WO2022032747A1 - Method for preparing sulfur-doped rese2/mxene composite material - Google Patents

Method for preparing sulfur-doped rese2/mxene composite material Download PDF

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WO2022032747A1
WO2022032747A1 PCT/CN2020/112568 CN2020112568W WO2022032747A1 WO 2022032747 A1 WO2022032747 A1 WO 2022032747A1 CN 2020112568 W CN2020112568 W CN 2020112568W WO 2022032747 A1 WO2022032747 A1 WO 2022032747A1
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rese
sulfur
mxene
doped
composite material
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PCT/CN2020/112568
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French (fr)
Chinese (zh)
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张业龙
周健文
徐晓丹
孙宏阳
李振瀚
宋伟东
郭月
温锦秀
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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 preparation method of a sulfur-doped ReSe 2 /MXene composite material.
  • Lithium-ion batteries have been rapidly developed in the fields of portable electronic communication equipment and electric vehicles.
  • the current reserves of lithium resources in the earth are relatively small, and with the increase of battery demand, the lithium resources are decreasing day by day, which limits the battery technology to a great extent. sustainable development. Therefore, it is necessary to develop a new type of battery to reduce the use of lithium ions.
  • Potassium and lithium are both the first main group elements, they have similar reserves and potentials, and potassium ions have a high potential platform, energy density and abundant storage capacity, so they have great development potential.
  • potassium-ion batteries still face enormous challenges.
  • MXene is a compound composed of transition metal carbides and nitrides or carbonitrides with an accordion-like morphology and abundant functional groups on the surface of the material.
  • Using it as a battery material has the following advantages: 1 its special structure shows an ultra-high specific surface area, which increases more active sites and ion contact area; 2 its better electrical conductivity makes the ion movement resistance small, so Reduce reaction kinetics; 3 Its surface functional groups can increase the hydrophilicity of materials, etc.
  • the electrochemical performance of MXene still has some defects, such as: small interlayer spacing, insufficient active sites, and poor conductivity.
  • ReSe 2 is a typical two-dimensional transition metal dichalcogenide (TMDCs), which exhibits a sandwich structure with weak interaction forces (van der Waals forces) between each layer, which can allow the insertion of ions without causing significant damage .
  • TMDCs transition metal dichalcogenide
  • one of the objectives of the present invention is to provide a sulfur-doped ReSe 2 /MXene composite material.
  • Another object of the present invention is to provide a method for preparing the above-mentioned sulfur-doped ReSe 2 /MXene composite material.
  • the present invention provides an application of a sulfur-doped ReSe 2 /MXene composite material, and the sulfur-doped ReSe 2 /MXene composite material is used for a potassium ion battery negative electrode.
  • the present invention adopts following technical scheme:
  • a preparation method of a sulfur-doped ReSe 2 /MXene composite material belongs to a solvothermal method, and specifically includes the following steps:
  • step (3) Grind the crude product obtained in step (3) to make it evenly distributed, put it into a corundum ark, heat it to 200-300°C in a tube furnace with protective gas, calcined for 2-4h, and naturally After cooling to room temperature, the calcined products were collected to obtain sulfur-doped ReSe 2 /MXene composites.
  • the solvent is at least one of N,N-dimethylformamide, cyclohexane, and xylene, preferably N,N-dimethylformamide;
  • the cleaning agent is water or ethanol At least one of them, preferably washed with deionized water and absolute ethanol alternately for 2-10 times.
  • the molar ratio of the MXene nanosheets, the ReSe 2 nanoparticles and the sulfur source is 1:1:0.01-0.9.
  • the MXene is one or more of Ti 3 C 2 T x , Ti 2 CT x , Nb 2 CT x , Ta 4 C 3 T x , Ti 3 CNT X ; for example, Ti 2 CT x , and then Such as Nb 2 CT x ; preferably, the mass ratio of Ti 3 C 2 T x and Ti 3 CNT X is 1:5-10, wherein T x is a surface functional group -O, -OH or -F.
  • the calcination can increase the crystallinity, and on the other hand, the sulfur atoms can be doped more fully, and the sulfur atoms partially replace the selenium atoms.
  • the sulfur source is one or more of sulfur powder, thiourea, and thioacetamide.
