WO2022032744A1 - Nbs2/mxene composite material and preparation method therefor - Google Patents

Nbs2/mxene composite material and preparation method therefor Download PDF

Info

Publication number
WO2022032744A1
WO2022032744A1 PCT/CN2020/112561 CN2020112561W WO2022032744A1 WO 2022032744 A1 WO2022032744 A1 WO 2022032744A1 CN 2020112561 W CN2020112561 W CN 2020112561W WO 2022032744 A1 WO2022032744 A1 WO 2022032744A1
Authority
WO
WIPO (PCT)
Prior art keywords
nbs
mxene
composite material
preparation
mxene composite
Prior art date
Application number
PCT/CN2020/112561
Other languages
French (fr)
Chinese (zh)
Inventor
张业龙
周健文
徐晓丹
孙宏阳
任蓝图
宋伟东
汪达
Original Assignee
五邑大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 五邑大学 filed Critical 五邑大学
Publication of WO2022032744A1 publication Critical patent/WO2022032744A1/en

Links

Images

Classifications

    • 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
    • H01M4/5815—Sulfides
    • 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, in particular to a NbS2/MXene composite material and a preparation method thereof.
  • Potassium-ion batteries are a potential new generation of energy technology, with the advantages of high energy density, long cycle life, large capacity, abundant natural resources of potassium element, and less pollution.
  • Electrode materials play an important role in the application of batteries. At present, the widely used electrode material in industrial batteries is graphite, but graphite has limited energy density and poor rate performance, which greatly limits the battery performance and its application potential. Therefore, exploring a A high-performance electrode material has important practical significance.
  • NbS 2 nanosheets is a potential electrode material.
  • the ion migration barrier value of NbS 2 is low, and the weak van der Waals force and large interlayer spacing between the nanosheets can improve the diffusion efficiency of potassium ions.
  • As an electrode material it has high specific capacity and long cycle life.
  • NbS 2 nanosheets have the defects of easy agglomeration and unstable structure, which will lead to rapid degradation of cycling performance during charge-discharge cycling.
  • MXene has a unique accordion-like multilayer structure and good electrical conductivity, and is considered as a potential electrode material.
  • the accordion-like multi-layer structure of MXene is beneficial to increase the contact area during ion diffusion; good electrical conductivity can accelerate the ion diffusion kinetics; surface functional groups can enhance the adsorption capacity.
  • 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.
  • one of the objectives of the present invention is to provide a NbS 2 /MXene composite material.
  • Another object of the present invention is to provide a method for preparing the above-mentioned NbS 2 /MXene composite material.
  • the present invention provides an application of the NbS 2 /MXene composite material, and the NbS 2 /MXene composite material is used for the negative electrode of a potassium ion battery.
  • the present invention adopts the following scheme:
  • step (3) adding an appropriate amount of MXene nanosheets and water to the mixed solution described in step (2), cleaning, stirring, and forming a suspension;
  • step (3) the suspension described in step (3) is moved into the reactor lining, the reactor is sealed in the oven, and the hydrothermal reaction is carried out to obtain a crude product;
  • the consumption of the niobium pentoxide in step (1) is 10-50 mmol; the consumption of the sulfur source is 20-100 mmol.
  • the calcination temperature in step (1) is 500-700°C, preferably 550-650°C, such as 500°C, 550°C, 600°C, 650°C, 700°C; the calcination time is 5-7h , preferably 5.5-6.5h, such as 5h, 5.5h, 6h, 6.5h, 7h.
  • the sulfur source is one or more of thioacetamide, sulfur powder, and thiourea.
  • the protective gas is one of nitrogen, helium and argon.
  • described dispersing solvent is one or more in N-methylpyrrolidone, sodium hydroxide, N,N-dimethylformamide; Preferably, with N-methylpyrrolidone and sodium hydroxide volume ratio 1: 1 mix.
  • the dosage of the N-methylpyrrolidone is 5-10ml, and the concentration is 0.5-5mg/L; the dosage of the sodium hydroxide is 5-10ml, and the concentration is 0.1-5mg/L.
  • the dosage of the MXene nanosheets in step (3) is 10-50 mmol; the dosage of the water is 20-60 mg.
  • the MXene is one or more of Ti 3 C 2 T X , Nb 2 C X , and V 3 C 2 T X ; preferably Ti 3 C 2 T X is used.
  • the cleaning in step (3) is ultrasonic cleaning, wherein the cleaning temperature is 25-50°C, such as 25°C, 30°C, 35°C, 40°C; the cleaning time is 4-6h, such as 4h, 5h, 6h ; The stirring is magnetic stirring, and the stirring time is 10-12h, such as 10h, 11h, 12h.
  • the oven temperature in step (4) is 150-250°C, preferably 180°C
  • the reaction time is 12-20h, preferably 13-18h, such as 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h.
  • the centrifugal speed in step (5) is 7000-12000r/min, preferably 8500r/min, and the centrifugation time is 5-20min, preferably 10min.
  • the temperature of vacuum drying is 50-140°C, preferably 90°C, and the drying time is 6-12h, such as 6h, 7h, 8h, 9h, 10h, 11h, 12h.
  • the molar ratio of the niobium pentoxide, the sulfur source and the MXene nanosheet is 1:1.5-2.5:1.
  • a NbS 2 /MXene composite material prepared by the above preparation method.
  • NbS 2 /MXene material an application of the above-mentioned NbS 2 /MXene material, the NbS 2 /MXene composite material is used for the negative electrode of potassium ion battery.
  • Beneficial effects of the present invention :
  • the NbS 2 /MXene composite material of the present invention has high electrochemical performance, the NbS 2 nanosheets are grown on MXene, and the layered stable structure increases the specific surface area and conductivity, preventing the agglomeration of NbS 2 and the obvious volume Swelling, weak interlayer interaction, and functional groups on the surface improve the conversion reaction and intercalation reaction of potassium ions, and promote the electrochemical performance of electrode materials;
  • the NbS 2 /MXene composite material of the present invention has lower charge transfer resistance, and the loading of NbS 2 nanosheets increases the interlayer spacing to expose more active edge sites, thereby improving the ion transfer efficiency;
  • NbS 2 /MXene composite material of the present invention has good cycle stability. It can be seen from Figures 2 to 5 that the cycle stability and specific capacity of the NbS 2 /MXene composite material of the present invention are better than those of NbS2 Materials, MXene materials and sulfur-doped MXene anode materials;
  • the NbS2/MXene composite material of the present invention is prepared by solid-phase vulcanization and a simple hydrothermal solvent method, the process is simple and effective, and the NbS2/MXene composite material has excellent performance in all aspects, which is conducive to popularization and application.
  • FIG. 1 is a scanning electron microscope image of the NbS 2 /MXene composite material in Example 1.
  • FIG. 1 is a scanning electron microscope image of the NbS 2 /MXene composite material in Example 1.
  • Example 2 is a graph showing the cycle performance of the potassium ion battery assembled with NbS 2 /MXene composite material in Example 1 at a current density of 100 mA/g.
  • Figure 3 shows the cycle performance of the potassium ion battery assembled with NbS 2 material at a current density of 100 mA/g.
