WO2022032743A1 - Cote2/mxene composite material and preparation method therefor - Google Patents

Cote2/mxene composite material and preparation method therefor Download PDF

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WO2022032743A1
WO2022032743A1 PCT/CN2020/112558 CN2020112558W WO2022032743A1 WO 2022032743 A1 WO2022032743 A1 WO 2022032743A1 CN 2020112558 W CN2020112558 W CN 2020112558W WO 2022032743 A1 WO2022032743 A1 WO 2022032743A1
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cote
mxene
composite material
mxene composite
preparation
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Chinese (zh)
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张业龙
徐晓丹
周健文
孙宏阳
陈浩
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
    • H01M4/136—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
    • H01M4/58—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
    • 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
    • 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 new energy, and in particular relates to a CoTe 2 /MXene composite material and a preparation method thereof.
  • lithium-ion batteries have achieved great success in the fields of electric vehicles and portable electronic devices.
  • the uneven distribution has led to the rising price of lithium-ion batteries, thus limiting their application in the field of energy storage. Therefore, the development of a new type of secondary alkali metal battery has extremely high social value.
  • Potassium resources are abundant in nature (the abundance of potassium in the earth's crust is 2.47%), the cost is low, the redox potential (K+/K, -2.936V relative to the standard hydrogen electrode potential) is close to lithium, with high energy density, cycling
  • commercial graphites with relatively low theoretical specific capacity and poor rate performance cannot fully meet the energy density requirements of high-performance batteries. Therefore, the study of anode materials for potassium-ion batteries with high specific capacity and good cycle stability has attracted extensive attention.
  • Transition metal compounds are ideal candidates for potassium-ion battery anode materials due to their high reversible specific capacity, high electrical conductivity, and reversible redox reactions.
  • transition metal compounds tend to exhibit huge volume expansion during charge-discharge cycles, resulting in pulverization of electrode materials, resulting in poor rate performance and rapid capacity decay during cycling. Therefore, how to solve the problems of poor rate performance and fast capacity decay during the cycling process of transition metal compounds has become a major technical obstacle in the field.
  • MXene As a new type of transition metal carbon or nitride, MXene has the advantages of excellent electrical conductivity and mechanical properties, high hydrophilic surface and ion transport properties due to its unique layered structure and abundant tunable components. It is hoped to overcome the problems of poor rate performance and rapid capacity decay during the cycling process of transition metal compounds, but the 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.
  • one of the objectives of the present invention is to provide a CoTe 2 /MXene composite material.
  • Another object of the present invention is to provide a preparation method of the CoTe 2 /MXene composite material.
  • the present invention provides an application of the CoTe 2 /MXene composite material, and the CoTe 2 /MXene composite material is applied to the negative electrode of a potassium ion battery.
  • the present invention adopts following technical scheme:
  • a preparation method of CoTe 2 /MXene composite material comprising the following steps:
  • step (2) adding the cobalt source and the reducing agent to the dispersion obtained in step (1), and the stirring time is 3-12h, such as 6h, 8h, 10h, 12h;
  • step (3) Transfer the dispersion liquid obtained in step (2) into a reaction kettle, put it in an oven, and heat up to 80-220°C, such as 80°C, 100°C, 140°C, 200°C, and the reaction time is 8-24h, such as 8h, 12h, 14h, 20h, 24h, and then naturally cooled to room temperature;
  • 80-220°C such as 80°C, 100°C, 140°C, 200°C
  • the reaction time is 8-24h, such as 8h, 12h, 14h, 20h, 24h, and then naturally cooled to room temperature
  • step (3) centrifuging the product obtained in step (3) and thoroughly cleaning with a cleaning agent
  • step (4) placing the product obtained in step (4) in a vacuum drying oven for drying to obtain the precursor Co(OH) 2 /MXene;
  • the quartz boat is placed in the tube furnace, wherein, the quartz boat containing the tellurium source is placed on the upstream of the tube furnace, a protective gas is introduced, and the temperature is heated to 300-300°C at a heating rate of 4-6°C/min. 1000°C, preferably 400°C, 600°C, 800°C, 1000°C, the holding time is 2-10h, such as 3h, 5h, 8h, 10h, and then naturally cooled to room temperature;
  • step (8) centrifuging the product obtained in step (7), thoroughly cleaning with a cleaning agent, and vacuum drying to obtain a CoTe 2 /MXene composite material.
  • the molar ratio of the MXene, the cobalt source and the reducing agent is 1:1:1-5, preferably 1:1:1-3, and more preferably 1:1:3.
  • the cobalt source is at least one of CoCl 2 ⁇ 6H 2 O, Co(NO 3 ) 2 ⁇ 6H 2 O, and CoSO 4 ⁇ 7H 2 O.
  • the tellurium source is at least one of tellurium powder, biphenyl ditellurium and sodium tellurite, wherein the particle size is 80-120 mesh, such as 100 mesh.
  • the MXene is at least one of Ti 3 C 2 T x , Ti 2 CT x , V 3 C 2 T x , Mo 3 N 2 T x , preferably Ti 3 N 2 T x , such as V 3 C 2 T x , T x is a surface functional group -O, -F or -OH.
  • the reducing agent is at least one of urea and NH 4 F.
  • the dispersant is at least one of N,N-dimethylformamide, ethanol, and ethylene glycol.
  • the dispersion liquid is heated to 80-220°C in the reaction kettle, preferably 120-180°C, such as 130°C, 150°C, 160°C, 180°C, and the reaction time is 8-24h , preferably 12-16h, such as 12h, 13h, 14h, 15h, 16h.
  • the protective gas is N or Ar
  • the gas flow rate is 100-300ml /min, such as 100ml/min, 120ml/min, 140ml/min, 160ml/min, 180ml/min, 200ml/min, 220ml/min , 230ml/min, 240ml/min, 260ml/min, 280ml/min, 300ml/min.
  • the cleaning agent is at least one of water and ethanol, preferably deionized water and absolute ethanol are used to thoroughly clean the products obtained in step (3) and step (7), and deionized water and anhydrous can be used. Alternate cleaning with ethanol 2-12 times, preferably 3-8 times.
  • the centrifugation speed described in step (4) and step (8) is 5000-8000r/min, such as 6000r/min, and the centrifugation time is 5-10min, such as 8min.
  • the temperature of vacuum drying in step (5) and step (8) is 50-80°C, preferably 60°C, and the drying time is 6-15h, such as 8h, 10h, 12h, 15h, preferably 10h; vacuum
  • the degree does not exceed 130Pa, such as 130Pa, 120Pa, 110Pa, 100Pa, 95Pa.
  • the loading amount of CoTe 2 in the CoTe 2 /MXene composite material is 50-150 wt %, preferably 50-90 wt %, more preferably 60-110 wt %, still more preferably 80-130 wt %, and then Further preferred is 90-150 wt%.
  • a CoTe 2 /MXene composite material is prepared by a preparation method of CoTe 2 /MXene composite material.
  • CoTe 2 /MXene composite material An application of CoTe 2 /MXene composite material, the CoTe 2 /MXene composite material is applied to the negative electrode of potassium ion battery.
  • the transition metal telluride CoTe 2 is grown on the MXene nanosheets, and the growth distribution of CoTe2 can expand the distance between the sheets, prevent the stacking of the MXene nanosheets, and increase the specific surface area of MXene;
  • the structure can provide effective structural support and prevent the agglomeration phenomenon of CoTe2 materials.