  • the particle size of the sulfur source is 50-150 mesh, such as 120 mesh;
  • the particle size of the ReSe2 nanoparticles is 10-100 nm, preferably 20-50 nm, such as 10 nm, 20 nm, 50 nm, 100 nm;
  • the size of the MXene nanosheet is 1-5 ⁇ m, for example, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m.
  • the sulfur doping amount in the sulfur-doped ReSe 2 /MXene composite material is 1-20 wt %, for example, 1-10 wt %, 3-12 wt %, 6-15 wt %.
  • step (3) the mixed solution is transferred into the reaction kettle and heated to 150-250°C in a microwave heating box, preferably 120-180°C, such as 140°C, 160°C, 180°C; the reaction time is 10- 18h, eg 12h, 15h, 18h.
  • the rotational speed of centrifugation described in step (3) is 6000-8000r/min, preferably 7500r/min; the centrifugation time is 5-10min, preferably 6-8min, such as 5min, 6min, 7min, 8min, 9min, 10min; the temperature of vacuum drying is 50-70°C, preferably 60°C, and the drying time is 8-12h, such as 10h, 11h, 12h.
  • the protective gas is one of argon, helium and nitrogen, preferably argon.
  • a sulfur-doped ReSe 2 /MXene composite material obtained by the above-mentioned preparation method of a sulfur-doped ReSe 2 /MXene composite material.
  • a potassium ion battery negative electrode includes the sulfur-doped ReSe 2 /MXene composite material.
  • the preparation method of the sulfur-doped ReSe 2 /MXene composite material of the present invention takes MXene as the main substrate, supports ReSe 2 on MXene, doped sulfur into the ReSe 2 /MXene composite, and reacts by heat treatment
  • the prepared sulfur-doped ReSe 2 /MXene composite material, MXene, ReSe 2 between the sulfur atoms to make up for their respective defects and deficiencies, has a synergistic effect, and maximizes the potassium storage performance of the composite material, specific capacity, Charge and discharge stability, electron transfer rate and other properties;
  • the special layered structure of MXene in the sulfur-doped ReSe2/MXene composite material of the present invention can effectively alleviate the problems such as electrical performance decline and structural collapse caused by the agglomeration or volume expansion of the negative electrode material during the cyclic charge-discharge process;
  • the loading of ReSe 2 effectively increases the interlayer spacing and increases the specific surface area; further, the doping of sulfur element exposes more active sites and vacancies in the ReSe 2 /MXene composite, improving the potassium storage performance of the material.
  • Fig. 1 is the scanning electron microscope image of the MXene material alone in Comparative Example 1;
  • Example 2 is a scanning electron microscope image of the sulfur-doped ReSe 2 /MXene composite material in Example 1;
  • Example 3 is a graph showing the cycle performance of the potassium-ion battery assembled with sulfur-doped ReSe 2 /MXene composite material in Example 1 at a current density of 100 mA/g.
  • Figure 4 is a graph of the cycle performance measured at a current density of 100 mA/g for a potassium-ion battery assembled with a single MXene negative electrode material in Comparative Example 1;
  • FIG. 6 is a graph showing the cycle performance of the potassium-ion battery assembled with ReSe 2 /MXene material in Comparative Example 3 at a current density of 100 mA/g.
  • the ReSe 2 nanoparticles were purchased from Shenzhen Six Carbon Technology Co., Ltd., model: ReSe 2 type crystal size 20-50 nm, purity: high-purity 99.999%, lattice type: semiconductor material, anisotropic material.
  • 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 sulfur-doped ReSe 2 /MXene composite material comprising the following steps:
  • step (3) Grind the crude product obtained in step (3) to a uniform distribution, put it into a corundum ark, heat it to 250° C. in a tube furnace fed with argon, calcine for 3 hours, naturally cool to room temperature, and collect the product, A sulfur-doped ReSe 2 /MXene composite was obtained.
  • the sulfur-doped ReSe 2 /MXene composite material, the conductive agent super P carbon and the polyvinylidene fluoride binder were mixed uniformly in a mass ratio of 8:1:1, and an appropriate amount of N-methylpyrrolidone was added, and stirred to form a uniform
  • the slurry was coated on the copper foil, dried and cut as the working electrode of the potassium ion battery, 1M KFSI EC (ethylene carbonate), PC (propylene carbonate) (1:1) was used as the electrolyte, and potassium metal sheet was used as the countermeasure. Electrodes and glass fibers were used as separators and assembled into 2032 type coin half cells; all assembly was performed in an inert atmosphere glove box.