  • Figure 4 shows the cycle performance of the potassium ion battery assembled with MXene material at a current density of 100 mA/g.
  • Figure 5 is a graph of the cycle performance of the potassium ion battery assembled with S material at a current density of 100 mA/g.
  • Figure 6 is a scanning electron microscope image of MXene.
  • Figure 7 is the XRD pattern of NbS2/MXene composite and MXene.
  • 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 NbS 2 /MXene composite material comprising the following steps:
  • NbS 2 /MXene composite 10 mg of super P and 10 mg of polyvinylidene fluoride binder and mix, add a small amount of N-methylpyrrolidone, coat on copper foil after stirring, and dry at 90 °C for 3 hours.
  • Use a microtome to cut the copper foil into a circular shape as the working electrode. After drying, put it into an inert atmosphere glove box with an oxygen and water content below 0.4 ppm.
  • Figure 1 is the scanning electron microscope image of the NbS 2 /MXene composite material in Example 1. It can be seen from the figure that the sample exhibits an organ-like multi-layer structure, and the NbS 2 material is evenly distributed on the surface of the MXene material without agglomeration, indicating that NbS 2 was successfully loaded on the surface of the MXene material. on MXene without destroying the MXene morphology.
  • Figure 6 is a scanning electron microscope image of MXene. By comparing Fig. 1 and Fig. 6, it can be seen that the successful loading of NbS increases the interlayer spacing of the MXene material, exposing more active edge sites.
  • FIG. 7 is the XRD pattern of the NbS2/MXene composite material and MXene. It can be seen from the figure that both NbS 2 /MXene composites and MXene have absorption peaks at 2 ⁇ of about 7 degrees and 9 degrees, respectively, corresponding to the (002) crystal plane. Compared with the absorption peaks of MXene, the characteristics of NbS 2 /MXene composites The peak shifts to a low angle, indicating that the lattice constant changes and the interplanar spacing increases, which indicates that the interplanar spacing of NbS 2 /MXene composites increases through the introduction of NbS 2 .
  • Figure 2 shows the cycle performance of the potassium ion battery assembled with the NbS 2 /MXene composite material in Example 1 at a current density of 100 mA/g. At the current density of /g, there is still a reversible capacity of 244.8 mA h/g after 100 cycles.
  • the material in this example has high reversible capacity and good cycle performance.
  • a preparation method of NbS 2 /MXene composite material comprising the following steps:
  • NbS 2 /MXene composite 10 mg of super P and 10 mg of polyvinylidene fluoride binder and mix, add a small amount of N-methylpyrrolidone, coat on copper foil after stirring, and dry at 90 °C for 3 hours.
  • Use a microtome to cut the copper foil into a circular shape as the working electrode. After drying, put it into an inert atmosphere glove box with an oxygen and water content below 0.4 ppm.
  • the potassium ion battery assembled with the NbS 2 /MXene composite material in this example still has a reversible capacity of 267.3 mA h/g after 100 cycles at a current density of 100 mA/g.
  • the material in this example has high reversible capacity and good cycle performance.
  • a preparation method of NbS 2 /MXene composite material comprising the following steps:
  • NbS 2 /MXene composite material 10 mg of super P and 10 mg of polyvinylidene fluoride binder and mix, add a small amount of N-methylpyrrolidone, coat on copper foil after stirring, and dry at 50 °C for 3 hours.
  • Use a microtome to cut the copper foil into a circular shape as the working electrode. After drying, put it into an inert atmosphere glove box with an oxygen and water content below 0.4 ppm.
  • the potassium ion battery assembled with NbS 2 /MXene composite material in this example still has a reversible capacity of 253.3 mA h/g after 100 cycles at a current density of 100 mA/g.
  • the material in this example has high reversible capacity and good cycle performance.
  • a preparation method of NbS 2 /MXene negative electrode material comprising the following steps:
  • NbS 2 /MXene composite 10 mg of super P and 10 mg of polyvinylidene fluoride binder and mix, add a small amount of N-methylpyrrolidone, coat on copper foil after stirring, and dry at 90 °C for 3 hours.
  • Use a microtome to cut the copper foil into a circular shape as the working electrode. After drying, put it into an inert atmosphere glove box with an oxygen and water content below 0.4 ppm.
  • the potassium ion battery assembled with the NbS2/MXene composite material in this example still has a reversible capacity of 272.9 mA h/g after 100 cycles at a current density of 100 mA/g.
  • the material in this example has high reversible capacity and good cycle performance.
  • NbS 2 material 10mg of super P and 10mg of polyvinylidene fluoride binder and mix, add a small amount of N-methylpyrrolidone, coat on copper foil after stirring, dry at 90°C for 3h, use 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.
  • NbS2 As an attractive electrode material, NbS2 has been used in battery material research due to its high rate capability and structural stability, and its good layered crystal structure allows multiple approaches to fabricate and integrate 2D nanostructures into in various applications.
  • NbS the limitations of NbS : nanosheets are prone to agglomeration and structurally unstable, which can lead to the degradation of electrochemical performance during charge-discharge cycling, poor electrical conductivity, limited theoretical capacity and cycling instability based on the intercalation mechanism, which greatly limit its performance. practical application.
  • FIG. 3 is a graph showing the cycle performance of the potassium ion battery assembled with the NbS2 material of the comparative example at a current density of 100 mA/g. It can be seen from the figure that the nanosheets are easily agglomerated and the structure is unstable during the charging and discharging process of the potassium ion battery assembled with NbS 2 material at a current density of 100 mA/g, and the specific capacity performance declines after 20 cycles.
  • 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-discharge process at a current density of 100 mA/g, but the specific capacity is small.
  • NbS2 nanosheets act as two-dimensional transition metal chalcogenides, and the weak van der Waals interaction between the layers improves the efficient diffusion of potassium ions.
  • the NbS2 /MXene composite material has more The layered structure increases the specific surface area and prevents significant volume expansion during material agglomeration and ion diffusion, in which weaker interlayer interactions and surface functional groups improve the conversion and intercalation reactions of potassium ions, which together promote the electrochemical performance of electrode materials Performance improvements.
  • the NbS 2 nanosheet of the NbS 2 /MXene composite material exposes more active edge sites during the growth of the MXene material, which improves the ion transfer efficiency and promotes the electrochemical performance of the electrode material. .
  • a preparation method of sulfur-doped MXene negative electrode material comprising the following steps:
  • Figure 5 shows the cycle performance of potassium-ion batteries assembled with sulfur-doped MXene battery anode materials at a current density of 100 mA/g.