  • CoTe 2 and MXene materials in the present invention have a synergistic effect, which is conducive to full infiltration between the electrode material and the electrolyte, and can provide more active sites and electron conduction channels, and greater transfer and ion adsorption. Area and vacancy, so the composite material can have outstanding performance in terms of specific capacity, cycle stability and battery capacity after 100 cycles. It is of great significance for the development and application of potassium-ion batteries.
  • the composite material of the present invention has high production efficiency, simple preparation method and low cost of raw materials, and is suitable for large-scale development and application of potassium ion batteries.
  • Fig. 1 is the scanning electron microscope picture of CoTe 2 /MXene composite material in embodiment 1;
  • Fig. 2 is the cycle performance graph measured under the current density of 100mA/g of the potassium ion battery assembled with CoTe 2 /Mxene composite material in Example 1;
  • Fig. 3 is the cycle performance graph measured under the current density of 100mA/g of potassium ion battery assembled with single MXene material in Comparative Example 1;
  • 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.
  • the present invention provides a preparation method of CoTe 2 /MXene composite material, wherein, for the synthesis method of CoTe 2 , please refer to:
  • a preparation method of CoTe 2 /MXene composite material comprising the following steps:
  • step (1) (2) adding 0.1 mmol Co(NO 3 ) 2 .6H 2 O and 0.1 mmol urea to the dispersion described in step (1), and stirring for 3 hours;
  • step (3) The dispersion liquid obtained in step (2) is moved into a reaction kettle with a capacity of 50ml, sealed and placed in an oven, heated to 80° C., maintained for 8h, and then cooled to room temperature;
  • step (3) the product obtained in step (3) was centrifuged for 5 minutes under the condition of 5000r/min, and the filter residue was washed alternately 3 times with deionized water and absolute ethanol;
  • step (4) drying the centrifuged product 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 the precursor Co(OH) 2 /MXene.
  • the quartz boat is placed in the tube furnace, wherein, the quartz boat with the tellurium powder is placed on the upstream of the tube furnace, high-purity Ar is introduced, the flow rate is 100ml/min, and the temperature rises at 4°C/min The rate of heating to 400 °C, holding for 2h, and then naturally cooled to room temperature;
  • step (8) centrifuging the product obtained in step (7) at 5000 r/min for 5 minutes, and alternately washing the filter residue 3 times with deionized water and absolute ethanol;
  • step (8) Drying the centrifuged product obtained in step (8) in a vacuum drying oven at a drying temperature of 60° C. and a drying time of 6 hours to finally obtain a CoTe 2 /MXene composite material.
  • the specific surface area of the CoTe 2 /MXene composite prepared in this example is 140.9 m 2 /g, and at a current density of 100 mA/g, after 100 cycles, the reversible specific capacity is 345 mAh/g, which is a pure CoTe 2 (100.7 mAh) /g) 3.43 times, and the CoTe 2 /MXene composite in this example showed good cycle stability and excellent rate performance.
  • a preparation method of CoTe 2 /MXene composite material comprising the following steps:
  • step (1) (2) adding 0.2 mmol Co(NO 3 ) 2 .6H 2 O and 0.25 mmol urea to the dispersion described in step (1), and stirring for 9 hours;
  • step (3) transferring the dispersion obtained in step (2) into a reaction kettle with a capacity of 50ml and sealing, placing it in an oven, heating to 150°C, keeping the temperature for 15h, and then cooling to room temperature;
  • step (3) the product obtained in step (3) was centrifuged for 8 minutes under the condition of 6000r/min, and the filter residue was washed alternately 3 times with deionized water and absolute ethanol;
  • step (4) drying the centrifuged product obtained in step (4) in a vacuum drying oven at a drying temperature of 60° C. and a drying time of 10 hours to obtain the precursor Co(OH) 2 /MXene.
  • the quartz boat is placed in the tube furnace, wherein, the quartz boat containing the tellurium powder is placed in the upstream of the tube furnace, and high-purity Ar is passed into it, and the flow rate is 200ml/min, and the temperature rises at 5°C/min. The rate of heating to 600 °C, holding for 6h, and then naturally cooled to room temperature;
  • step (7) centrifuging the product obtained in step (7) at 6000 r/min for 8 minutes, and washing the filter residue 3 times with deionized water and absolute ethanol respectively;
  • step (8) Drying the centrifuged product obtained in step (8) in a vacuum drying oven at a drying temperature of 60° C. and a drying time of 10 hours to finally obtain a CoTe 2 /MXene composite material.
  • the specific surface area of the CoTe 2 /MXene composite prepared in this example is 211.9 m 2 /g, and at a current density of 100 mA/g, after 100 cycles, the reversible specific capacity is 450 mAh/g, which is a pure CoTe 2 (100.7 mAh) /g) 4.47 times, and the CoTe 2 /MXene composite in this example showed good cycle stability and excellent rate performance.
  • a preparation method of CoTe 2 /MXene composite material comprising the following steps:
  • step (1) (2) adding 0.1 mmol Co(NO 3 ) 2 .6H 2 O and 0.2 mmol urea to the dispersion described in step (1), and stirring for 12 hours;
  • step (3) The dispersion liquid obtained in step (2) is moved into a reaction kettle with a capacity of 50ml, sealed and placed in an oven, heated to 220° C., maintained for 24h, and then cooled to room temperature;
  • step (3) the product obtained in step (3) is centrifuged for 10 minutes under the condition of 8000 r/min, and after alternately washing the filter residue 3 times with deionized water and absolute ethanol;
  • step (4) drying the centrifuged product obtained in step (4) in a vacuum drying oven at a drying temperature of 60° C. and a drying time of 15 hours to obtain the precursor Co(OH) 2 /MXene.
  • the quartz boat is placed in the tube furnace, wherein, the quartz boat with the tellurium powder is placed on the upstream of the tube furnace, and high-purity Ar is passed into it, the flow rate is 300ml/min, and the temperature rises at 6°C/min The rate of heating to 1000 °C, holding for 10h, and then naturally cooled to room temperature;
  • step (7) the product obtained in step (7) was centrifuged for 10 minutes under the condition of 8000 r/min, and washed with deionized water and absolute ethanol for 3 times respectively;
  • step (8) Drying the centrifuged product obtained in step (8) in a vacuum drying oven at a drying temperature of 60° C. and a drying time of 15 hours to finally obtain a CoTe 2 /MXene composite material.
  • the specific surface area of the CoTe 2 /MXene composite prepared in this example is 197.5 m 2 /g, and at a current density of 100 mA/g, after 100 cycles, the reversible specific capacity is 403 mAh/g, which is a pure CoTe 2 (100.7 mAh/g), and the CoTe 2 /MXene composite in this example showed good cycle stability and excellent rate performance.
  • 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.
  • Figure 4 shows the cycle performance of the potassium ion battery assembled with MXene material at a current density of 100 mA/g.
  • the potassium ion battery assembled with MXene material has good cycle stability during the charge and discharge process at a current density of 100 mA/g, but the specific capacity is small, which is 61.1 mA h/g.
  • the preparation method of single NiTe 2 material includes the following steps:
  • step (2) The dispersion liquid obtained in step (1) is moved into a reaction kettle with a capacity of 100ml, sealed, placed in an oven, heated to 80° C., maintained for 8h, and then cooled to room temperature;
  • step (3) the product obtained in step (2) was centrifuged for 5 minutes under the condition of 5000r/min, and the filter residue was washed 3 times with deionized water and absolute ethanol respectively;
  • step (3) (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 6 hours to obtain the precursor Co(OH) 2 /MXene.