  • the potassium ion battery assembled with the sulfur-doped ReSe 2 /MXene composite negative electrode material in this example has a reversible capacity of 326.6 mA h/g after 100 cycles at a current density of 100 mA/g, which is the best solution for the potassium ion battery assembled with the undoped MXene negative electrode material.
  • the reversible capacity of the ion battery is 5.3 times (61.1 mA h/g), 3.18 times that of the pure ReSe 2 anode material (102.4 mA h/g), and 1.14 times that of the ReSe 2 /MXene anode material (286.2 mA h/g),
  • the sulfur-doped ReSe 2 /MXene composite anode material in this example has good potassium storage performance and charge-discharge cycle performance.
  • a preparation method of sulfur-doped ReSe 2 /MXene composite material comprising the following steps:
  • step (3) Grind the crude product obtained in step (3) to a uniform distribution, put it into a corundum ark, heat it to 280° C. for 3 hours in a tube furnace fed with argon, cool it naturally to room temperature, and collect the product to obtain Sulfur-doped ReSe 2 /MXene composites.
  • the sulfur-doped ReSe 2 /MXene composite material, the conductive agent super P carbon and the polyvinylidene fluoride binder were mixed uniformly in a mass ratio of 8:1:1, and an appropriate amount of N-methylpyrrolidone was added, and stirred to form a uniform
  • the slurry was coated on the copper foil, dried and cut as the working electrode of the potassium ion battery, 1M KFSI EC (ethylene carbonate), PC (propylene carbonate) (1:1) was used as the electrolyte, and potassium metal sheet was used as the countermeasure. Electrodes and glass fibers were used as separators and assembled into 2032 type coin half cells; all assembly was performed in an inert atmosphere glove box.
  • the potassium ion battery assembled with the sulfur-doped ReSe 2 /MXene composite negative electrode material in this example has a reversible capacity of 335.2 mA h/g after 100 cycles at a current density of 100 mA/g, which is the best solution for the potassium ion battery assembled with the undoped MXene negative electrode material.
  • the reversible capacity of the ion battery is 5.4 times (61.1 mA h/g), 3.27 times that of the pure ReSe 2 anode material (102.4 mA h/g), and 1.17 times that of the ReSe 2 /MXene anode material (286.2 mA h/g),
  • the sulfur-doped ReSe 2 /MXene composite anode material in this example has good potassium storage performance and charge-discharge cycle performance.
  • a preparation method of sulfur-doped ReSe 2 /MXene composite material comprising the following steps:
  • step (3) Grind the crude product obtained in step (3) to a uniform distribution, put it into a corundum ark, heat it to 280° C. in a tubular furnace fed with argon, calcine for 3 hours, naturally cool to room temperature, and collect the product, A sulfur-doped ReSe 2 /MXene composite was obtained.
  • the sulfur-doped ReSe 2 /MXene composite material, the conductive agent super P carbon and the polyvinylidene fluoride binder were mixed uniformly in a mass ratio of 8:1:1, and an appropriate amount of N-methylpyrrolidone was added, and stirred to form a uniform
  • the slurry was coated on the copper foil, dried and cut as the working electrode of the potassium ion battery, with 1M KFSI EC (ethylene carbonate), PC (propylene carbonate) (1:1) as the electrolyte and metal potassium sheet as the countermeasure. Electrodes and glass fibers were used as separators and assembled into 2032 type coin half cells; all assembly was performed in an inert atmosphere glove box.
  • the potassium ion battery assembled with the sulfur-doped ReSe 2 /MXene composite negative electrode material in this example has a reversible capacity of 313.4 mA h/g after 100 cycles at a current density of 100 mA/g, which is the negative electrode of an undoped MXene potassium ion battery.
  • the reversible capacity (61.1mA h/g) is 5.1 times, which is 3.06 times that of pure ReSe 2 anode material (102.4 mA h/g), and 1.09 times that of ReSe 2 /MXene anode material (286.2 mA h/g).
  • the sulfur-doped ReSe 2 /MXene composite anode material of the embodiment has very stable charge-discharge cycle performance.