Abstract

MXene and NbS 2 are selected as raw materials to prepare an NbS 2/MXene composite material by solid-phase vulcanization and hydrothermal solvent methods. A multilayer structure of the composite material increases the specific surface area and prevents the material from agglomerating and the volume in an ion diffusion process from obviously expanding; during the growth of an NbS 2 nanosheet, more active edge sites of the material are exposed, a weak interlayer interaction and a surface functional group improve the conversion reaction and intercalation reaction of potassium ions, and thus the improvement of electrochemical performance of an electrode material is facilitated. Experiments show that the NbS 2/MXene composite material has high reversible capacity and good cycling stability. The preparation method is simple and reasonable, the material is low in cost, and the method is safe and efficient.

Description

一种NbS 2/MXene复合材料及其制备方法 A kind of NbS 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NbS2/MXene复合材料及其制备方法。The invention belongs to the technical field of new energy, in particular to a NbS2/MXene composite material and a preparation method thereof.
背景技术Background technique
随着混合动力汽车和便携式电子设备的发展，需要高容量高性能的储能装置来满足未来电子产品的需求。钾离子电池是有潜力的新一代能源技术，具有能量密度高、循环寿命长、容量大、钾元素自然资源丰富、污染少等优势。电极材料在电池的应用中起着重要作用，目前工业电池中广泛使用的电极材料是石墨，但石墨的能量密度有限，速率性能不佳，大大限制了电池性能及其应用潜力，因此，探索一种高性能电极材料具有重要的现实意义。With the development of hybrid vehicles and portable electronic devices, high-capacity and high-performance energy storage devices are required to meet the demands of future electronic products. Potassium-ion batteries are a potential new generation of energy technology, with the advantages of high energy density, long cycle life, large capacity, abundant natural resources of potassium element, and less pollution. Electrode materials play an important role in the application of batteries. At present, the widely used electrode material in industrial batteries is graphite, but graphite has limited energy density and poor rate performance, which greatly limits the battery performance and its application potential. Therefore, exploring a A high-performance electrode material has important practical significance.
近年来二维过渡金属硫族化合物(包括MoS 2、WS 2、VS 2、CrS 2、TiS 2、NiTe 2和CoTe 2等)优异的电化学性能引起了人们的关注。其中NbS 2纳米片是一种具有潜力的电极材料，NbS 2的离子迁移势垒值低，且纳米片各层之间较弱的范德华力和较大的层间距可以提高钾离子的扩散效率，作为电极材料比容量高，循环寿命长。但NbS 2纳米片具有易团聚且结构不稳定的缺陷，在充放电循环过程中会导致循环性能快速衰减。 In recent years, the excellent electrochemical properties of two-dimensional transition metal chalcogenides (including MoS 2 , WS 2 , VS 2 , CrS 2 , TiS 2 , NiTe 2 and CoTe 2 ) have attracted much attention. Among them, NbS 2 nanosheets is a potential electrode material. The ion migration barrier value of NbS 2 is low, and the weak van der Waals force and large interlayer spacing between the nanosheets can improve the diffusion efficiency of potassium ions. As an electrode material, it has high specific capacity and long cycle life. However, NbS 2 nanosheets have the defects of easy agglomeration and unstable structure, which will lead to rapid degradation of cycling performance during charge-discharge cycling.
MXene具有独特的手风琴状的多层结构和良好的导电性，被认为是一种具有发展潜力的电极材料。MXene手风琴状的多层结构有利于增加离子扩散时接触面积；良好的导电性可以加快离子扩散动力学；表面官能团可以使吸附能力增强。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。MXene has a unique accordion-like multilayer structure and good electrical conductivity, and is considered as a potential electrode material. The accordion-like multi-layer structure of MXene is beneficial to increase the contact area during ion diffusion; good electrical conductivity can accelerate the ion diffusion kinetics; surface functional groups can enhance the adsorption capacity. 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.
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NbS 2/MXene复合材料。本发明的另一目的在于提供上述NbS 2/MXene复合材料的制备方法。进一步的，本发明提供一种NbS 2/MXene复合材料的应用，将所述NbS 2/MXene复合材料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 NbS 2 /MXene composite material. Another object of the present invention is to provide a method for preparing the above-mentioned NbS 2 /MXene composite material. Further, the present invention provides an application of the NbS 2 /MXene composite material, and the NbS 2 /MXene composite material is used for the negative electrode of a potassium ion battery.
本发明采用以下方案：The present invention adopts the following scheme:
一种NbS 2/MXene复合材料及其制备方法，包括如下制备步骤： A NbS 2 /MXene composite material and a preparation method thereof, comprising the following preparation steps:
(1)称取适量五氧化二铌和硫源装载在两个单独的刚玉方舟中，通入气氛气体，分别放置于的管式炉中的气流中游和上游，逐步升温，煅烧，冷却后收集中游的刚玉方舟中黑色物质NbS 2粉末，真空储存； (1) Weigh an appropriate amount of niobium pentoxide and sulfur source and load them in two separate corundum arks, pass into the atmosphere gas, place them in the midstream and upstream of the gas flow in the tube furnace respectively, gradually heat up, calcine, and collect after cooling The black substance NbS 2 powder in the corundum ark in the middle reaches, stored in vacuum;
(2)将黑色NbS 2粉末置于烧杯中，加入适量分散溶剂，充分混匀，均匀分布混合液； (2) Place the black NbS 2 powder in a beaker, add an appropriate amount of dispersing solvent, mix well, and evenly distribute the mixed solution;
(3)取适量MXene纳米片和水加入步骤(2)所述的混合溶液中，清洗，搅拌，形成悬浊液；(3) adding an appropriate amount of MXene nanosheets and water to the mixed solution described in step (2), cleaning, stirring, and forming a suspension;
(4)将步骤(3)所述悬浊液移入反应釜内衬，将反应釜密封在烘箱中，水热反应，得到粗产物；(4) the suspension described in step (3) is moved into the reactor lining, the reactor is sealed in the oven, and the hydrothermal reaction is carried out to obtain a crude product;
(5)将粗产物用去离子水清洗2-5次，优选的为3次，离心，弃滤液，干燥，得到NbS 2/MXene复合材料。 (5) Wash the crude product with deionized water 2-5 times, preferably 3 times, centrifuge, discard the filtrate, and dry to obtain the NbS 2 /MXene composite material.
进一步地，步骤(1)中所述五氧化二铌的用量为10-50mmol；所述硫源的用量为20-100mmol。Further, the consumption of the niobium pentoxide in step (1) is 10-50 mmol; the consumption of the sulfur source is 20-100 mmol.
进一步地，步骤(1)中所述煅烧温度为500-700℃，优选的为550-650℃，例如500℃、550℃、600℃、650℃、700℃；所述煅烧时间为5-7h，优选的为5.5-6.5h，例如5h，5.5h，6h，6.5h，7h。Further, the calcination temperature in step (1) is 500-700°C, preferably 550-650°C, such as 500°C, 550°C, 600°C, 650°C, 700°C; the calcination time is 5-7h , preferably 5.5-6.5h, such as 5h, 5.5h, 6h, 6.5h, 7h.
进一步地，所述硫源为硫代乙酰胺、硫粉、硫脲中的一种或多种。Further, the sulfur source is one or more of thioacetamide, sulfur powder, and thiourea.
进一步地，步骤(1)中保护气体为氮气、氦气、氩气中的一种。Further, in step (1), the protective gas is one of nitrogen, helium and argon.
进一步地，所述分散溶剂为N-甲基吡咯烷酮、氢氧化钠、N，N-二甲基甲酰胺中的一种或多种；优选用N-甲基吡咯烷酮和氢氧化钠体积比1:1混合。Further, described dispersing solvent is one or more in N-methylpyrrolidone, sodium hydroxide, N,N-dimethylformamide; Preferably, with N-methylpyrrolidone and sodium hydroxide volume ratio 1: 1 mix.