  • the quartz boat is placed in the tube furnace, wherein, the quartz boat with the tellurium powder is placed on the upstream of the tube furnace, and high-purity Ar is introduced, the flow rate is 100ml/min, and the temperature rises at 4°C/min Speed heating to 400°C, hold for 2h, and then naturally cool to room temperature;
  • step (6) centrifuging the product obtained in step (6) at 5000 r/min for 5 minutes, and washing 3 times with deionized water and absolute ethanol respectively;
  • step (7) Drying the centrifuged product obtained in step (7) in a vacuum drying oven at a drying temperature of 60° C. and a drying time of 6 hours to finally obtain a CoTe 2 /MXene composite material.
  • the specific surface area of the CoTe 2 material prepared in this comparative example is 45.6 m 2 /g, and the reversible capacity is 100.7 mAh/g after 100 cycles at a current density of 100 mA/g.
  • the specific surface area was measured by the BET specific surface area test method, and the loading amount of CoTe 2 was analyzed by X-ray energy dispersive spectroscopy (EDS). Please refer to the specific examples for the specific capacity after 100 cycles.
  • EDS X-ray energy dispersive spectroscopy
  • FIG. 1 is a scanning electron microscope image of the CoTe 2 /MXene composite material in Example 1. It can be seen from Figure 1 that some CoTe 2 nanoparticles are uniformly grown on the surface of the MXene material, and some CoTe 2 nanoparticles are uniformly grown between the lamellae and at the edges, without agglomeration, showing one end closed and the other open. Accordion-like layered structure.
  • the growth distribution of CoTe 2 can expand the distance and specific surface area between the lamellae; the lamellar structure of MXene material can provide effective structural support and prevent the agglomeration phenomenon of CoTe 2 material.
  • Figure 3 is a graph of the cycle performance of the potassium ion battery assembled with a single MXene material in Comparative Example 1 at a current density of 100 mA/g; it can be seen from the figure that the MXene material has good cycle stability, but the specific capacity is very small, which is It is caused by the too small interlayer spacing of the MXene material itself.
  • Figure 2 is a graph showing the cycle performance of the potassium ion battery assembled with CoTe 2 /Mxene composite material in Example 1 at a current density of 100 mA/g ; battery capacity and good cycle performance.
  • the transition metal telluride CoTe 2 is grown on MXene nanosheets, and the growth distribution of CoTe 2 can expand the distance between the sheets, prevent the stacking of MXene nanosheets, and increase the specific surface area of MXene; the lamellar structure of MXene materials can provide Effective structural support to prevent the agglomeration of CoTe 2 materials.
  • the interaction between the two is conducive to the full infiltration between the electrode material and the electrolyte, which can provide more active sites and electron conduction channels, and larger transfer and ion adsorption areas and vacancies. It can have outstanding performance in terms of specific capacity, cycle stability and battery capacity. It is of great significance for the development and application of potassium-ion batteries.

Abstract

A method for preparing a CoTe2/MXene composite material. The method comprises the following steps: adding an MXene material into a dispersing agent, and formulating same into a dispersion with a concentration of 1-10mg/ml; adding a cobalt source and a reducing agent into the dispersion, and stirring and dissolving same to obtain a mixed solution; heating, cooling, centrifuging, washing and drying the mixed solution to obtain a precursor, Co(OH)2/MXene; heating the Co(OH)2/MXene precursor and a tellurium source in a molar ratio of 1:1-6, and cooling same to obtain a crude product; and centrifuging the crude product at a rotation speed of 5000-8000 r/min for 5-10 min, and washing and drying same to obtain a CoTe2/MXene composite material. The CoTe2/MXene composite material is applied to the negative electrode of a potassium ion battery, has good cycle stability, a relatively high specific capacity and an excellent rate capacity, further has the advantages of having a low cost, abundant resources, a simple preparation method, etc., and is suitable for the large-scale production and application of potassium ion batteries.

Description

一种CoTe 2/MXene复合材料及其制备方法 A CoTe 2/MXene composite material and preparation method thereof 技术领域technical field
本发明属于新能源技术领域，具体涉及一种CoTe 2/MXene复合材料及其制备方法。 The invention belongs to the technical field of new energy, and in particular relates to a CoTe 2 /MXene composite material and a preparation method thereof.
背景技术Background technique
21世纪以来，随着现代社会对能源需求量的不断提高，化石能源不断消耗，日趋衰竭，环境问题日趋严重，严重影响了人类社会的可持续发展，为此，研究开发新型可再生清洁能源已经成为目前的研究重点。Since the 21st century, with the continuous increase of energy demand in modern society, fossil energy has been continuously consumed and depleted, and environmental problems have become increasingly serious, which has seriously affected the sustainable development of human society. Therefore, research and development of new renewable and clean energy has been become the focus of current research.
目前，锂离子电池作为一种二次电池储能***已经在电动汽车和便携电子设备等领域取得了巨大的成功，同时，随着锂离子电池的使用量不断增加，锂资源大量消耗，且资源分布不均，导致锂离子电池价格节节攀升，从而限制了其在储能领域中的应用。因此，开发一种新型的二次碱金属电池具有极高的社会价值。At present, as a secondary battery energy storage system, lithium-ion batteries have achieved great success in the fields of electric vehicles and portable electronic devices. The uneven distribution has led to the rising price of lithium-ion batteries, thus limiting their application in the field of energy storage. Therefore, the development of a new type of secondary alkali metal battery has extremely high social value.
钾资源在自然界中储量丰富(钾元素在地壳中丰度为2.47％)，成本低廉，氧化还原电位(K+/K，-2.936V相对于标准氢电极电位)接近锂，具有能量密度高，循环使用寿命长以及倍率性能好等优势，而具有相对低的理论比容量和较差的倍率性能的商业石墨不能完全满足高性能电池的能量密度要求。因此，研究具有高比容量和良好循环稳定性的钾离子电池负极材料引起人们的广泛关注。Potassium resources are abundant in nature (the abundance of potassium in the earth's crust is 2.47%), the cost is low, the redox potential (K+/K, -2.936V relative to the standard hydrogen electrode potential) is close to lithium, with high energy density, cycling However, commercial graphites with relatively low theoretical specific capacity and poor rate performance cannot fully meet the energy density requirements of high-performance batteries. Therefore, the study of anode materials for potassium-ion batteries with high specific capacity and good cycle stability has attracted extensive attention.
过渡金属化合物因其具有较高的可逆比容量，较高的导电性以及可逆的氧化还原反应等优势成为钾离子电池负极材料的理想候选者。然而，在充放电循环过程中过渡金属化合物易表现出巨大的体积膨胀，造成电极材料粉碎，从而导致循环过程中倍率性能差，容量衰减快等问题。因此，如何解决过渡金属化合物循环过程中倍率性能差，容量衰减快等问题成为本领域的一大技术障碍。Transition metal compounds are ideal candidates for potassium-ion battery anode materials due to their high reversible specific capacity, high electrical conductivity, and reversible redox reactions. However, transition metal compounds tend to exhibit huge volume expansion during charge-discharge cycles, resulting in pulverization of electrode materials, resulting in poor rate performance and rapid capacity decay during cycling. Therefore, how to solve the problems of poor rate performance and fast capacity decay during the cycling process of transition metal compounds has become a major technical obstacle in the field.