  • a preparation method of sulfur-doped ReSe 2 /MXene composite material comprising the following steps:
  • step (3) Grind the crude product obtained in step (3) to a uniform distribution, put it into a corundum ark, heat it to 300° C. in a tube furnace fed with argon, calcine for 3 hours, naturally cool to room temperature, and collect the product , the sulfur-doped ReSe 2 /MXene composites were obtained.
  • the sulfur-doped ReSe 2 /MXene composite material, the conductive agent super P carbon and the polyvinylidene fluoride binder were mixed uniformly in a mass ratio of 8:1:1, and an appropriate amount of N-methylpyrrolidone was added, and stirred to form a uniform
  • the slurry was coated on the copper foil, dried and cut as the working electrode of the potassium ion battery, 1M KFSI EC (ethylene carbonate), PC (propylene carbonate) (1:1) was used as the electrolyte, and potassium metal sheet was used as the countermeasure. Electrodes and glass fibers were used as separators and assembled into 2032 type coin half cells; all assembly was performed in an inert atmosphere glove box.
  • the potassium ion battery assembled with the sulfur-doped ReSe 2 /MXene composite negative electrode material in this example has a reversible capacity of 344.1 mA h/g after 100 cycles at a current density of 100 mA/g, which is the negative electrode of an undoped MXene potassium ion battery.
  • the reversible capacity (61.1mA h/g) is 5.6 times, which is 3.36 times that of pure ReSe 2 anode material (102.4 mA h/g), and 1.2 times that of ReSe 2 /MXene anode material (286.2 mA h/g).
  • the sulfur-doped ReSe 2 /MXene composite anode material of the embodiment has very stable charge-discharge cycle performance.
  • step (3) Grind the crude product obtained in step (3) to a uniform distribution, put it into a corundum ark, heat it to 280° C. for 3 hours in a tube furnace fed with argon, cool it naturally to room temperature, and collect the product to obtain ReSe 2 /MXene composites.
  • FIG. 1 is a scanning electron microscope image of the single MXene material in Comparative Example 1
  • FIG. 2 is a scanning electron microscope image of the sulfur-doped ReSe 2 /MXene composite material in Example 1.
  • the MXene material used in the present invention presents a multi-layered structure with no impurities on the surface, but the interlayer spacing is small.
  • the MXene composite material after doping still retains the original accordion-like layered structure, while the layered The spacing increases significantly, and there is no agglomeration on the surface of the MXene material, indicating that the sulfur-doped ReSe 2 /MXene composite material is successfully prepared in this example.
  • Figures 3-6 are respectively the sulfur-doped ReSe 2 /MXene composite material in Example 1, the pure MXene negative electrode material in Comparative Example 1, the single ReSe 2 negative electrode material in Comparative Example 2, and the ReSe 2 /MXene material in Comparative Example 3.
  • the pure MXene anode material in Comparative Example 1 has a very low reversible capacity of only 61.1 mA h/g;
  • Figure 5 the single ReSe 2 anode material in Comparative Example 2, the specific capacity declines after 10 cycles , this is because the single ReSe 2 anode material is easy to agglomerate, has an unstable structure, and has poor charge and discharge performance;
  • the ReSe 2 /MXene material in Comparative Example 3 has good potassium storage performance during the charge and discharge process, and has a relatively With high specific capacity and stable charge-discharge performance, the battery performance is still not ideal, and its electrochemical performance needs to be further improved.
  • the patent of the present invention uses MXene as the main substrate, the synthesized ReSe 2 is supported on MXene, and sulfur is doped into the ReSe 2 /MXene composite, and the sulfur-doped ReSe 2 /MXene is prepared by heat treatment reaction. composite material.
  • the obtained sulfur-doped ReSe2/MXene composite has good conductivity, increased interlayer spacing, and large specific surface area.
  • the special layered structure of MXene can effectively slow down the agglomeration or volume expansion of the negative electrode material during the cyclic charge-discharge process.
  • the electrical performance decline and structural collapse of the ReSe 2 can effectively increase the interlayer spacing and increase the specific surface area; further, the doping of sulfur element exposes more active sites and vacancies in the ReSe 2 /MXene composite, and then Improve the potassium storage properties of the material. Therefore, MXene, ReSe 2 , and sulfur atoms can compensate for their respective defects and deficiencies, and have a synergistic effect, which maximizes the potassium storage performance, specific capacity, charge-discharge stability, electron transfer rate and other properties of the composite. . Meanwhile, the preparation process is simple and the performance is controllable.