进一步地，所述N-甲基吡咯烷酮的用量为5-10ml，浓度为0.5-5mg/L；所述氢氧化钠用量为5-10ml，浓度为0.1-5mg/L。Further, the dosage of the N-methylpyrrolidone is 5-10ml, and the concentration is 0.5-5mg/L; the dosage of the sodium hydroxide is 5-10ml, and the concentration is 0.1-5mg/L.
进一步地，步骤(3)中所述MXene纳米片的用量为10-50mmol；所述水的用量为20-60mg。Further, the dosage of the MXene nanosheets in step (3) is 10-50 mmol; the dosage of the water is 20-60 mg.
进一步地，所述MXene为Ti 3C 2T X、Nb 2CT X、V 3C 2T X中的一种或多种；优选用Ti 3C 2T X。 Further, the MXene is one or more of Ti 3 C 2 T X , Nb 2 C X , and V 3 C 2 T X ; preferably Ti 3 C 2 T X is used.
进一步地，步骤(3)中所述清洗为超声波清洗，其中清洗温度为25-50℃，例如25℃、30℃、35℃、40℃；清洗时间为4-6h，例如4h、5h、6h；所述搅拌为磁力搅拌，搅拌时间为10-12h，例如10h、11h、12h。Further, the cleaning in step (3) is ultrasonic cleaning, wherein the cleaning temperature is 25-50°C, such as 25°C, 30°C, 35°C, 40°C; the cleaning time is 4-6h, such as 4h, 5h, 6h ; The stirring is magnetic stirring, and the stirring time is 10-12h, such as 10h, 11h, 12h.
进一步地，步骤(4)中所述烘箱温度为150-250℃，优选的为180℃，反应时间12-20h，优选的为13-18h，例如12h、13h、14h、15h、16h、17h、18h、19h、20h。Further, the oven temperature in step (4) is 150-250°C, preferably 180°C, the reaction time is 12-20h, preferably 13-18h, such as 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h.
进一步地，步骤(5)中所述离心速度为7000-12000r/min，优选8500r/min，离心时间5-20min，优选的为10min。真空干燥的温度为50-140℃，优选90℃，干燥时间为6-12h，例如6h、7h、8h、9h、10h、11h、12h。Further, the centrifugal speed in step (5) is 7000-12000r/min, preferably 8500r/min, and the centrifugation time is 5-20min, preferably 10min. The temperature of vacuum drying is 50-140°C, preferably 90°C, and the drying time is 6-12h, such as 6h, 7h, 8h, 9h, 10h, 11h, 12h.
进一步地，所述五氧化二铌、硫源和MXene纳米片的摩尔比为1：1.5-2.5：1。Further, the molar ratio of the niobium pentoxide, the sulfur source and the MXene nanosheet is 1:1.5-2.5:1.
一种由上述制备方法制得的NbS 2/MXene复合材料。 A NbS 2 /MXene composite material prepared by the above preparation method.
一种上述NbS 2/MXene材料的应用，将所述NbS 2/MXene复合材料用于钾离子电池负极。本发明的有益效果： An application of the above-mentioned NbS 2 /MXene material, the NbS 2 /MXene composite material is used for the negative electrode of potassium ion battery. Beneficial effects of the present invention:
(1)本发明的NbS 2/MXene复合材料具有较高的电化学性能，NbS 2纳米片生长在MXene上，层状的稳定结构增加了比表面积和导电性，防止NbS 2的团聚和体积明显膨胀，较弱的层 间相互作用，表面的官能团改善了钾离子的转化反应和插层反应，促进电极材料的电化学性能提升； (1) The NbS 2 /MXene composite material of the present invention has high electrochemical performance, the NbS 2 nanosheets are grown on MXene, and the layered stable structure increases the specific surface area and conductivity, preventing the agglomeration of NbS 2 and the obvious volume Swelling, weak interlayer interaction, and functional groups on the surface improve the conversion reaction and intercalation reaction of potassium ions, and promote the electrochemical performance of electrode materials;
(2)本发明的NbS 2/MXene复合材料具有较低的电荷转移电阻，NbS 2纳米片的负载增加了层间距暴露出更多活性边缘位点，提高离子迁移效率； (2) The NbS 2 /MXene composite material of the present invention has lower charge transfer resistance, and the loading of NbS 2 nanosheets increases the interlayer spacing to expose more active edge sites, thereby improving the ion transfer efficiency;
(3)本发明的NbS 2/MXene复合材料具有良好的循环稳定性，从图2-图5中可以看出，本发明NbS 2/MXene复合材料的循环稳定性和比容量大小要优于NbS2材料、MXene材料及硫掺杂MXene负极材料； (3) The NbS 2 /MXene composite material of the present invention has good cycle stability. It can be seen from Figures 2 to 5 that the cycle stability and specific capacity of the NbS 2 /MXene composite material of the present invention are better than those of NbS2 Materials, MXene materials and sulfur-doped MXene anode materials;
(4)本发明所述NbS2/MXene复合材料利用固相硫化和简单水热溶剂法制备，过程简单有效，NbS2/MXene复合材料各方面性能优异，利于推广和应用。(4) The NbS2/MXene composite material of the present invention is prepared by solid-phase vulcanization and a simple hydrothermal solvent method, the process is simple and effective, and the NbS2/MXene composite material has excellent performance in all aspects, which is conducive to popularization and application.
附图说明Description of drawings
图1是实施例1中NbS 2/MXene复合材料的扫描电镜图。 FIG. 1 is a scanning electron microscope image of the NbS 2 /MXene composite material in Example 1. FIG.
图2是实施例1中NbS 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。 2 is a graph showing the cycle performance of the potassium ion battery assembled with NbS 2 /MXene composite material in Example 1 at a current density of 100 mA/g.
图3为NbS 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 shows the cycle performance of the potassium ion battery assembled with NbS 2 material at a current density of 100 mA/g.
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.
图5为S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 5 is a graph of the cycle performance of the potassium ion battery assembled with S material at a current density of 100 mA/g.
图6为MXene的扫描电镜图。Figure 6 is a scanning electron microscope image of MXene.
图7为NbS2/MXene复合材料与MXene的XRD图。Figure 7 is the XRD pattern of NbS2/MXene composite and MXene.
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做进一步说明，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NbS 2/MXene复合材料的制备方法，包括以下步骤： A preparation method of NbS 2 /MXene composite material, comprising the following steps:
(1)称取25mmol五氧化二铌和50mmol硫粉装在两个单独的刚玉方舟中，分别放置于氦气保护气氛的管式炉中的气流中游和上游，逐步升温至550℃煅烧5h，冷却后收集中游的刚玉方舟中黑色NbS 2粉末，真空储存。 (1) Weigh 25mmol of niobium pentoxide and 50mmol of sulfur powder and put them in two separate corundum arks, place them in the midstream and upstream of the gas flow in a tube furnace in a helium protective atmosphere, and gradually heat up to 550°C for calcination for 5h, After cooling, the black NbS 2 powder in the corundum ark in the midstream was collected and stored in vacuum.
(2)将黑色NbS 2粉末加入烧杯中，加入5ml的N-甲基吡咯烷酮和5ml的氢氧化钠分 散溶剂并充分搅拌形成均匀分布混合液，之后称取25mmol的MXene纳米片(Ti 3C 2T X)和20ml的水加入烧杯中混合形成悬浊液，在温度25℃的超声波清洗仪中处理4h，然后磁力搅拌10h； (2) Add black NbS 2 powder into a beaker, add 5 ml of N-methylpyrrolidone and 5 ml of sodium hydroxide dispersion solvent and stir well to form a uniformly distributed mixed solution, then weigh 25 mmol of MXene nanosheets (Ti 3 C 2 T X ) and 20ml of water were added to the beaker and mixed to form a suspension, which was treated in an ultrasonic cleaner at a temperature of 25°C for 4h, and then magnetically stirred for 10h;
(3)将烧杯的悬浊液移入反应釜内衬，将反应釜密封在180℃烘箱中水热反应12h；(3) The suspension of the beaker was moved into the inner lining of the reactor, and the reactor was sealed in a 180°C oven for hydrothermal reaction for 12h;
(4)将反应后的反应釜内衬取出，产物用去离子水清洗3次，之后放入离心机在8500r/min条件下离心5min，得到的产物放入真空干燥箱中90℃下12h得到NbS 2/MXene复合材料。 (4) Take out the lining of the reaction kettle after the reaction, wash the product with deionized water for 3 times, then put it into a centrifuge and centrifuge for 5 minutes under the condition of 8500 r/min, and put the obtained product into a vacuum drying box at 90 ° C for 12 h to obtain NbS 2 /MXene composites.
