiments.
其中，所述材料如无特别说明均可以在商业途径可得；Wherein, the materials can be commercially available unless otherwise specified;
所述Ti 3C 2T x纳米颗粒购自北京北科新材科技有限公司，编号BK2020011814，尺寸大小：1-5μm，纯度：99％，产品应用领域：储能，催化，分析化学等。 The Ti 3 C 2 T x nanoparticles were purchased from Beijing Beike New Material Technology Co., Ltd., number BK2020011814, size: 1-5 μm, purity: 99%, product application fields: energy storage, catalysis, analytical chemistry, etc.
所述方法如无特别说明均为常规方法。The methods are conventional methods unless otherwise specified.
实施例1Example 1
一种VO 2/MXene复合材料的制备方法，包括以下步骤： A preparation method of VO 2 /MXene composite material, comprising the following steps:
(1)取300mg MXene(Ti 3C 2T x)加入到N，N-二甲基甲酰胺中，配置成10mg/ml的分散液，磁力搅拌1小时； (1) Take 300 mg of MXene (Ti 3 C 2 T x ) and add it to N,N-dimethylformamide, configure it into a 10 mg/ml dispersion, and stir magnetically for 1 hour;
(2)将0.3mol NH 4VO 3与0.6mol草酸加入步骤(1)所述分散液中，搅拌6小时，得到混合液； (2) adding 0.3 mol NH 4 VO 3 and 0.6 mol oxalic acid to the dispersion described in step (1), and stirring for 6 hours to obtain a mixed solution;
(3)将步骤(2)混合液移入容量为50ml反应釜中密封后放置在烘箱中，加热至110℃，保温12h，然后冷却至室温，得到悬浊液；(3) transferring the mixed solution of step (2) into a reaction kettle with a capacity of 50ml and sealing, placing it in an oven, heating to 110°C, keeping the temperature for 12h, and then cooling to room temperature to obtain a suspension;
(4)将步骤(3)所述的悬浊液，在4000r/min条件下离心4分钟，用去离子水和无水乙醇交替对滤渣洗涤3次，收集沉淀物；(4) the suspension described in step (3) was centrifuged for 4 minutes under the condition of 4000r/min, and the filter residue was washed 3 times with deionized water and absolute ethanol alternately, and the precipitate was collected;
(5)将步骤(4)得到的沉淀物在真空干燥箱中进行干燥，干燥温度60℃，干燥时间6小时，得到粗产物；(5) drying the precipitate obtained in step (4) in a vacuum drying oven at a drying temperature of 60° C. and a drying time of 6 hours to obtain a crude product;
(6)将步骤(5)所得粗产物放置于石英舟中，将石英舟放于管式炉中，通入高纯度Ar，流速为150ml/min，以5℃/min的升温速率加热至400℃，保温3h，然后自然冷却到室温，得到VO 2/MXene复合材料。 (6) the crude product obtained in step (5) is placed in a quartz boat, the quartz boat is placed in a tube furnace, high-purity Ar is introduced, and the flow rate is 150ml/min, and heated to 400 ℃ with a heating rate of 5°C/min ℃, kept for 3h, and then naturally cooled to room temperature to obtain VO 2 /MXene composites.
将VO 2/MXene复合材料与聚偏氟乙烯、碳黑按质量比为8：1：1的比例混合，加入适量的N-甲基吡咯烷酮，搅拌，形成均匀浆料并涂覆在集流体上，经真空干燥、切片后，制成钾离子电池负极片。 Mix the VO 2 /MXene composite material with polyvinylidene fluoride and carbon black in a mass ratio of 8:1:1, add an appropriate amount of N-methylpyrrolidone, stir to form a uniform slurry and coat it on the current collector , after vacuum drying and slicing, the negative electrode sheet of potassium ion battery is made.