Abstract

A method for preparing a sulfur-doped ReSe2/MXene composite material, comprising: using MXene as a main substrate; loading synthesized ReSe2 on MXene; doping a ReSe2/MXene complex with a sulfur element; and preparing a sulfur-doped ReSe2/MXene composite material by means of a heat treatment reaction. The sulfur-doped ReSe2/MXene composite material has good conductivity, an increased interlayer spacing, and a large specific surface area. The specific layered structure of MXene effectively mitigates the problems such as electrical performance degradation and structural collapse caused by the agglomeration or volume expansion of negative electrode materials during the cycle of charging and discharging.; the load of ReSe2 effectively increases the interlayer spacing and increases the specific surface area; furthermore, due to doping of the sulfur element, more active sites and vacancies of the ReSe2/MXene composite material are exposed, thereby improving the potassium storage performance of the material. MXene, ReSe2, and sulfur atoms can overcome respective defects and deficiencies, and have a synergistic effect, thereby improving, to the greatest extent, the potassium storage performance of the composite material, and properties such as the specific capacity, charging and discharging stability, and the electron transfer rate. Moreover, the preparation process is simple, and the performance is controllable.

Description

一种硫掺杂ReSe 2/MXene复合材料的制备方法 A sulfur-doped ReSe Preparation method of 2/MXene composites 技术领域technical field
本发明属于新能源技术领域，具体涉及一种硫掺杂ReSe 2/MXene复合材料的制备方法。 The invention belongs to the technical field of new energy, and in particular relates to a preparation method of a sulfur-doped ReSe 2 /MXene composite material.
背景技术Background technique
锂离子电池已经在便携电子通讯设备和电动汽车等领域得到了高速发展，然而目前锂资源在地球储量较少，且随着电池需求的增加使锂资源日益减少，很大程度地限制了电池技术的持续发展。因此需要开发一种新型电池，以减少锂离子的使用。钾与锂同为第一主族元素，他们具有相似的储量和电位，而且钾离子具有较高的电位平台、能量密度和丰富的存储量，因而具有巨大的发展潜力。但在实际应用中，钾离子电池仍面临着巨大的挑战。Lithium-ion batteries have been rapidly developed in the fields of portable electronic communication equipment and electric vehicles. However, the current reserves of lithium resources in the earth are relatively small, and with the increase of battery demand, the lithium resources are decreasing day by day, which limits the battery technology to a great extent. sustainable development. Therefore, it is necessary to develop a new type of battery to reduce the use of lithium ions. Potassium and lithium are both the first main group elements, they have similar reserves and potentials, and potassium ions have a high potential platform, energy density and abundant storage capacity, so they have great development potential. However, in practical applications, potassium-ion batteries still face enormous challenges.
MXene是一种由过渡金属碳化物和氮化物或碳氮化物构成的化合物，其形态类似手风琴且材料表面有丰富官能团。将其作为电池材料，具有以下优势：①其特殊的结构表现出超高的比表面积，增加了更多的活性位点和离子接触面积；②其较好的导电性能使离子移动阻力小，从而降低反应动力学；③其表面官能团可以增加材料亲水性等。但MXene的电化学性能仍存在一些缺陷，比如：层间距较小、活性位点不足、导电性差等。MXene is a compound composed of transition metal carbides and nitrides or carbonitrides with an accordion-like morphology and abundant functional groups on the surface of the material. Using it as a battery material has the following advantages: ① its special structure shows an ultra-high specific surface area, which increases more active sites and ion contact area; ② its better electrical conductivity makes the ion movement resistance small, so Reduce reaction kinetics; ③ Its surface functional groups can increase the hydrophilicity of materials, etc. However, the electrochemical performance of MXene still has some defects, such as: small interlayer spacing, insufficient active sites, and poor conductivity.
ReSe 2是典型的二维过渡金属硫族化合物(TMDCs)，其呈现一种三明治结构，其中每层之间具有微弱的相互作用力(范德华力)，可以允许离子的***而不造成明显的破坏。作为负电极材料，具有优异的电化学性能，但导电性差和容易团聚等缺陷严重限制了其发展。 ReSe 2 is a typical two-dimensional transition metal dichalcogenide (TMDCs), which exhibits a sandwich structure with weak interaction forces (van der Waals forces) between each layer, which can allow the insertion of ions without causing significant damage . As a negative electrode material, it has excellent electrochemical performance, but its development is seriously limited by its poor conductivity and easy agglomeration.