MXene作为一种新型的过渡金属碳或氮化物，因其独特的层状结构和丰富可调的组分使得MXene具有优异的导电性和机械性能、高亲水表面和离子传输性能的优势，有希望克服过渡金属化合物循环过程中倍率性能差，容量衰减快等问题，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。As a new type of transition metal carbon or nitride, MXene has the advantages of excellent electrical conductivity and mechanical properties, high hydrophilic surface and ion transport properties due to its unique layered structure and abundant tunable components. It is hoped to overcome the problems of poor rate performance and rapid capacity decay during the cycling process of transition metal compounds, but the 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.
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CoTe 2/MXene复合材料。本发明的另一目的在于提供所述CoTe 2/MXene复合材料的制备方法。进一步的，本发明提供一种CoTe 2/MXene复合材料的应用，将所述CoTe 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 CoTe 2 /MXene composite material. Another object of the present invention is to provide a preparation method of the CoTe 2 /MXene composite material. Further, the present invention provides an application of the CoTe 2 /MXene composite material, and the CoTe 2 /MXene composite material is applied to the 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CoTe 2/MXene复合材料的制备方法，包括以下步骤： A preparation method of CoTe 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1-10mg/ml的分散液，优选的为1-8mg/ml，更优选的为3-9mg/ml，进一步优选的为4-6mg/ml，然后搅拌2-6h，例如2h、3h、4h、5h、6h；(1) Add the MXene material to the dispersing agent, and prepare a dispersion liquid with a concentration of 1-10 mg/ml, preferably 1-8 mg/ml, more preferably 3-9 mg/ml, and further preferably 4-6 mg /ml, then stir for 2-6h, for example 2h, 3h, 4h, 5h, 6h;
(2)将钴源与还原剂加入到步骤(1)所得分散液中，搅拌时间为3-12h，例如6h、8h、10h、12h；(2) adding the cobalt source and the reducing agent to the dispersion obtained in step (1), and the stirring time is 3-12h, such as 6h, 8h, 10h, 12h;
(3)将步骤(2)所得分散液转移至反应釜中，放入烘箱中，升温至80-220℃，例如80℃、100℃、140℃、200℃，反应时间为8-24h，例如8h、12h、14h、20h、24h，然后自然冷却至室温；(3) Transfer the dispersion liquid obtained in step (2) into a reaction kettle, put it in an oven, and heat up to 80-220°C, such as 80°C, 100°C, 140°C, 200°C, and the reaction time is 8-24h, such as 8h, 12h, 14h, 20h, 24h, and then naturally cooled to room temperature;
(4)将步骤(3)所得产物离心，用清洗剂彻底清洗；(4) centrifuging the product obtained in step (3) and thoroughly cleaning with a cleaning agent;
(5)将步骤(4)所得产物置于真空干燥箱中进行干燥，得到前驱体Co(OH) 2/MXene； (5) placing the product obtained in step (4) in a vacuum drying oven for drying to obtain the precursor Co(OH) 2 /MXene;
(6)将步骤(5)所得前驱体Co(OH) 2/MXene与碲源以1：1～6，优选的为1：2～4，进一步优选的为1：3～6的摩尔比，分别放置于两个石英舟中； (6) using the precursor Co(OH) 2 /MXene obtained in step (5) to the tellurium source in a molar ratio of 1:1-6, preferably 1:2-4, more preferably 1:3-6, respectively placed in two quartz boats;
(7)将石英舟放于管式炉中，其中，将盛放碲源的石英舟放置于管式炉的上游，通入保护气体，以4～6℃/min的升温速率加热至300-1000℃，优选的为400℃、600℃、800℃、1000℃，保温时间为2-10h，例如3h、5h、8h、10h，然后自然冷却到室温；(7) The quartz boat is placed in the tube furnace, wherein, the quartz boat containing the tellurium source is placed on the upstream of the tube furnace, a protective gas is introduced, and the temperature is heated to 300-300°C at a heating rate of 4-6°C/min. 1000°C, preferably 400°C, 600°C, 800°C, 1000°C, the holding time is 2-10h, such as 3h, 5h, 8h, 10h, and then naturally cooled to room temperature;
(8)将步骤(7)所得产物离心，用清洗剂彻底清洗，真空干燥，得到CoTe 2/MXene复合材料。 (8) centrifuging the product obtained in step (7), thoroughly cleaning with a cleaning agent, and vacuum drying to obtain a CoTe 2 /MXene composite material.
进一步地，所述MXene、钴源与还原剂按照摩尔比为1：1：1～5，优选的为1：1：1～3，进一步优选的为1：1：3的摩尔比。Further, the molar ratio of the MXene, the cobalt source and the reducing agent is 1:1:1-5, preferably 1:1:1-3, and more preferably 1:1:3.
进一步地，所述钴源为CoCl 2·6H 2O、Co(NO 3) 2·6H 2O、CoSO 4·7H 2O中的至少一种。 Further, the cobalt source is at least one of CoCl 2 ·6H 2 O, Co(NO 3 ) 2 ·6H 2 O, and CoSO 4 ·7H 2 O.
进一步地，所述碲源为碲粉、联苯二碲、亚碲酸钠中的至少一种，其中粒径为80-120目，例如100目。Further, the tellurium source is at least one of tellurium powder, biphenyl ditellurium and sodium tellurite, wherein the particle size is 80-120 mesh, such as 100 mesh.
进一步地，所述MXene为Ti 3C 2T x、Ti 2CT x、V 3C 2T x、Mo 3N 2T x中的至少一种，优选的为Ti 3N 2T x，例如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 , Ti 2 CT x , V 3 C 2 T x , Mo 3 N 2 T x , preferably Ti 3 N 2 T x , such as V 3 C 2 T x , T x is a surface functional group -O, -F or -OH.
进一步地，所述还原剂为尿素、NH 4F中的至少一种。 Further, the reducing agent is at least one of urea and NH 4 F.
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)中所述分散液在反应釜中升温至80-220℃，优选的为120-180℃，例如130℃、150℃、160℃、180℃，反应时间为8-24h，优选的为12-16h，例如12h、13h、14h、15h、16h。Further, in the step (3), the dispersion liquid is heated to 80-220°C in the reaction kettle, preferably 120-180°C, such as 130°C, 150°C, 160°C, 180°C, and the reaction time is 8-24h , preferably 12-16h, such as 12h, 13h, 14h, 15h, 16h.
进一步地，所述保护气体为N 2或Ar，气体流速为100-300ml/min，例如100ml/min、 120ml/min、140ml/min、160ml/min、180ml/min、200ml/min、220ml/min、230ml/min、240ml/min、260ml/min、280ml/min、300ml/min。 Further, the protective gas is N or Ar, and the gas flow rate is 100-300ml /min, such as 100ml/min, 120ml/min, 140ml/min, 160ml/min, 180ml/min, 200ml/min, 220ml/min , 230ml/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，优选的为用去离子水和无水乙醇彻底清洗步骤(3)和步骤(7)所得产物，可以用去离子水和无水乙醇交替清洗2-12次，优选的为3-8次。Further, the cleaning agent is at least one of water and ethanol, preferably deionized water and absolute ethanol are used to thoroughly clean the products obtained in step (3) and step (7), and deionized water and anhydrous can be used. Alternate cleaning with ethanol 2-12 times, preferably 3-8 times.