称取80mg的NbS 2/MXene复合材料、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 NbS 2 /MXene composite, 10 mg of super P and 10 mg of polyvinylidene fluoride binder and mix, add a small amount of N-methylpyrrolidone, coat on copper foil after stirring, and dry at 90 °C for 3 hours. Use a microtome to cut the copper foil into a circular shape as the working electrode. After drying, put it into an inert atmosphere glove box with an oxygen and water content below 0.4 ppm. Use a metal potassium sheet as the counter electrode and glass fiber as the diaphragm to assemble into a 2032 type. Button Battery.
图1是实施例1中NbS 2/MXene复合材料的扫描电镜图，从图中可见，样品呈现风琴状多层结构，NbS 2材料均匀分布在MXene材料表面无团聚现象，表明NbS 2成功负载在MXene上且不会破坏MXene形态。 Figure 1 is the scanning electron microscope image of the NbS 2 /MXene composite material in Example 1. It can be seen from the figure that the sample exhibits an organ-like multi-layer structure, and the NbS 2 material is evenly distributed on the surface of the MXene material without agglomeration, indicating that NbS 2 was successfully loaded on the surface of the MXene material. on MXene without destroying the MXene morphology.
图6为MXene的扫描电镜图。通过图1和图6的对比，可以看出NbS 2的成功负载增加了MXene材料的层间距，暴露出更多活性边缘位点。 Figure 6 is a scanning electron microscope image of MXene. By comparing Fig. 1 and Fig. 6, it can be seen that the successful loading of NbS increases the interlayer spacing of the MXene material, exposing more active edge sites.
进一步地，图7为NbS2/MXene复合材料与MXene的XRD图。由图可见，NbS 2/MXene复合材料与MXene两者分别在2θ约7度和9度处有吸收峰，对应(002)晶面，相比较于MXene的吸收峰，NbS 2/MXene复合材料特征峰向低角移动，表明晶格常数发生改变，晶面间距增大，体现NbS 2/MXene复合材料的晶面间距通过NbS 2的引入而增大。 Further, FIG. 7 is the XRD pattern of the NbS2/MXene composite material and MXene. It can be seen from the figure that both NbS 2 /MXene composites and MXene have absorption peaks at 2θ of about 7 degrees and 9 degrees, respectively, corresponding to the (002) crystal plane. Compared with the absorption peaks of MXene, the characteristics of NbS 2 /MXene composites The peak shifts to a low angle, indicating that the lattice constant changes and the interplanar spacing increases, which indicates that the interplanar spacing of NbS 2 /MXene composites increases through the introduction of NbS 2 .
图2是实施例1中NbS 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，从图中可见，NbS 2/MXene复合负极材料组装钾离子电池在100mA/g的电流密度下循环100圈仍有244.8mA h/g的可逆容量，本实施案例材料具有高的可逆容量和良好的循环性能。 Figure 2 shows the cycle performance of the potassium ion battery assembled with the NbS 2 /MXene composite material in Example 1 at a current density of 100 mA/g. At the current density of /g, there is still a reversible capacity of 244.8 mA h/g after 100 cycles. The material in this example has high reversible capacity and good cycle performance.
实施例2Example 2
一种NbS 2/MXene复合材料的制备方法，包括以下步骤： A preparation method of NbS 2 /MXene composite material, comprising the following steps:
(1)称取30mmol的五氧化二铌和60mmol的硫粉装在两个单独的刚玉方舟中，分别放置于氦气保护气氛的管式炉中的气流中游和上游，逐步升温至600℃煅烧5.5h，冷却后收集中游的刚玉方舟中黑色NbS 2粉末，真空储存。 (1) Weigh 30mmol of niobium pentoxide and 60mmol of sulfur powder and put them in two separate corundum arks, place them in the midstream and upstream of the gas flow in the tube furnace of helium protective atmosphere, and gradually heat up to 600 ° C for calcination 5.5h, after cooling, the black NbS 2 powder in the corundum ark in the middle reaches was collected and stored in vacuum.
(2)将黑色NbS 2粉末加入烧杯中，加入7ml的N-甲基吡咯烷酮和7ml的氢氧化钠分散溶剂并充分搅拌形成均匀分布混合液，之后称取30mmol的MXene纳米片(Ti 3C 2T X)和30ml的水加入烧杯中混合形成悬浊液，在温度30℃的超声波清洗仪中处理5h，然后磁力搅 拌11h； (2) Add black NbS 2 powder into a beaker, add 7 ml of N-methylpyrrolidone and 7 ml of sodium hydroxide dispersion solvent and stir well to form a uniformly distributed mixed solution, then weigh 30 mmol of MXene nanosheets (Ti 3 C 2 ) T X ) and 30ml of water were added to the beaker and mixed to form a suspension, which was treated in an ultrasonic cleaner at a temperature of 30°C for 5h, and then magnetically stirred for 11h;
(3)将烧杯的悬浊液移入反应釜内衬，将反应釜密封在200℃烘箱中水热反应15h；(3) Move the suspension of the beaker into the inner lining of the reactor, and seal the reactor in a 200°C oven for hydrothermal reaction for 15h;
(4)将反应后的反应釜内衬取出，产物用去离子水清洗4次，之后放入离心机在9000r/min条件下离心10min，得到的产物放入真空干燥箱中100℃下8h得到NbS 2/MXene复合材料。 (4) Take out the lining of the reaction kettle after the reaction, wash the product with deionized water for 4 times, then put it into a centrifuge and centrifuge for 10 minutes under the condition of 9000 r/min, and put the obtained product into a vacuum drying box at 100 ° C for 8 hours to obtain NbS 2 /MXene composites.
称取80mg的NbS 2/MXene复合材料、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 NbS 2 /MXene composite, 10 mg of super P and 10 mg of polyvinylidene fluoride binder and mix, add a small amount of N-methylpyrrolidone, coat on copper foil after stirring, and dry at 90 °C for 3 hours. Use a microtome to cut the copper foil into a circular shape as the working electrode. After drying, put it into an inert atmosphere glove box with an oxygen and water content below 0.4 ppm. Use a metal potassium sheet as the counter electrode and glass fiber as the diaphragm to assemble into a 2032 type. Button Battery.
本实施例NbS 2/MXene复合材料组装钾离子电池在100mA/g的电流密度下循环100圈仍有267.3mA h/g的可逆容量，本实施案例材料具有高的可逆容量和良好的循环性能。 The potassium ion battery assembled with the NbS 2 /MXene composite material in this example still has a reversible capacity of 267.3 mA h/g after 100 cycles at a current density of 100 mA/g. The material in this example has high reversible capacity and good cycle performance.
实施例3Example 3
一种NbS 2/MXene复合材料的制备方法，包括以下步骤： A preparation method of NbS 2 /MXene composite material, comprising the following steps:
(1)称取40mmol的五氧化二铌和80mmol的硫粉装在两个单独的刚玉方舟中，分别放置于氦气保护气氛的管式炉中的气流中游和上游，逐步升温至650℃煅烧6h，冷却后收集中游的刚玉方舟中黑色NbS 2粉末，真空储存。 (1) Weigh 40mmol of niobium pentoxide and 80mmol of sulfur powder and put them in two separate corundum arks, place them in the midstream and upstream of the gas flow in the tube furnace of helium protective atmosphere, and gradually heat up to 650 ° C for calcination 6h, after cooling, the black NbS 2 powder in the corundum ark in the middle reaches was collected and stored in vacuum.
(2)将黑色NbS 2粉末加入烧杯中，加入9ml的N-甲基吡咯烷酮和9ml的氢氧化钠分散溶剂并充分搅拌形成均匀分布混合液，之后称取40mmol的MXene纳米片(Ti3C2Tx)和40ml的水加入烧杯中混合形成悬浊液，在温度40℃的超声波清洗仪中处理5.5h，然后磁力搅拌11.5h； (2) Add black NbS 2 powder into a beaker, add 9 ml of N-methylpyrrolidone and 9 ml of sodium hydroxide dispersion solvent and stir well to form a uniformly distributed mixed solution, then weigh 40 mmol of MXene nanosheets (Ti3C2Tx) and 40 ml of The water was added to the beaker and mixed to form a suspension, which was treated in an ultrasonic cleaner at a temperature of 40°C for 5.5h, and then magnetically stirred for 11.5h;