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硫掺杂ReSe 2/MXene复合材料。本发明的另一目的在于提供上述硫掺杂ReSe 2/MXene复合材料的制备方法。进一步的，本发明提供一种硫掺杂ReSe 2/MXene复合材料的应用，将所述硫掺杂ReSe 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 sulfur-doped ReSe 2 /MXene composite material. Another object of the present invention is to provide a method for preparing the above-mentioned sulfur-doped ReSe 2 /MXene composite material. Further, the present invention provides an application of a sulfur-doped ReSe 2 /MXene composite material, and the sulfur-doped ReSe 2 /MXene composite material is used for a potassium ion battery negative electrode.
本发明采用以下技术方案：The present invention adopts following technical scheme:
一种硫掺杂ReSe 2/MXene复合材料的制备方法，所述制备方法属于溶剂热法，具体包括以下步骤： A preparation method of a sulfur-doped ReSe 2 /MXene composite material, the preparation method belongs to a solvothermal method, and specifically includes the following steps:
(1)将ReSe 2纳米颗粒、适量溶剂和水充分混匀，得到分散液； (1) fully mixing ReSe 2 nanoparticles, an appropriate amount of solvent and water to obtain a dispersion;
(2)将MXene纳米片、分散液、硫源和水混合，并在20℃-50℃下超声处理0.5-1h，配制成浓度为1-100mg/ml的混合液，然后搅拌1-5h；(2) Mix MXene nanosheets, dispersion liquid, sulfur source and water, and ultrasonically treat at 20°C-50°C for 0.5-1h to prepare a mixed solution with a concentration of 1-100mg/ml, and then stir for 1-5h;
(3)将搅拌后的混合液移入反应釜在微波加热箱中，加热至150-250℃下反应10-24h，并自然冷却至室温，离心，用清洗剂反复洗涤，然后在真空干燥箱中烘干，得到粗产物；(3) Transfer the stirred mixture into the reaction kettle in a microwave heating box, heat it to 150-250 ° C for 10-24 hours, and naturally cool to room temperature, centrifuge, repeatedly wash with a cleaning agent, and then put it in a vacuum drying box Dry to obtain crude product;
(4)将步骤(3)得到的粗产物进行研磨，使其分布均匀，并放入刚玉方舟中，在通入保护气体的管式炉中加热至200-300℃，煅烧2-4h，自然冷却至室温后收集煅烧产物，得到硫掺杂ReSe 2/MXene复合材料。 (4) Grind the crude product obtained in step (3) to make it evenly distributed, put it into a corundum ark, heat it to 200-300°C in a tube furnace with protective gas, calcined for 2-4h, and naturally After cooling to room temperature, the calcined products were collected to obtain sulfur-doped ReSe 2 /MXene composites.
进一步地，所述溶剂为N,N-二甲基甲酰胺、环己烷、二甲苯中的至少一种，优选用N,N-二甲基甲酰胺；所述清洗剂为水、乙醇中的至少一种，优选用去离子水和无水乙醇交替清洗2-10次。Further, the solvent is at least one of N,N-dimethylformamide, cyclohexane, and xylene, preferably N,N-dimethylformamide; the cleaning agent is water or ethanol At least one of them, preferably washed with deionized water and absolute ethanol alternately for 2-10 times.
进一步地，所述MXene纳米片、ReSe 2纳米颗粒和硫源的摩尔比为1：1：0.01-0.9。 Further, the molar ratio of the MXene nanosheets, the ReSe 2 nanoparticles and the sulfur source is 1:1:0.01-0.9.
进一步地，所述MXene为Ti 3C 2T x、Ti 2CT x、Nb 2CT x、Ta 4C 3T x、Ti 3CNT X中的一种或多种；例如Ti 2CT x，再如Nb 2CT x；优选地，Ti 3C 2T x和Ti 3CNT X的质量比为1：5-10，其中T x为表面官能团-O、-OH或-F。 Further, the MXene is one or more of Ti 3 C 2 T x , Ti 2 CT x , Nb 2 CT x , Ta 4 C 3 T x , Ti 3 CNT X ; for example, Ti 2 CT x , and then Such as Nb 2 CT x ; preferably, the mass ratio of Ti 3 C 2 T x and Ti 3 CNT X is 1:5-10, wherein T x is a surface functional group -O, -OH or -F.