进一步地，步骤(4)和步骤(8)中所述离心转速为5000-8000r/min，例如6000r/min，离心时间为5-10min，例如8min。Further, the centrifugation speed described in step (4) and step (8) is 5000-8000r/min, such as 6000r/min, and the centrifugation time is 5-10min, such as 8min.
进一步地，步骤(5)和步骤(8)中真空干燥的温度为50-80℃，优选的为60℃，干燥时间6-15h，例如8h、10h、12h、15h，优选的为10h；真空度不超过130Pa，例如130Pa、120Pa、110Pa、100Pa、95Pa。Further, the temperature of vacuum drying in step (5) and step (8) is 50-80°C, preferably 60°C, and the drying time is 6-15h, such as 8h, 10h, 12h, 15h, preferably 10h; vacuum The degree does not exceed 130Pa, such as 130Pa, 120Pa, 110Pa, 100Pa, 95Pa.
进一步地，所述CoTe 2/MXene复合材料中CoTe 2负载量为50-150wt％，优选的为50-90wt％，进一步优选的为60-110wt％，更进一步优选的为80-130wt％，再进一步优选的为90-150wt％。 Further, the loading amount of CoTe 2 in the CoTe 2 /MXene composite material is 50-150 wt %, preferably 50-90 wt %, more preferably 60-110 wt %, still more preferably 80-130 wt %, and then Further preferred is 90-150 wt%.
一种CoTe 2/MXene复合材料的制备方法制备得到的CoTe 2/MXene复合材料。 A CoTe 2 /MXene composite material is prepared by a preparation method of CoTe 2 /MXene composite material.
一种CoTe 2/MXene复合材料的应用，将所述CoTe 2/MXene复合材料应用于钾离子电池负极。 An application of CoTe 2 /MXene composite material, the CoTe 2 /MXene composite material is applied to the negative electrode of potassium ion battery.
本发明的有益效果：Beneficial effects of the present invention:
(1)本发明将渡金属碲化物CoTe 2生长在MXene纳米片上，CoTe 2的生长分布可以扩大片层之间的距离，防止MXene纳米片堆叠，增大MXene比表面积；MXene材料的片层状结构可以提供有效结构支撑，阻止CoTe 2材料的团聚现象。 (1) In the present invention, the transition metal telluride CoTe 2 is grown on the MXene nanosheets, and the growth distribution of CoTe2 can expand the distance between the sheets, prevent the stacking of the MXene nanosheets, and increase the specific surface area of MXene; The structure can provide effective structural support and prevent the agglomeration phenomenon of CoTe2 materials.
(2)本发明中的CoTe 2和MXene材料具有协同增效作用，有利于电极材料与电解液之间充分浸润，可以提供更多的活性位点和电子传导通道，更大的转移和离子吸附面积与空位，因而复合材料在循环100圈后的比容量，循环稳定性和电池容量方面能具有突出的表现。对于钾离子电池的开发和应用具有重要意义。 (2) The CoTe 2 and MXene materials in the present invention have a synergistic effect, which is conducive to full infiltration between the electrode material and the electrolyte, and can provide more active sites and electron conduction channels, and greater transfer and ion adsorption. Area and vacancy, so the composite material can have outstanding performance in terms of specific capacity, cycle stability and battery capacity after 100 cycles. It is of great significance for the development and application of potassium-ion batteries.
(3)本发明的复合材料生产效率高，制备方法简单，原料成本低廉，适合钾离子电池的大规模开发和应用。(3) The composite material of the present invention has high production efficiency, simple preparation method and low cost of raw materials, and is suitable for large-scale development and application of potassium ion batteries.
附图说明Description of drawings
图1是实施例1中CoTe 2/MXene复合材料的扫描电镜图； Fig. 1 is the scanning electron microscope picture of CoTe 2 /MXene composite material in embodiment 1;
图2是实施例1中CoTe 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 graph measured under the current density of 100mA/g of the potassium ion battery assembled with CoTe 2 /Mxene composite material in Example 1;
图3是对比例1中单独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；Fig. 3 is the cycle performance graph measured under the current density of 100mA/g of potassium ion battery assembled with single MXene material in Comparative Example 1;
图4是对比例2中单独CoTe 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。 4 is a graph of the cycle performance measured at a current density of 100 mA/g for the potassium-ion battery assembled with CoTe 2 material alone in Comparative Example 2.
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.
本发明提供一种CoTe 2/MXene复合材料的制备方法，其中，CoTe 2的合成方法请参见： The present invention provides a preparation method of CoTe 2 /MXene composite material, wherein, for the synthesis method of CoTe 2 , please refer to:
“肖培培,朱永春,钱逸泰.在CTAB辅助下通过Te纳米棒原位模板法合成花样CoTe_2超细纳米棒束[C].”；"Xiao Peipei, Zhu Yongchun, Qian Yitai. Synthesis of patterned CoTe_2 ultrafine nanorod bundles by in situ templating of Te nanorods with the aid of CTAB [C].";
“中国仪表功能材料学会、江苏大学、《功能材料》期刊、《功能材料信息》期刊.2009中国功能材料科技与产业高层论坛论文集.”；"China Instrumentation Functional Materials Society, Jiangsu University, Journal of Functional Materials, Journal of Functional Materials Information. 2009 China Functional Materials Technology and Industry High-level Forum Proceedings.";
“中国仪表功能材料学会、江苏大学、《功能材料》期刊、《功能材料信息》期刊:中国仪器仪表学会仪表材料分会,2009:799-800.”。"China Society of Instrumentation Functional Materials, Jiangsu University, Journal of Functional Materials, Journal of Functional Materials Information: Instrumentation Materials Branch of China Society for Instrumentation and Control, 2009: 799-800.".
实施例1Example 1
一种CoTe 2/MXene复合材料的制备方法，包括以下步骤： A preparation method of CoTe 2 /MXene composite material, comprising the following steps:
(1)取0.1mmol MXene(Ti 3C 2T x)加入到N，N-二甲基甲酰胺中，配置成1mg/ml的分散液，磁力搅拌2小时； (1) Take 0.1 mmol of MXene (Ti 3 C 2 T x ) and add it to N,N-dimethylformamide to form a dispersion of 1 mg/ml, and stir magnetically for 2 hours;
(2)将0.1mmol Co(NO 3) 2·6H 2O与0.1mmol尿素加入步骤(1)所述分散液中，并搅拌3小时； (2) adding 0.1 mmol Co(NO 3 ) 2 .6H 2 O and 0.1 mmol urea to the dispersion described in step (1), and stirring for 3 hours;
(3)将步骤(2)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80℃，保温8h，然后冷却至室温；(3) The dispersion liquid obtained in step (2) is moved into a reaction kettle with a capacity of 50ml, sealed and placed in an oven, heated to 80° C., maintained for 8h, and then cooled to room temperature;
(4)将步骤(3)得到的产物，在5000r/min条件下离心5分钟，用去离子水和无水乙醇交替洗涤滤渣3次；(4) the product obtained in step (3) was centrifuged for 5 minutes under the condition of 5000r/min, and the filter residue was washed alternately 3 times with deionized water and absolute ethanol;
(5)将步骤(4)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6小时，得到前驱体Co(OH) 2/MXene。 (5) drying the centrifuged product 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 the precursor Co(OH) 2 /MXene.