本实施例所制备的VO 2/MXene复合材料，经电化学测试表明，在电流密度为100mA/g下，经100圈循环，可逆比容量为338mAh/g，是单纯VO 2(103.6mAh/g)的3.26倍，是未掺杂MXene(61.1mA h/g)的5.5倍，且本实施例中VO 2/MXene复合材料表现出优异的储钾性能。 The electrochemical test of the VO 2 /MXene composite prepared in this example shows that at a current density of 100 mA/g, after 100 cycles, the reversible specific capacity is 338 mAh/g, which is a pure VO 2 (103.6 mAh/g ) is 3.26 times that of undoped MXene (61.1 mA h/g), and 5.5 times that of undoped MXene (61.1 mA h/g), and the VO 2 /MXene composite in this example exhibits excellent potassium storage performance.
实施例2Example 2
一种VO 2/MXene复合材料的制备方法，包括以下步骤： A preparation method of VO 2 /MXene composite material, comprising the following steps:
(1)取1000mg MXene(Ti 3C 2T x)加入到N，N-二甲基甲酰胺中，配置成50mg/ml的分散液，磁力搅拌4小时； (1) Take 1000 mg of MXene (Ti 3 C 2 T x ) and add it to N,N-dimethylformamide, configure it into a dispersion of 50 mg/ml, and stir magnetically for 4 hours;
(2)将0.5mol NH 4VO 3与2mol草酸加入步骤(1)所述分散液中，并搅拌14小时，得到混合液； (2) adding 0.5mol NH 4 VO 3 and 2mol oxalic acid to the dispersion described in step (1), and stirring for 14 hours to obtain a mixed solution;
(3)将步骤(2)所得混合液移入容量为50ml反应釜中密封后放置在烘箱中，加热至180℃，保温20h，然后冷却至室温，得到悬浊液；(3) transfer the mixed solution obtained in step (2) into a reaction kettle with a capacity of 50ml and seal it, place it in an oven, heat to 180°C, keep the temperature for 20h, and then cool to room temperature to obtain a suspension;
(4)将步骤(3)得到的得到悬浊液，在6000r/min条件下离心6分钟，用去离子水和无水乙醇对滤渣交替洗涤3次后，收集沉淀物；(4) the suspension obtained in step (3) is centrifuged for 6 minutes under the condition of 6000 r/min, and after alternately washing the filter residue 3 times with deionized water and absolute ethanol, the precipitate is collected;
(5)将步骤(4)得到的沉淀物在真空干燥箱中进行干燥，干燥温度60℃，干燥时间9小时，得到粗产物；(5) drying the precipitate obtained in step (4) in a vacuum drying oven at a drying temperature of 60° C. and a drying time of 9 hours to obtain a crude product;
(6)将步骤(5)所得粗产物放置于石英舟中，将石英舟放于管式炉中，通入高纯度Ar，流速为220ml/min，以7℃/min的升温速率加热至800℃，保温8h，然后自然冷却到室温，得到VO 2/MXene复合材料。 (6) place the crude product obtained in step (5) in a quartz boat, place the quartz boat in a tube furnace, feed high-purity Ar, flow rate is 220ml/min, heat to 800 with a heating rate of 7°C/min ℃, kept for 8 h, and then naturally cooled to room temperature to obtain VO 2 /MXene composites.
将VO 2/MXene复合材料与聚偏氟乙烯、碳黑按质量比为8：1：1的比例混合，加入适量的N-甲基吡咯烷酮，搅拌，形成均匀浆料并涂覆在集流体上，经真空干燥、切片后，制成钾离子电池负极片。 Mix the VO 2 /MXene composite material with polyvinylidene fluoride and carbon black in a mass ratio of 8:1:1, add an appropriate amount of N-methylpyrrolidone, stir to form a uniform slurry and coat it on the current collector , after vacuum drying and slicing, the negative electrode sheet of potassium ion battery is made.
本实施例所制备的VO 2/MXene复合材料，经电化学测试表明，在电流密度为100mA/g下，经100圈循环，可逆比容量为466mAh/g，是单纯VO 2(103.6mAh/g)的4.50倍，是未掺杂MXene(61.1mA h/g)的7.6倍，且本实施例中VO 2/MXene复合材料表现出优异的储钾性能。 The electrochemical test of the VO 2 /MXene composite prepared in this example shows that at a current density of 100 mA/g and 100 cycles, the reversible specific capacity is 466 mAh/g, which is a pure VO 2 (103.6 mAh/g ) is 4.50 times that of undoped MXene (61.1 mA h/g), and 7.6 times that of undoped MXene (61.1 mA h/g), and the VO 2 /MXene composite in this example exhibits excellent potassium storage performance.