进一步地，所述煅烧一方面可以增加结晶度，一方面可以使硫原子掺杂更充分，硫原子部分取代硒原子。Further, on the one hand, the calcination can increase the crystallinity, and on the other hand, the sulfur atoms can be doped more fully, and the sulfur atoms partially replace the selenium atoms.
进一步地，所述硫源为硫粉、硫脲、硫代乙酰胺中的一种或多种。Further, the sulfur source is one or more of sulfur powder, thiourea, and thioacetamide.
进一步地，所述硫源的粒径为50-150目，例如120目；所述ReSe2纳米颗粒的粒径为10nm-100nm，优选的为20-50nm，例如10nm，20nm，50nm，100nm；所述MXene纳米片的尺寸为1-5μm，例如1μm，2μm，3μm，4μm，5μm。Further, the particle size of the sulfur source is 50-150 mesh, such as 120 mesh; the particle size of the ReSe2 nanoparticles is 10-100 nm, preferably 20-50 nm, such as 10 nm, 20 nm, 50 nm, 100 nm; The size of the MXene nanosheet is 1-5 μm, for example, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm.
进一步地，所述硫掺杂ReSe 2/MXene复合材料中硫掺杂量为1-20wt％，例如1-10wt％，3-12wt％，6-15wt％。 Further, the sulfur doping amount in the sulfur-doped ReSe 2 /MXene composite material is 1-20 wt %, for example, 1-10 wt %, 3-12 wt %, 6-15 wt %.
进一步地，步骤(3)中所述混合液移入反应釜在微波加热箱中加热至150-250℃，优选的为120-180℃，例如140℃、160℃、180℃；反应时间为10-18h，例如12h、15h、18h。Further, in step (3), the mixed solution is transferred into the reaction kettle and heated to 150-250°C in a microwave heating box, preferably 120-180°C, such as 140°C, 160°C, 180°C; the reaction time is 10- 18h, eg 12h, 15h, 18h.
进一步地，步骤(3)中所述离心的转速为6000-8000r/min，优选的为7500r/min；离心时间为5-10min，优选的为6-8min，例如5min、6min、7min、8min、9min、10min；真空干燥的温度为50-70℃，优选60℃，干燥时间为8-12h，例如10h、11h、12h。Further, the rotational speed of centrifugation described in step (3) is 6000-8000r/min, preferably 7500r/min; the centrifugation time is 5-10min, preferably 6-8min, such as 5min, 6min, 7min, 8min, 9min, 10min; the temperature of vacuum drying is 50-70°C, preferably 60°C, and the drying time is 8-12h, such as 10h, 11h, 12h.
进一步地，步骤(4)中保护气体为氩气、氦气、氮气中的一种，优选的为氩气。Further, in step (4), the protective gas is one of argon, helium and nitrogen, preferably argon.
一种上述硫掺杂ReSe 2/MXene复合材料的制备方法制得的硫掺杂ReSe 2/MXene复合材料。 A sulfur-doped ReSe 2 /MXene composite material obtained by the above-mentioned preparation method of a sulfur-doped ReSe 2 /MXene composite material.
一种钾离子电池负极，其包括所述硫掺杂ReSe 2/MXene复合材料。 A potassium ion battery negative electrode includes the sulfur-doped ReSe 2 /MXene composite material.