(6)将0.1mmol前驱体Co(OH) 2/MXene与0.2mmol碲粉分别放置于两个石英舟中； (6) 0.1 mmol precursor Co(OH) 2 /MXene and 0.2 mmol tellurium powder were placed in two quartz boats respectively;
(7)将石英舟放于管式炉中，其中，将放有碲粉的石英舟置于管式炉的上游，通入高纯 度Ar，流速为100ml/min，以4℃/min的升温速率加热至400℃，保温2h，然后自然冷却到室温；(7) the quartz boat is placed in the tube furnace, wherein, the quartz boat with the tellurium powder is placed on the upstream of the tube furnace, high-purity Ar is introduced, the flow rate is 100ml/min, and the temperature rises at 4°C/min The rate of heating to 400 ℃, holding for 2h, and then naturally cooled to room temperature;
(8)将步骤(7)所得产物在5000r/min条件下离心5分钟，用去离子水和无水乙醇交替洗涤滤渣3次；(8) centrifuging the product obtained in step (7) at 5000 r/min for 5 minutes, and alternately washing the filter residue 3 times with deionized water and absolute ethanol;
(9)将步骤(8)所得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6小时，最终得到CoTe 2/MXene复合材料。 (9) Drying the centrifuged product obtained in step (8) in a vacuum drying oven at a drying temperature of 60° C. and a drying time of 6 hours to finally obtain a CoTe 2 /MXene composite material.
将CoTe 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 CoTe 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CoTe 2/MXene复合材料比表面积为140.9m 2/g，在电流密度为100mA/g下，经100圈循环，可逆比容量为345mAh/g，是单纯CoTe 2(100.7mAh/g)的3.43倍，且本实施例中CoTe 2/MXene复合材料表现出良好的循环稳定性以及优异的倍率性能。 The specific surface area of the CoTe 2 /MXene composite prepared in this example is 140.9 m 2 /g, and at a current density of 100 mA/g, after 100 cycles, the reversible specific capacity is 345 mAh/g, which is a pure CoTe 2 (100.7 mAh) /g) 3.43 times, and the CoTe 2 /MXene composite in this example showed good cycle stability and excellent rate performance.
实施例2Example 2
一种CoTe 2/MXene复合材料的制备方法，包括以下步骤： A preparation method of CoTe 2 /MXene composite material, comprising the following steps:
(1)取0.2mmol MXene(Ti 3C 2T x)加入到N，N-二甲基甲酰胺中，配置成5mg/ml的分散液，磁力搅拌4小时； (1) Take 0.2 mmol of MXene (Ti 3 C 2 T x ) and add it to N,N-dimethylformamide, configure it into a dispersion of 5 mg/ml, and stir magnetically for 4 hours;
(2)将0.2mmol Co(NO 3) 2·6H 2O与0.25mmol尿素加入步骤(1)所述分散液中，并搅拌9小时； (2) adding 0.2 mmol Co(NO 3 ) 2 .6H 2 O and 0.25 mmol urea to the dispersion described in step (1), and stirring for 9 hours;
(3)将步骤(2)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150℃，保温15h，然后冷却至室温；(3) transferring the dispersion obtained in step (2) into a reaction kettle with a capacity of 50ml and sealing, placing it in an oven, heating to 150°C, keeping the temperature for 15h, and then cooling to room temperature;
(4)将步骤(3)得到的产物在6000r/min条件下离心8分钟，用去离子水和无水乙醇交替洗涤滤渣3次；(4) the product obtained in step (3) was centrifuged for 8 minutes under the condition of 6000r/min, and the filter residue was washed alternately 3 times with deionized water and absolute ethanol;
(5)将步骤(4)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10小时，得到前驱体Co(OH) 2/MXene。 (5) drying the centrifuged product obtained in step (4) in a vacuum drying oven at a drying temperature of 60° C. and a drying time of 10 hours to obtain the precursor Co(OH) 2 /MXene.
(6)将0.2mmol前驱体Co(OH) 2/MXene与0.4mmol碲粉分别放置于两个石英舟中； (6) Place 0.2 mmol of the precursor Co(OH) 2 /MXene and 0.4 mmol of tellurium powder in two quartz boats respectively;
(7)将石英舟放于管式炉中，其中，将盛放碲粉的石英舟置于管式炉的上游，通入高纯度Ar，流速为200ml/min，以5℃/min的升温速率加热至600℃，保温6h，然后自然冷却到室温；(7) the quartz boat is placed in the tube furnace, wherein, the quartz boat containing the tellurium powder is placed in the upstream of the tube furnace, and high-purity Ar is passed into it, and the flow rate is 200ml/min, and the temperature rises at 5°C/min. The rate of heating to 600 ℃, holding for 6h, and then naturally cooled to room temperature;
(8)将步骤(7)所得产物在6000r/min条件下离心8分钟，用去离子水和无水乙醇分别洗涤滤渣3次；(8) centrifuging the product obtained in step (7) at 6000 r/min for 8 minutes, and washing the filter residue 3 times with deionized water and absolute ethanol respectively;
(9)将步骤(8)所得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 10小时，最终得到CoTe 2/MXene复合材料。 (9) Drying the centrifuged product obtained in step (8) in a vacuum drying oven at a drying temperature of 60° C. and a drying time of 10 hours to finally obtain a CoTe 2 /MXene composite material.
将CoTe 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 CoTe 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CoTe 2/MXene复合材料比表面积为211.9m 2/g，在电流密度为100mA/g下，经100圈循环，可逆比容量为450mAh/g，是单纯CoTe 2(100.7mAh/g)的4.47倍，且本实施例中CoTe 2/MXene复合材料表现出良好的循环稳定性以及优异的倍率性能。 The specific surface area of the CoTe 2 /MXene composite prepared in this example is 211.9 m 2 /g, and at a current density of 100 mA/g, after 100 cycles, the reversible specific capacity is 450 mAh/g, which is a pure CoTe 2 (100.7 mAh) /g) 4.47 times, and the CoTe 2 /MXene composite in this example showed good cycle stability and excellent rate performance.
实施例3Example 3
一种CoTe 2/MXene复合材料的制备方法，包括以下步骤： A preparation method of CoTe 2 /MXene composite material, comprising the following steps:
(1)取0.1mmol 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6小时； (1) Take 0.1 mmol 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 6 hours;
(2)将0.1mmol Co(NO 3) 2·6H 2O与0.2mmol尿素加入步骤(1)所述分散液中，并搅拌12小时； (2) adding 0.1 mmol Co(NO 3 ) 2 .6H 2 O and 0.2 mmol urea to the dispersion described in step (1), and stirring for 12 hours;
(3)将步骤(2)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220℃，保温24h，然后冷却至室温；(3) The dispersion liquid obtained in step (2) is moved into a reaction kettle with a capacity of 50ml, sealed and placed in an oven, heated to 220° C., maintained for 24h, and then cooled to room temperature;
(4)将步骤(3)得到的产物，在8000r/min条件下离心10分钟，用去离子水和无水乙醇交替洗涤滤渣3次后；(4) the product obtained in step (3) is centrifuged for 10 minutes under the condition of 8000 r/min, and after alternately washing the filter residue 3 times with deionized water and absolute ethanol;
(5)将步骤(4)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15小时，得到前驱体Co(OH) 2/MXene。 (5) drying the centrifuged product obtained in step (4) in a vacuum drying oven at a drying temperature of 60° C. and a drying time of 15 hours to obtain the precursor Co(OH) 2 /MXene.