实施例3Example 3
一种VO 2/MXene复合材料的制备方法，包括以下步骤： A preparation method of VO 2 /MXene composite material, comprising the following steps:
(1)取3000mg MXene(Ti 3C 2T x)加入到N，N-二甲基甲酰胺中，配置成100mg/ml的分散液，磁力搅拌6小时； (1) Take 3000mg of MXene (Ti 3 C 2 T x ) and add it to N,N-dimethylformamide, configure it into a dispersion of 100 mg/ml, and stir magnetically for 6 hours;
(2)将0.5mol NH 4VO 3与3mol草酸加入步骤(1)所述分散液中，并搅拌20小时，得到混合液； (2) adding 0.5mol NH 4 VO 3 and 3mol oxalic acid to the dispersion described in step (1), and stirring for 20 hours to obtain a mixed solution;
(3)将步骤(2)所得混合液移入容量为50ml反应釜中密封后放置在烘箱中，加热至240℃，保温24h，然后冷却至室温，得到悬浊液；(3) transferring the mixed solution obtained in step (2) into a reaction kettle with a capacity of 50ml and sealing, placing it in an oven, heating to 240° C., keeping the temperature for 24h, and then cooling to room temperature to obtain a suspension;
(4)将步骤(3)得到的悬浊液，在8000r/min条件下离心8分钟，用去离子水和无水乙醇对滤渣交替洗涤3次后，收集沉淀物；(4) the suspension obtained in step (3) was centrifuged for 8 minutes under the condition of 8000 r/min, and after alternately washing the filter residue 3 times with deionized water and absolute ethanol, the precipitate was collected;
(5)将步骤(4)得到的淀物在真空干燥箱中进行干燥，干燥温度60℃，干燥时间12小时，得到粗产物；(5) drying the precipitate obtained in step (4) in a vacuum drying oven at a drying temperature of 60° C. and a drying time of 12 hours to obtain a crude product;
(6)将步骤(5)所得粗产物放置于石英舟中，将石英舟放于管式炉中，通入高纯度Ar，流速为300ml/min，以8℃/min的升温速率加热至1000℃，保温10h，然后自然冷却到室温，得到VO 2/MXene复合材料。 (6) place the crude product obtained in step (5) in a quartz boat, place the quartz boat in a tube furnace, feed high-purity Ar, flow rate is 300ml/min, heat to 1000 with a heating rate of 8°C/min ℃, kept for 10 h, and then naturally cooled to room temperature to obtain VO 2 /MXene composites.
将VO 2/MXene复合材料与聚偏氟乙烯、碳黑按质量比为8：1：1的比例混合，加入适量的N-甲基吡咯烷酮，搅拌，形成均匀浆料并涂覆在集流体上，经真空干燥、切片后，制成钾离子电池负极片。 Mix the VO 2 /MXene composite material with polyvinylidene fluoride and carbon black in a mass ratio of 8:1:1, add an appropriate amount of N-methylpyrrolidone, stir to form a uniform slurry and coat it on the current collector , after vacuum drying and slicing, the negative electrode sheet of potassium ion battery is made.
本实施例所制备的VO 2/MXene复合材料，经电化学测试表明，在电流密度为100mA/g下，经100圈循环，可逆比容量为421mAh/g，是单纯VO 2(103.6mAh/g)的4.06倍，是未掺杂MXene(61.1mA h/g)的6.9倍，且本实施例中VO 2/MXene复合材料表现出优异的储钾性能。 The electrochemical test of the VO 2 /MXene composite prepared in this example shows that the reversible specific capacity is 421mAh/g after 100 cycles at a current density of 100mA/g, which is a pure VO 2 (103.6mAh/g) ) is 4.06 times that of undoped MXene (61.1 mA h/g), and the VO 2 /MXene composite in this example exhibits excellent potassium storage performance.