(3)将烧杯的悬浊液移入反应釜内衬，将反应釜密封在220℃烘箱中水热反应20h；(3) The suspension of the beaker was moved into the inner lining of the reactor, and the reactor was sealed in a 220°C oven for hydrothermal reaction for 20h;
(4)将反应后的反应釜内衬取出，产物用去离子水清洗3次，之后放入离心机在10000r/min条件下离心15min，得到的产物放入真空干燥箱中90℃下10h得到NbS 2/MXene复合材料。 (4) Take out the lining of the reaction kettle after the reaction, wash the product with deionized water for 3 times, then put it into a centrifuge and centrifuge for 15 minutes under the condition of 10000 r/min, and put the obtained product into a vacuum drying box at 90 ° C for 10 h to obtain NbS 2 /MXene composites.
称取80mg的NbS 2/MXene复合材料、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，50℃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 NbS 2 /MXene composite material, 10 mg of super P and 10 mg of polyvinylidene fluoride binder and mix, add a small amount of N-methylpyrrolidone, coat on copper foil after stirring, and dry at 50 °C for 3 hours. Use a microtome to cut the copper foil into a circular shape as the working electrode. After drying, put it into an inert atmosphere glove box with an oxygen and water content below 0.4 ppm. Use a metal potassium sheet as the counter electrode and glass fiber as the diaphragm to assemble into a 2032 type. Button Battery.
本实施例NbS 2/MXene复合材料组装钾离子电池在100mA/g的电流密度下循环100圈仍有253.3mA h/g的可逆容量，本实施案例材料具有高的可逆容量和良好的循环性能。 The potassium ion battery assembled with NbS 2 /MXene composite material in this example still has a reversible capacity of 253.3 mA h/g after 100 cycles at a current density of 100 mA/g. The material in this example has high reversible capacity and good cycle performance.
实施例4Example 4
一种NbS 2/MXene负极材料的制备方法，包括以下步骤： A preparation method of NbS 2 /MXene negative electrode material, comprising the following steps:
(1)称取15mmol的五氧化二铌和30mmol的硫粉装在两个单独的刚玉方舟中，分别放置于氦气保护气氛的管式炉中的气流中游和上游，逐步升温至700℃煅烧7h，冷却后收集中游的刚玉方舟中黑色NbS 2粉末，真空储存。 (1) Weigh 15mmol of niobium pentoxide and 30mmol of sulfur powder and put them in two separate corundum arks, place them in the midstream and upstream of the gas flow in the tube furnace of helium protective atmosphere, and gradually heat up to 700 ° C for calcination 7h, after cooling, the black NbS 2 powder in the corundum ark in the middle reaches was collected and stored in vacuum.
(2)将黑色NbS 2粉末加入烧杯中，加入10ml的N-甲基吡咯烷酮和10ml的氢氧化钠分散溶剂并充分搅拌形成均匀分布混合液，之后称取10mmol的MXene纳米片(Ti 3C 2T X)和60ml的水加入烧杯中混合形成悬浊液，在温度50℃的超声波清洗仪中处理6h，然后磁力搅拌12h； (2) Add black NbS 2 powder into a beaker, add 10 ml of N-methylpyrrolidone and 10 ml of sodium hydroxide dispersion solvent and stir well to form a uniformly distributed mixed solution, then weigh 10 mmol of MXene nanosheets (Ti 3 C 2 T X ) and 60ml of water were added to the beaker and mixed to form a suspension, which was treated in an ultrasonic cleaner at a temperature of 50°C for 6h, and then magnetically stirred for 12h;
(3)将烧杯的悬浊液移入反应釜内衬，将反应釜密封在250℃烘箱中水热反应18h；(3) The suspension of the beaker was moved into the inner lining of the reactor, and the reactor was sealed in a 250°C oven for hydrothermal reaction for 18h;
(4)将反应后的反应釜内衬取出，产物用去离子水清洗3次，之后放入离心机在12000r/min条件下离心20min，得到的产物放入真空干燥箱中140℃下6h得到NbS 2/MXene复合材料。 (4) Take out the lining of the reactor after the reaction, wash the product with deionized water 3 times, then put it into a centrifuge and centrifuge for 20 minutes under the condition of 12000 r/min, and put the obtained product into a vacuum drying box at 140 ° C for 6 hours to obtain NbS 2 /MXene composites.
称取80mg的NbS 2/MXene复合材料、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 NbS 2 /MXene composite, 10 mg of super P and 10 mg of polyvinylidene fluoride binder and mix, add a small amount of N-methylpyrrolidone, coat on copper foil after stirring, and dry at 90 °C for 3 hours. Use a microtome to cut the copper foil into a circular shape as the working electrode. After drying, put it into an inert atmosphere glove box with an oxygen and water content below 0.4 ppm. Use a metal potassium sheet as the counter electrode and glass fiber as the diaphragm to assemble into a 2032 type. Button Battery.
本实施例NbS2/MXene复合材料组装钾离子电池在100mA/g的电流密度下循环100圈仍有272.9mA h/g的可逆容量，本实施案例材料具有高的可逆容量和良好的循环性能。The potassium ion battery assembled with the NbS2/MXene composite material in this example still has a reversible capacity of 272.9 mA h/g after 100 cycles at a current density of 100 mA/g. The material in this example has high reversible capacity and good cycle performance.
对比例1Comparative Example 1
称取80mg的NbS 2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 80mg of NbS 2 material, 10mg of super P and 10mg of polyvinylidene fluoride binder and mix, add a small amount of N-methylpyrrolidone, coat on copper foil after stirring, dry at 90°C for 3h, use 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.
作为一种有吸引力的电极材料，NbS 2高倍率性能和结构稳定性而被用于电池材料研究，其良好的层状晶体结构允许有多种方法来制备二维纳米结构并将其集成到各种应用中。但是，NbS 2的局限性：纳米片易团聚且结构不稳定，在充放电循环过程中会导致电化学性能的退化，导电性差，基于***机制的有限理论容量和循环不稳定极大地限制了其实际应用。 As an attractive electrode material, NbS2 has been used in battery material research due to its high rate capability and structural stability, and its good layered crystal structure allows multiple approaches to fabricate and integrate 2D nanostructures into in various applications. However, the limitations of NbS : nanosheets are prone to agglomeration and structurally unstable, which can lead to the degradation of electrochemical performance during charge-discharge cycling, poor electrical conductivity, limited theoretical capacity and cycling instability based on the intercalation mechanism, which greatly limit its performance. practical application.
图3为该对比例NbS2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，NbS 2材料组装钾离子电池在100mA/g的电流密度下充放电过程中纳米片易团聚且结构不稳定，比容量在循环20圈后性能衰退。 FIG. 3 is a graph showing the cycle performance of the potassium ion battery assembled with the NbS2 material of the comparative example at a current density of 100 mA/g. It can be seen from the figure that the nanosheets are easily agglomerated and the structure is unstable during the charging and discharging process of the potassium ion battery assembled with NbS 2 material at a current density of 100 mA/g, and the specific capacity performance declines after 20 cycles.
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。Weigh 80mg of MXene material, 10mg of super P and 10mg 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。It can be seen from the figure that the potassium-ion battery assembled with MXene material has good cycle stability during the charge-discharge process at a current density of 100 mA/g, but the specific capacity is small.