(6)将0.1mmol前驱体Co(OH) 2/MXene与0.44mmol碲粉分别放置于两个石英舟中； (6) Place 0.1 mmol of the precursor Co(OH) 2 /MXene and 0.44 mmol of tellurium powder in two quartz boats respectively;
(7)将石英舟放于管式炉中，其中，将放有碲粉的石英舟置于管式炉的上游，通入高纯度Ar，流速为300ml/min，以6℃/min的升温速率加热至1000℃，保温10h，然后自然冷却到室温；(7) the quartz boat is placed in the tube furnace, wherein, the quartz boat with the tellurium powder is placed on the upstream of the tube furnace, and high-purity Ar is passed into it, the flow rate is 300ml/min, and the temperature rises at 6°C/min The rate of heating to 1000 ℃, holding for 10h, and then naturally cooled to room temperature;
(8)将步骤(7)所得产物用在8000r/min条件下离心10分钟，去离子水和无水乙醇分别洗涤3次；(8) the product obtained in step (7) was centrifuged for 10 minutes under the condition of 8000 r/min, and washed with deionized water and absolute ethanol for 3 times respectively;
(9)将步骤(8)所得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15小时，最终得到CoTe 2/MXene复合材料。 (9) Drying the centrifuged product obtained in step (8) in a vacuum drying oven at a drying temperature of 60° C. and a drying time of 15 hours to finally obtain a CoTe 2 /MXene composite material.
将CoTe 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 CoTe 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CoTe 2/MXene复合材料比表面积为197.5m 2/g，在电流密度为100 mA/g下，经100圈循环，可逆比容量为403mAh/g，是单纯CoTe 2(100.7mAh/g)的4.01倍，且本实施例中CoTe 2/MXene复合材料表现出良好的循环稳定性以及优异的倍率性能。 The specific surface area of the CoTe 2 /MXene composite prepared in this example is 197.5 m 2 /g, and at a current density of 100 mA/g, after 100 cycles, the reversible specific capacity is 403 mAh/g, which is a pure CoTe 2 (100.7 mAh/g), and the CoTe 2 /MXene composite in this example showed good cycle stability and excellent rate performance.
对比例1Comparative Example 1
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。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.
图4为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 shows the cycle performance of the potassium ion battery assembled with MXene material at a current density of 100 mA/g.
由图可见，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，为61.1mA h/g。It can be seen from the figure that the potassium ion battery assembled with MXene material has good cycle stability during the charge and discharge process at a current density of 100 mA/g, but the specific capacity is small, which is 61.1 mA h/g.
对比例2：Comparative Example 2:
单独NiTe 2材料的制备方法，包括以下步骤： The preparation method of single NiTe 2 material includes the following steps:
(1)将0.1mmol Co(NO 3) 2·6H 2O与0.1mmol尿素加入到N，N-二甲基甲酰胺中，配置成1mg/ml的分散液，并搅拌3小时； (1) 0.1 mmol Co(NO 3 ) 2 .6H 2 O and 0.1 mmol urea were added to N,N-dimethylformamide, configured into a dispersion of 1 mg/ml, and stirred for 3 hours;
(2)将步骤(1)所得分散液移入容量为100ml反应釜中密封后放置在烘箱中，加热至80℃，保温8h，然后冷却至室温；(2) The dispersion liquid obtained in step (1) is moved into a reaction kettle with a capacity of 100ml, sealed, placed in an oven, heated to 80° C., maintained for 8h, and then cooled to room temperature;
(3)将步骤(2)得到的产物，在5000r/min条件下离心5分钟，用去离子水和无水乙醇分别洗涤滤渣3次；(3) the product obtained in step (2) was centrifuged for 5 minutes under the condition of 5000r/min, and the filter residue was washed 3 times with deionized water and absolute ethanol respectively;
(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6小时，得到前驱体Co(OH) 2/MXene。 (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 6 hours to obtain the precursor Co(OH) 2 /MXene.
(5)将0.1mmol前驱体Co(OH) 2/MXene与0.2mmol碲粉分别放置于两个石英舟中； (5) 0.1 mmol precursor Co(OH) 2 /MXene and 0.2 mmol tellurium powder were placed in two quartz boats respectively;
(6)将石英舟放于管式炉中，其中，将放有碲粉的石英舟置于管式炉的上游，通入高纯度Ar，流速为100ml/min，以4℃/min的升温速度加热至400℃，保温2h，然后自然冷却到室温；(6) the quartz boat is placed in the tube furnace, wherein, the quartz boat with the tellurium powder is placed on the upstream of the tube furnace, and high-purity Ar is introduced, the flow rate is 100ml/min, and the temperature rises at 4°C/min Speed heating to 400°C, hold for 2h, and then naturally cool to room temperature;
(7)将步骤(6)所得产物在5000r/min条件下离心5分钟，用去离子水和无水乙醇分别洗涤3次；(7) centrifuging the product obtained in step (6) at 5000 r/min for 5 minutes, and washing 3 times with deionized water and absolute ethanol respectively;
(8)将步骤(7)所得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6小时，最终得到CoTe 2/MXene复合材料。 (8) Drying the centrifuged product obtained in step (7) in a vacuum drying oven at a drying temperature of 60° C. and a drying time of 6 hours to finally obtain a CoTe 2 /MXene composite material.
将单纯的CoTe 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N-甲基吡咯烷酮，搅拌，形成均匀浆料后涂覆在集流体上，经真空干燥、切片后，制备钾离子电池负极极片。 Mix pure CoTe 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. After vacuum drying and slicing, the negative pole piece of potassium ion battery was prepared.
本对比例所制备的CoTe 2材料比表面积为45.6m 2/g，在100mA/g的电流密度下，经100圈循环，可逆容量为100.7mAh/g。 The specific surface area of the CoTe 2 material prepared in this comparative example is 45.6 m 2 /g, and the reversible capacity is 100.7 mAh/g after 100 cycles at a current density of 100 mA/g.
将各组材料进行比表面积，CoTe 2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, CoTe 2 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，CoTe 2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 loading amount of CoTe 2 was analyzed by X-ray energy dispersive spectroscopy (EDS). Please refer to the specific examples for the specific capacity after 100 cycles. The performance test results of each group are shown in Table 1.
表1：性能测试Table 1: Performance Testing
Figure PCTCN2020112558-appb-000001
Figure PCTCN2020112558-appb-000001
图1是实施例1中CoTe 2/MXene复合材料的扫描电镜图。从图1可以看出，有一些CoTe 2纳米颗粒均匀地生长在MXene材料表面，还有一些CoTe 2纳米颗粒均匀地生长在片层间和边缘处，无团聚现象，呈现出一端闭合一端打开的手风琴状层状结构。CoTe 2的生长分布可以扩大片层之间的距离和比表面积；MXene材料的片层状结构可以提供有效结构支撑，阻止CoTe 2材料的团聚现象。 1 is a scanning electron microscope image of the CoTe 2 /MXene composite material in Example 1. It can be seen from Figure 1 that some CoTe 2 nanoparticles are uniformly grown on the surface of the MXene material, and some CoTe 2 nanoparticles are uniformly grown between the lamellae and at the edges, without agglomeration, showing one end closed and the other open. Accordion-like layered structure. The growth distribution of CoTe 2 can expand the distance and specific surface area between the lamellae; the lamellar structure of MXene material can provide effective structural support and prevent the agglomeration phenomenon of CoTe 2 material.