对比例1Comparative Example 1
单纯VO 2材料的制备方法，包括以下步骤： The preparation method of pure VO material includes the following steps:
(1)将0.5mol NH 4VO 3与3mol草酸加入到N，N-二甲基甲酰胺中，配置成100mg/ml的分散液，并搅拌20小时； (1) 0.5mol NH 4 VO 3 and 3mol oxalic acid were added to N,N-dimethylformamide to form a dispersion of 100 mg/ml, and stirred for 20 hours;
(2)将步骤(1)所得分散液移入容量为50ml反应釜中密封后放置在烘箱中，加热至240℃，保温24h，然后冷却至室温；(2) The dispersion liquid obtained in step (1) is transferred into a reaction kettle with a capacity of 50ml, sealed and placed in an oven, heated to 240° C., maintained for 24h, and then cooled to room temperature;
(3)将步骤(2)得到的产物，用去离子水和无水乙醇交替洗涤3次后，用离心机在8000r/min条件下离心8分钟；(3) the product obtained in step (2) was washed 3 times with deionized water and dehydrated alcohol alternately, and centrifuged for 8 minutes under the condition of 8000 r/min with a centrifuge;
(4)将步骤(3)得到的离心产物在真空干燥箱中进行干燥，干燥温度60℃，干燥时间12小时。(4) Drying the centrifuged product obtained in step (3) in a vacuum drying oven at a drying temperature of 60° C. and a drying time of 12 hours.
(5)将步骤(4)所得产物放置于石英舟中，将石英舟放于管式炉中，通入高纯度Ar，流速为300ml/min，以8℃/min的升温速率加热至1000℃，保温10h，然后自然冷却到室温，得到所述VO 2复合材料。 (5) placing the product obtained in step (4) in a quartz boat, placing the quartz boat in a tube furnace, feeding high-purity Ar, the flow rate of 300ml/min, and heating to 1000°C with a temperature increase rate of 8°C/min , kept for 10h, and then naturally cooled to room temperature to obtain the VO 2 composite material.
将VO 2材料与聚偏氟乙烯、碳黑按质量比为8：1：1的比例混合，加入适量的N-甲基吡咯烷酮，搅拌，形成均匀浆料并涂覆在集流体上，经真空干燥、切片后，制成钾离子电池负极片。 Mix the VO 2 material with polyvinylidene fluoride and carbon black in a mass ratio of 8:1:1, add an appropriate amount of N-methylpyrrolidone, stir to form a uniform slurry and coat it on the current collector, vacuum After drying and slicing, the negative electrode sheet of potassium ion battery is made.
本对比例所制备的VO 2材料，经电化学测试表明，在电流密度为100mA/g下，经100圈循环，可逆比容量为103.6mAh/g。 The electrochemical test of the VO 2 material prepared in this comparative example shows that the reversible specific capacity is 103.6mAh/g after 100 cycles at a current density of 100mA/g.
对比例2Comparative Example 2
称取80mg的MXene材料、10mg的super P和10mg的聚偏氟乙烯粘结剂混合，加入少量N-甲基吡咯烷酮，搅拌后涂在铜箔上，90℃温度下干燥3h，用切片机将铜箔裁剪圆形作为工作电极，干燥后放入氧和水含量都低于0.4ppm的惰性气氛手套箱中，以金属钾片为对电极，玻璃纤维为隔膜，组装成2032型纽扣电池。在电流密度为100mA/g下，经100圈循环，可逆比容量为61.1mA h/g。Weigh 80 mg of MXene material, 10 mg of super P and 10 mg of polyvinylidene fluoride binder and mix, add a small amount of N-methylpyrrolidone, coat it on copper foil after stirring, dry at 90 °C for 3 hours, and slice it with a microtome. The copper foil was cut into a circular shape as the working electrode. After drying, it was placed in an inert atmosphere glove box with an oxygen and water content below 0.4 ppm. A 2032 button battery was assembled with a metal potassium sheet as the counter electrode and glass fiber as the separator. At a current density of 100 mA/g, the reversible specific capacity was 61.1 mA h/g after 100 cycles.