NbS 2纳米片作为二维过渡金属硫族化合物，各层之间较弱的范德华相互作用提高了钾离子的有效扩散，相对于单独的NbS 2材料组装钾离子电池，NbS 2/MXene复合材料多层状结构增加了比表面积并防止材料团聚和离子扩散过程的体积明显膨胀，其中较弱的层间相互作用和表面官能团改善了钾离子的转化反应和插层反应，共同促进电极材料的电化学性能提升。相对于单独的MXene材料组装钾离子电池，NbS 2/MXene复合材料的NbS 2纳米片在MXene材料生长时材料暴露出更多活性边缘位点，提高离子迁移效率，促进电极材料的电化学性能提升。 NbS2 nanosheets act as two-dimensional transition metal chalcogenides, and the weak van der Waals interaction between the layers improves the efficient diffusion of potassium ions. Compared with the single NbS2 material to assemble a potassium ion battery, the NbS2 /MXene composite material has more The layered structure increases the specific surface area and prevents significant volume expansion during material agglomeration and ion diffusion, in which weaker interlayer interactions and surface functional groups improve the conversion and intercalation reactions of potassium ions, which together promote the electrochemical performance of electrode materials Performance improvements. Compared with the K-ion battery assembled by the MXene material alone, the NbS 2 nanosheet of the NbS 2 /MXene composite material exposes more active edge sites during the growth of the MXene material, which improves the ion transfer efficiency and promotes the electrochemical performance of the electrode material. .
对比例3Comparative Example 3
一种硫掺杂MXene负极材料的制备方法，包括以下步骤：A preparation method of sulfur-doped MXene negative electrode material, comprising the following steps:
(1)称量25mg的Ti 3C 2T X与45mg的硫脲，分别放置于石英舟的两端，将放有硫脲的一端放置在管式炉的上游； (1) Weigh 25 mg of Ti 3 C 2 T X and 45 mg of thiourea, place them on both ends of the quartz boat, and place the end with thiourea on the upstream of the tube furnace;
(2)在气体流速大小为160ml/min高纯氩气(纯度≥99.8％)保护氛围下，从室温20℃以1.5℃/min升温至170℃，保持2h后，再以0.5℃/min降温至100℃，在100℃下保持2h，再降到室温，冷却后用去离子水对样品进行洗涤，真空干燥得到最终的样品。(2) Under the protective atmosphere of high-purity argon gas (purity ≥99.8%) with a gas flow rate of 160ml/min, the temperature is raised from room temperature 20°C at 1.5°C/min to 170°C, maintained for 2 hours, and then cooled at 0.5°C/min to 100 °C, kept at 100 °C for 2 h, then lowered to room temperature, washed with deionized water after cooling, and vacuum dried to obtain the final sample.
(3)钾离子电池负极制备：称取80mg的硫掺杂MXene电池负极材料、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。(3) Preparation of negative electrode for potassium ion battery: Weigh 80 mg of sulfur-doped MXene battery negative electrode material, 10 mg of super P and 10 mg of polyvinylidene fluoride binder and mix, add a small amount of N-methylpyrrolidone, and coat on copper after stirring. On the foil, dry at 90 °C for 3 hours, cut the copper foil into a circular shape with a microtome as the working electrode, and put it into an inert atmosphere glove box with an oxygen and water content below 0.4 ppm after drying, with a metal potassium sheet as the counter electrode , glass fiber as separator, assembled into 2032 type button battery.
图5为硫掺杂MXene电池负极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 5 shows the cycle performance of potassium-ion batteries assembled with sulfur-doped MXene battery anode materials at a current density of 100 mA/g.
由图可见，硫掺杂MXene电池负极材料组装钾离子电池在100mA/g的电流密度下充放电过程中虽然比容量和循环稳定性有了一定改善，但是比容量仍然明显小于NbS2/MXene复合材料。It can be seen from the figure that although the specific capacity and cycle stability of the potassium-ion battery assembled with the anode material of sulfur-doped MXene battery are improved at a current density of 100 mA/g, the specific capacity is still significantly smaller than that of the NbS2/MXene composite material. .
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NbS 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 NbS 2 /Mxene composite material, characterized in that it comprises the following preparation steps:
    (1)将五氧化二铌和硫源在保护气氛，500-700℃下，煅烧5-7h，冷却后收集黑色NbS 2粉末，真空储存； (1) Niobium pentoxide and sulfur source are calcined at 500-700°C for 5-7h in a protective atmosphere, and after cooling, black NbS 2 powder is collected and stored in vacuum;
    (2)将NbS 2粉末分散在溶剂中，制成混合液； ( 2 ) disperse the NbS powder in a solvent to make a mixed solution;
    (3)取适量MXene纳米片和水加入步骤(2)所述的混合液中，形成悬浊液；(3) adding an appropriate amount of MXene nanosheets and water to the mixture described in step (2) to form a suspension;
    (4)将步骤(3)所述悬浊液在150-250℃下水热反应12-20h，得到粗产物；(4) hydrothermally react the suspension described in step (3) at 150-250 ° C for 12-20 h to obtain a crude product;
    (5)粗产物洗涤，干燥，得到NbS 2/MXene复合材料。 (5) The crude product was washed and dried to obtain the NbS 2 /MXene composite material.
  2. 根据权利要求1所述的NbS 2/MXene复合材料的制备方法，其特征在于，所述硫源为硫代乙酰胺、硫粉、硫脲中的一种或多种。 The preparation method of NbS 2 /MXene composite material according to claim 1, wherein the sulfur source is one or more of thioacetamide, sulfur powder, and thiourea.
  3. 权利要求1所述的NbS 2/MXene复合材料的制备方法，其特征在于，步骤(1)中保护气氛为氮气、氦气、氩气中的一种。 The preparation method of NbS 2 /MXene composite material according to claim 1, wherein the protective atmosphere in step (1) is one of nitrogen, helium and argon.
  4. 根据权利要求1所述的NbS 2/MXene复合材料的制备方法，其特征在于，所述分散溶剂为N-甲基吡咯烷酮、氢氧化钠、N，N-二甲基甲酰胺中的一种或多种。 The preparation method of NbS 2 /MXene composite material according to claim 1, wherein the dispersing solvent is one of N-methylpyrrolidone, sodium hydroxide, N,N-dimethylformamide or variety.
  5. 根据权利要求1所述的NbS 2/MXene复合材料的制备方法，其特征在于，所述MXene为Ti 3C 2T X、Nb 2CT X、V 3C 2T X中的一种或多种。 The preparation method of NbS 2 /MXene composite material according to claim 1, wherein the MXene is one or more of Ti 3 C 2 T X , Nb 2 CT X and V 3 C 2 T X .
  6. 根据权利要求1所述的NbS 2/MXene复合材料的制备方法，其特征在于，步骤(3)为：取适量MXene纳米片和水加入步骤(2)所述的混合液中，进行超声波清洗，搅拌，形成悬浊液。 The preparation method of NbS 2 /MXene composite material according to claim 1, wherein step (3) is: adding an appropriate amount of MXene nanosheets and water into the mixed solution of step (2), and performing ultrasonic cleaning, Stir to form a suspension.
  7. 根据权利要求1所述的NbS 2/MXene复合材料的制备方法，其特征在于，五氧化二铌、硫源和MXene纳米片的摩尔比为1：1.5-2.5：1。 The preparation method of NbS 2 /MXene composite material according to claim 1, wherein the molar ratio of niobium pentoxide, sulfur source and MXene nanosheet is 1:1.5-2.5:1.
  8. 根据权利要求1所述的NbS 2/MXene复合材料的制备方法，其特征在于，步骤(5)中所述离心为7000-12000r/min下离心5-20min；所述干燥为50-140℃真空干燥6-12h。 The preparation method of NbS 2 /MXene composite material according to claim 1, wherein the centrifugation in step (5) is centrifugation at 7000-12000r/min for 5-20min; the drying is vacuum at 50-140°C Dry for 6-12h.
  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得的NbS 2/MXene复合材料。 A potassium ion battery negative electrode, characterized in that it comprises the NbS 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 .
PCT/CN2020/112561 2020-08-10 2020-08-31 Nbs2/mxene composite material and preparation method therefor WO2022032744A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202010794949.9 2020-08-10
CN202010794949.9A CN112018347A (en) 2020-08-10 2020-08-10 NbS2/MXene composite material and preparation method thereof