图3是对比例1中单独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；由图可见，MXene材料具有良好的循环稳定性，但比容量很小，这是由于本身的MXene材料层间距过小所致。Figure 3 is a graph of the cycle performance of the potassium ion battery assembled with a single MXene material in Comparative Example 1 at a current density of 100 mA/g; it can be seen from the figure that the MXene material has good cycle stability, but the specific capacity is very small, which is It is caused by the too small interlayer spacing of the MXene material itself.
图4是对比例2中单独CoTe 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。由图可见，单独CoTe 2材料具有一定的储钾能力，但在充放电过程中由于易团聚比容量下降较快，循环性能不稳定。 4 is a graph of the cycle performance measured at a current density of 100 mA/g for the potassium-ion battery assembled with CoTe 2 material alone in Comparative Example 2. It can be seen from the figure that the single CoTe 2 material has a certain potassium storage capacity, but during the charge and discharge process, the specific capacity decreases rapidly due to the easy agglomeration, and the cycle performance is unstable.
图2是实施例1中CoTe 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；与图3-4相比，CoTe 2/MXene复合材料显示出高的电池容量和良好的循环性能。这是因为渡金属碲化物CoTe 2生长在MXene纳米片上，CoTe 2的生长分布可以扩大片层之间的距离，防止MXene纳米片堆叠，增大MXene比表面积；MXene材料的片层状结构可以提供有效结构支撑，阻止CoTe 2材料的团聚现象。两者相互作用，有利于电极材料与电解液之间充分浸润，可以提供更多的活性位点和电子传导通道，更大的转移和离子吸附面积与 空位，因而复合材料在循环100圈后的比容量，循环稳定性和电池容量方面能具有突出的表现。对于钾离子电池的开发和应用具有重要意义。 Figure 2 is a graph showing the cycle performance of the potassium ion battery assembled with CoTe 2 /Mxene composite material in Example 1 at a current density of 100 mA/g ; battery capacity and good cycle performance. This is because the transition metal telluride CoTe 2 is grown on MXene nanosheets, and the growth distribution of CoTe 2 can expand the distance between the sheets, prevent the stacking of MXene nanosheets, and increase the specific surface area of MXene; the lamellar structure of MXene materials can provide Effective structural support to prevent the agglomeration of CoTe 2 materials. The interaction between the two is conducive to the full infiltration between the electrode material and the electrolyte, which can provide more active sites and electron conduction channels, and larger transfer and ion adsorption areas and vacancies. It can have outstanding performance in terms of specific capacity, cycle stability and battery capacity. It is of great significance for the development and application of potassium-ion batteries.
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CoTe 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 CoTe 2 /MXene composite material, characterized in that, comprising the following preparation steps:
    (1)将MXene材料加入分散剂中，配制成浓度为1-10mg/ml的分散液；(1) adding the MXene material to the dispersing agent, and preparing a dispersion liquid with a concentration of 1-10 mg/ml;
    (2)将钴源与还原剂按照摩尔比为1：1～5的比例加入步骤(1)所述分散液中，搅拌溶解，得到混合液；(2) adding the cobalt source and the reducing agent into the dispersion solution described in step (1) in a molar ratio of 1:1 to 5, stirring and dissolving to obtain a mixed solution;
    (3)将步骤(2)所述混合液加热至80-220℃，反应8-24h，冷却，离心，洗涤，干燥，得到前驱体Co(OH) 2/MXene； (3) heating the mixed solution in step (2) to 80-220° C., reacting for 8-24 hours, cooling, centrifuging, washing, and drying to obtain the precursor Co(OH) 2 /MXene;
    (4)将步骤(3)所述前驱体Co(OH) 2/MXene与碲源按照摩尔比为1：1～6的比例分别放置于两个石英舟中，在氮气气氛下，加热至300-1000℃，保温2-10h，冷却，得到粗产物； (4) The precursor Co(OH) 2 /MXene and the tellurium source described in step (3) were placed in two quartz boats in a molar ratio of 1:1 to 6, respectively, and heated to 300 in a nitrogen atmosphere. -1000°C, keep warm for 2-10h, and cool to obtain crude product;
    (5)将步骤(4)所述粗产物离心，洗涤，干燥，得到CoTe 2/MXene复合材料； (5) centrifuging the crude product described in step (4), washing and drying to obtain CoTe 2 /MXene composite material;
  2. 根据权利要求1所述的CoTe 2/MXene复合材料的制备方法，其特征在于，所述MXene为Ti 3C 2T x、Ti 2CT x、V 3C 2T x、Mo 3N 2T x中的至少一种。 The preparation method of CoTe 2 /MXene composite material according to claim 1, wherein the MXene is Ti 3 C 2 T x , Ti 2 CT x , V 3 C 2 T x , Mo 3 N 2 T x at least one of them.
  3. 根据权利要求1所述的CoTe 2/MXene复合材料的制备方法，其特征在于，所述钴源为CoCl 2·6H 2O、Co(NO 3) 2·6H 2O、CoSO 4·7H 2O中的至少一种，优选的，所述碲源为碲粉、联苯二碲、亚碲酸钠中的至少一种。 The preparation method of CoTe 2 /MXene composite material according to claim 1, wherein the cobalt source is CoCl 2 ·6H 2 O, Co(NO 3 ) 2 ·6H 2 O, CoSO 4 ·7H 2 O At least one of them, preferably, the tellurium source is at least one of tellurium powder, biphenyl ditellurium, and sodium tellurite.
  4. 根据权利要求1所述的CoTe 2/MXene复合材料的制备方法，其特征在于，所述还原剂为尿素、NH 4F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 CoTe 2 /MXene composite material according to claim 1, wherein the reducing agent is at least one of urea and NH 4 F; preferably, the cleaning agent is water or ethanol at least one.
  5. 根据权利要求1所述的CoTe 2/MXene复合材料的制备方法，其特征在于，所述CoTe 2/MXene复合材料中CoTe 2负载量为50-150wt％。 The method for preparing a CoTe 2 /MXene composite material according to claim 1, wherein the CoTe 2 loading in the CoTe 2 /MXene composite material is 50-150wt%.
  6. 根据权利要求1所述的CoTe 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。 The method for preparing a CoTe 2 /MXene composite material according to claim 1, wherein the dispersant is at least one of N,N-dimethylformamide, ethanol, and ethylene glycol.
  7. 根据权利要求1所述的CoTe 2/MXene复合材料的制备方法，其特征在于，所述保护气体为N 2或Ar，气体流速为100-300ml/min。 The method for preparing a CoTe 2 /MXene composite material according to claim 1, wherein the protective gas is N 2 or Ar, and the gas flow rate is 100-300 ml/min.
  8. 根据权利要求1所述的CoTe 2/MXene复合材料的制备方法，其特征在于，步骤(3)和步骤(5)中真空干燥的温度为50-80℃，干燥时间6-15h，真空度不超过130Pa。 The preparation method of CoTe 2 /MXene composite material according to claim 1, characterized in that, in step (3) and step (5), the temperature of vacuum drying is 50-80° C., the drying time is 6-15h, and the vacuum degree is not more than 130Pa.
  9. 一种根据权利要求1-8中任一项所述的制备方法制备得到的CoTe 2/MXene复合材料。 A CoTe 2 /MXene composite material prepared by the preparation method according to any one of claims 1-8.
  10. 一种钾离子电池负极，其特征在于，其包括权利要求9所述的CoTe 2/MXene复合材料。 A potassium ion battery negative electrode, characterized in that it comprises the CoTe 2 /MXene composite material according to claim 9 .
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