图1是实施例3中VO 2/MXene复合材料的扫描电镜图，从图1可以看出VO 2/MXene复合材料中VO 2纳米材料均匀分布在MXene材料片层表面，VO 2纳米材料为20nm左右，VO 2纳米材料与基体结合良好，可以扩大片层之间的距离，无团聚现象，表明VO 2/MXene复合材料的层状结构成功制备且有效增加层间距和比表面积。 Figure 1 is the scanning electron microscope image of the VO 2 /MXene composite material in Example 3. It can be seen from Figure 1 that the VO 2 nanomaterial in the VO 2 /MXene composite material is uniformly distributed on the surface of the MXene material sheet, and the VO 2 nanomaterial is 20nm. Around, the VO2 nanomaterials are well combined with the matrix, which can expand the distance between the lamellae without agglomeration, indicating that the layered structure of the VO2/ MXene composite was successfully prepared and effectively increased the interlayer spacing and specific surface area.
图2-4分别是实施例3、对比例1、对比例2的钾离子电池在100mA/g的电流密度下所测的循环性能图。Figures 2-4 are graphs of the cycle performances of the potassium ion batteries of Example 3, Comparative Example 1, and Comparative Example 2 measured at a current density of 100 mA/g, respectively.
从图2-4可以看出，与单纯的VO 2材料相比，VO 2/MXene复合材料显示出高的电池容量和良好的循环性能。MXene材料组装钾离子电池在100mA/g的电流密度下充放电过程中良 好的循环稳定性，但比容量较小。VO 2/MXene材料的层状结构对于比表面积和电解液离子附着活性位点有贡献，VO 2材料和MXene之间有范德华力，而且表面官能团可以和材料形成化学键；与单纯的MXene材料相比，VO 2材料可以在MXene层间生长结晶，有利于层间距的增加，扩大比表面积，相互作用防止团聚，在循环200圈后仍然保持稳定的容量，而且更大的转移和离子吸附面积，双电层电容性能良好，使储存钾离子能力提高，材料的比容量显著增加。可见VO 2材料与MXene材料具有协同增效作用。 It can be seen from Figures 2-4 that the VO2/ MXene composites show high battery capacity and good cycling performance compared to the pure VO2 material. The potassium-ion battery assembled with MXene material exhibits good cycling stability during charge-discharge at a current density of 100 mA/g, but has a small specific capacity. The layered structure of the VO 2 /MXene material contributes to the specific surface area and the active sites for ion attachment in the electrolyte, there is van der Waals force between the VO 2 material and MXene, and the surface functional groups can form chemical bonds with the material; compared with pure MXene materials , VO2 material can grow crystals between MXene layers, which is beneficial to the increase of interlayer spacing, enlarges the specific surface area, prevents agglomeration by interaction, still maintains stable capacity after 200 cycles, and larger transfer and ion adsorption area, double The electric layer capacitance has good performance, which improves the ability to store potassium ions and significantly increases the specific capacity of the material. It can be seen that the VO2 material has a synergistic effect with the MXene material.
将各组材料进行比表面积，VO2负载量和循环100圈后的比容量的测试，测试方法为：Each group of materials was tested for specific surface area, VO2 loading and specific capacity after 100 cycles of circulation. The test methods are:
比表面积用BET比表面积测试法，VO2负载量使用X射线能谱分析(EDS)，循环100圈后的比容量请见各具体实例。各组的性能测试结果请参见表1。The specific surface area was measured by the BET specific surface area test method, and the VO2 load was analyzed by X-ray energy dispersive spectroscopy (EDS). The performance test results of each group are shown in Table 1.
表1：性能测试Table 1: Performance Testing
Figure PCTCN2020112566-appb-000001
Figure PCTCN2020112566-appb-000001
以上所述仅为本发明的具体实施例，并非因此限制本发明的专利范围，凡是利用本发明作的等效变换，或直接或间接运用在其它相关的技术领域，均同理包括在本发明的专利保护范围之中。The above descriptions are only specific embodiments of the present invention, and are not intended to limit the scope of the present invention. All equivalent transformations made by the present invention, or directly or indirectly applied in other related technical fields, are similarly included in the present invention. within the scope of patent protection.