Publications (1)

Publication Number Publication Date
WO2022032744A1 true WO2022032744A1 (en) 2022-02-17

Family

ID=73499158

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/112561 WO2022032744A1 (en) 2020-08-10 2020-08-31 Nbs2/mxene composite material and preparation method therefor

Country Status (2)

Country Link
CN (1) CN112018347A (en)
WO (1) WO2022032744A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114784455A (en) * 2022-04-06 2022-07-22 山东大学 Diaphragm, preparation method thereof and battery application
CN115050586A (en) * 2022-06-27 2022-09-13 陕西科技大学 MXene nanosheet-aspergillus niger carbonized carbon composite material and preparation method and application thereof
CN115498357A (en) * 2022-07-07 2022-12-20 陕西科技大学 Functional composite diaphragm based on tantalum-based MXene derivative and preparation method and application thereof
CN116334650A (en) * 2023-02-23 2023-06-27 之江实验室 MoS 2 MXene/NF composite material, preparation and application thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112928342B (en) * 2021-02-08 2022-06-03 安徽大学 Multifunctional zinc ion micro battery and preparation method and application thereof
CN114220961B (en) * 2022-02-21 2022-07-19 浙江大学 Composite nano material for sodium ion battery and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105826556A (en) * 2016-03-27 2016-08-03 华南理工大学 Ultrathin-layered NbS2, preparing method thereof and application of ultrathin-layered NbS2 to lithium/sodium-ion battery
US20170067167A1 (en) * 2014-03-06 2017-03-09 True 2 Materials Pte Ltd Method for manufacture of films and foams
CN108516528A (en) * 2018-04-12 2018-09-11 大连理工大学 A kind of three dimensional composite structure and its universal synthesis method based on three-dimensional MXene
CN109817921A (en) * 2019-01-22 2019-05-28 五邑大学 A kind of sulfur doping MXene negative electrode material and its preparation method and application
CN109817918A (en) * 2019-01-22 2019-05-28 五邑大学 Sulfur doping MXene composite material and preparation method and application

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103311546B (en) * 2013-05-24 2015-10-14 深圳华粤宝电池有限公司 The preparation method of lithium ion cell electrode sheet
CN108963211A (en) * 2018-06-28 2018-12-07 上海电力学院 A kind of titanium carbide load stannous sulfide composite negative pole material
CN109183156A (en) * 2018-11-08 2019-01-11 西北工业大学 A kind of disulphide monocrystalline and its preparation method and application
CN111229256B (en) * 2018-11-28 2023-05-26 中国科学院大连化学物理研究所 Supported single-layer and few-layer two-dimensional transition metal sulfide catalyst and preparation method thereof
CN111111722B (en) * 2020-01-21 2022-04-08 南京航空航天大学 Metal sulfide/MXene composite catalyst for water electrolysis and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170067167A1 (en) * 2014-03-06 2017-03-09 True 2 Materials Pte Ltd Method for manufacture of films and foams
CN105826556A (en) * 2016-03-27 2016-08-03 华南理工大学 Ultrathin-layered NbS2, preparing method thereof and application of ultrathin-layered NbS2 to lithium/sodium-ion battery
CN108516528A (en) * 2018-04-12 2018-09-11 大连理工大学 A kind of three dimensional composite structure and its universal synthesis method based on three-dimensional MXene
CN109817921A (en) * 2019-01-22 2019-05-28 五邑大学 A kind of sulfur doping MXene negative electrode material and its preparation method and application
CN109817918A (en) * 2019-01-22 2019-05-28 五邑大学 Sulfur doping MXene composite material and preparation method and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHU JIAJIE, ALSHAREEF HUSAM N., SCHWINGENSCHLÖGL UDO: "Functionalized NbS 2 as cathode for Li- and Na-ion batteries", APPLIED PHYSICS LETTERS, vol. 111, no. 4, 24 July 2017 (2017-07-24), 2 Huntington Quadrangle, Melville, NY 11747, pages 043903, XP055901277, ISSN: 0003-6951, DOI: 10.1063/1.4985694 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114784455A (en) * 2022-04-06 2022-07-22 山东大学 Diaphragm, preparation method thereof and battery application
CN115050586A (en) * 2022-06-27 2022-09-13 陕西科技大学 MXene nanosheet-aspergillus niger carbonized carbon composite material and preparation method and application thereof
CN115050586B (en) * 2022-06-27 2024-04-12 陕西科技大学 MXene nanosheet-aspergillus niger carbonized carbon composite material and preparation method and application thereof
CN115498357A (en) * 2022-07-07 2022-12-20 陕西科技大学 Functional composite diaphragm based on tantalum-based MXene derivative and preparation method and application thereof
CN116334650A (en) * 2023-02-23 2023-06-27 之江实验室 MoS 2 MXene/NF composite material, preparation and application thereof

Also Published As

Publication number Publication date
CN112018347A (en) 2020-12-01

Similar Documents

Publication Publication Date Title
WO2022032744A1 (en) Nbs2/mxene composite material and preparation method therefor
CN113675408B (en) MoS for high-performance potassium ion battery 2 /Ti 3 C 2 Preparation method of MXene composite material
WO2022032743A1 (en) Cote2/mxene composite material and preparation method therefor
Chu et al. NiO nanocrystals encapsulated into a nitrogen-doped porous carbon matrix as highly stable Li-ion battery anodes
CN109473650B (en) MoO (MoO)2/rGO composite material and preparation method and application thereof
CN112490446B (en) Preparation method of Co-CNT @ CF three-dimensional self-supporting lithium-sulfur battery positive electrode material
WO2022032745A1 (en) Vo2/mxene composite material, preparation method therefor and use thereof
CN105883940B (en) Preparation method of block NiS2 and application of block NiS2 to sodium-ion battery
CN110311092B (en) SnO (stannic oxide)2carbon/V2O5Application of/graphene composite nano material as battery negative electrode material
CN113410443B (en) Preparation method and application of high-stability copper intercalation manganese dioxide electrode material
CN110042503B (en) MoSe2@ C electrospun hollow nanofiber and preparation method and application thereof
CN110581264B (en) High-performance nickel-zinc battery negative electrode active material and preparation method thereof
CN109473643B (en) CoSe2Preparation method and application of graphene composite material
CN110838583B (en) Carbon nanotube/M-phase vanadium dioxide composite structure, preparation method thereof and application thereof in water-based zinc ion battery
WO2022032747A1 (en) Method for preparing sulfur-doped rese2/mxene composite material
CN112010291B (en) Preparation method and application of nickel-doped molybdenum disulfide/graphene three-dimensional composite material
WO2021196430A1 (en) Lithium-ion battery negative electrode material and preparation method therefor
CN112968173A (en) Porous carbon-coated sulfur vacancy composite electrode material, preparation method thereof and circular electrode adopting material
CN112357956A (en) Carbon/titanium dioxide coated tin oxide nanoparticle/carbon assembled mesoporous sphere material and preparation and application thereof
CN113517427A (en) Preparation method and application of carbon-coated antimony/antimony trisulfide composite material
CN112635726A (en) Bentonite-based composite material and preparation method and application thereof
CN110212176A (en) A kind of graphene/molybdenum disulfide nano ball/carbon black composite material preparation method
CN112038599B (en) Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery
CN113054170B (en) Preparation method of nickel-nickel molybdenum oxide-graphene composite material and application of nickel-nickel molybdenum oxide-graphene composite material in lithium ion battery
CN111725003B (en) Cubic iron-based oxyhydroxide/graphene composite material for supercapacitor and preparation method thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20949241

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20949241

Country of ref document: EP

Kind code of ref document: A1