Claims (10)

  1. 一种VO 2/MXene复合材料的制备方法，其特征在于，包括如下制备步骤： A preparation method of VO 2 /MXene composite material, characterized in that it comprises the following preparation steps:
    (1)将MXene材料加入分散剂中，配制成浓度为10-100mg/ml的分散液；(1) adding the MXene material to the dispersing agent, and preparing a dispersion liquid with a concentration of 10-100 mg/ml;
    (2)将钒源与还原剂按照1：2-6的摩尔比加入到步骤(1)所述分散液中，搅拌溶解，得到混合液；(2) adding vanadium source and reducing agent to the dispersion liquid described in step (1) according to the molar ratio of 1:2-6, stirring and dissolving to obtain mixed liquid;
    (3)将步骤(2)所述混合液在110-240℃下反应10-30h，得到悬浊液，过滤，离心，洗涤，干燥得到粗产物；(3) reacting the mixed solution in step (2) at 110-240° C. for 10-30 h to obtain a suspension, filtering, centrifuging, washing, and drying to obtain a crude product;
    (4)将步骤(3)所述粗产物在保护气氛中，加热至400-1100℃，保温2-12h，冷却，得到VO 2/MXene复合材料。 (4) The crude product of step (3) is heated to 400-1100° C. in a protective atmosphere, kept for 2-12 hours, and cooled to obtain a VO 2 /MXene composite material.
  2. 根据权利要求1所述的VO 2/MXene复合材料的制备方法，其特征在于，所述MXene为Ti 3C 2T x、V 3C 2T x、Mo 3N 2T x中的至少一种。 The preparation method of VO 2 /MXene composite material according to claim 1, wherein the MXene is at least one of Ti 3 C 2 T x , V 3 C 2 T x and Mo 3 N 2 T x .
  3. 根据权利要求1所述的VO 2/MXene复合材料的制备方法，其特征在于，所述钒源为NH 4VO、NaVO 3中的至少一种。 The preparation method of VO 2 /MXene composite material according to claim 1, wherein the vanadium source is at least one of NH 4 VO and NaVO 3 .
  4. 根据权利要求1所述的VO 2/MXene复合材料的制备方法，其特征在于，所述还原剂为草酸、抗坏血酸中的至少一种。 The preparation method of VO 2 /MXene composite material according to claim 1, wherein the reducing agent is at least one of oxalic acid and ascorbic acid.
  5. 根据权利要求1所述的VO 2/MXene复合材料的制备方法，其特征在于，所述分散剂为N，N-二甲基甲酰胺、乙醇、乙二醇中的至少一种；优选的，所述清洗剂为水、乙醇中的至少一种。 The preparation method of VO 2 /MXene composite material according to claim 1, wherein the dispersant is at least one of N,N-dimethylformamide, ethanol, and ethylene glycol; preferably, The cleaning agent is at least one of water and ethanol.
  6. 根据权利要求1所述的VO 2/MXene复合材料的制备方法，其特征在于，所述保护气体为Ar或N 2中的任意一种，气体流速为150-300ml/min。 The preparation method of VO 2 /MXene composite material according to claim 1, wherein the protective gas is any one of Ar or N 2 , and the gas flow rate is 150-300ml/min.
  7. 根据权利要求1所述的VO 2/MXene复合材料的制备方法，其特征在于，步骤(5)中真空干燥的温度为50-70℃，干燥时间5-12h，真空度不超过131Pa。 The preparation method of VO 2 /MXene composite material according to claim 1, characterized in that, in step (5), the temperature of vacuum drying is 50-70°C, the drying time is 5-12h, and the vacuum degree is not more than 131Pa.
  8. 根据权利要求1所述的VO 2/MXene复合材料的制备方法，其特征在于，所述VO 2/MXene复合材料中VO 2负载量为40-180wt％。 The method for preparing a VO 2 /MXene composite material according to claim 1, wherein the VO 2 loading in the VO 2 /MXene composite material is 40-180wt%.
  9. 一种钾离子电池负极，其特征在于，其包括权利要求1-8中任一项所述的制备方法制备得到的VO 2/MXene复合材料。 A potassium ion battery negative electrode, characterized in that it comprises the VO 2 /MXene composite material prepared by the preparation method according to any one of claims 1-8.
  10. 一种钾离子电池，其特征在于，其包括权利要求9所述的电池负极。A potassium ion battery, characterized in that it comprises the battery negative electrode of claim 9 .
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