本发明的有益效果：Beneficial effects of the present invention:
(1)本发明的硫掺杂ReSe 2/MXene复合材料的制备方法，以MXene为主要基底，将ReSe 2负载在MXene上，将硫元素掺杂到ReSe 2/MXene复合物中，经热处理反应制得硫掺杂ReSe 2/MXene复合材料，MXene，ReSe 2，硫原子之间以弥补各自的缺陷和不足，具有协同增效作用，最大程度地提高了复合材料的储钾性能，比容量、充放电稳定性、电子转移速率等性能； (1) The preparation method of the sulfur-doped ReSe 2 /MXene composite material of the present invention takes MXene as the main substrate, supports ReSe 2 on MXene, doped sulfur into the ReSe 2 /MXene composite, and reacts by heat treatment The prepared sulfur-doped ReSe 2 /MXene composite material, MXene, ReSe 2 , between the sulfur atoms to make up for their respective defects and deficiencies, has a synergistic effect, and maximizes the potassium storage performance of the composite material, specific capacity, Charge and discharge stability, electron transfer rate and other properties;
(2)本发明的硫掺杂ReSe2/MXene复合材料中MXene特殊的层状结构有效减缓在循环充放电过程中由于负极材料的团聚或体积膨胀而带来的电学性能下降、结构塌陷等问题；ReSe 2的负载有效提高了层间距，增大比表面积；进一步地，硫元素的掺杂使ReSe 2/MXene复合材料暴露更多活性位点与空位，提高材料的储钾性能。 (2) The special layered structure of MXene in the sulfur-doped ReSe2/MXene composite material of the present invention can effectively alleviate the problems such as electrical performance decline and structural collapse caused by the agglomeration or volume expansion of the negative electrode material during the cyclic charge-discharge process; The loading of ReSe 2 effectively increases the interlayer spacing and increases the specific surface area; further, the doping of sulfur element exposes more active sites and vacancies in the ReSe 2 /MXene composite, improving the potassium storage performance of the material.
(3)本发明制备工艺简单安全，成本低廉，有利于推广硫掺杂ReSe 2/MXene复合材料作为钾离子电池负极材料的应用。 (3) The preparation process of the invention is simple and safe, and the cost is low, which is beneficial to popularize the application of the sulfur-doped ReSe 2 /MXene composite material as the negative electrode material of potassium ion battery.
附图说明Description of drawings
图1是对比例1中单独的MXene材料的扫描电镜图；Fig. 1 is the scanning electron microscope image of the MXene material alone in Comparative Example 1;
图2是实施例1中硫掺杂ReSe 2/MXene复合材料的扫描电镜图； 2 is a scanning electron microscope image of the sulfur-doped ReSe 2 /MXene composite material in Example 1;
图3是实施例1中硫掺杂ReSe 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。 3 is a graph showing the cycle performance of the potassium-ion battery assembled with sulfur-doped ReSe 2 /MXene composite material in Example 1 at a current density of 100 mA/g.
图4是对比例1中单独的MXene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 4 is a graph of the cycle performance measured at a current density of 100 mA/g for a potassium-ion battery assembled with a single MXene negative electrode material in Comparative Example 1;
图5是对比例2中单独的ReSe 2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。 5 is a graph of the cycle performance measured at a current density of 100 mA/g for the potassium ion battery assembled with the ReSe 2 anode material alone in Comparative Example 2.
图6是对比例3中ReSe 2/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。 6 is a graph showing the cycle performance of the potassium-ion battery assembled with ReSe 2 /MXene material in Comparative Example 3 at a current density of 100 mA/g.
具体实施方式detailed description
为了更好的解释本发明，现结合以下具体实施例做进一步说明，但是本发明不限于具体 实施例。In order to better explain the present invention, now in conjunction with the following specific embodiments to further illustrate, but the present invention is not limited to 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ReSe 2纳米颗粒购自深圳六碳科技有限公司，型号：ReSe 2型晶体大小20-50nm，纯度：高纯99.999％，晶格种类：半导体材料，各向异性材料。 The ReSe 2 nanoparticles were purchased from Shenzhen Six Carbon Technology Co., Ltd., model: ReSe 2 type crystal size 20-50 nm, purity: high-purity 99.999%, lattice type: semiconductor material, anisotropic material.
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
一种硫掺杂ReSe 2/MXene复合材料的制备方法，包括以下步骤： A preparation method of sulfur-doped ReSe 2 /MXene composite material, comprising the following steps:
(1)将0.1mmol的ReSe 2纳米颗粒、10ml的N,N-二甲基甲酰胺(DMF)和5ml的超纯水充分搅拌混匀，得到悬浊液； (1) fully stirring and mixing 0.1 mmol of ReSe nanoparticles, 10 ml of N,N-dimethylformamide (DMF) and 5 ml of ultrapure water to obtain a suspension;
(2)将0.1mmol的MXene(Ti 3C 2T x)纳米片、悬浊液、0.06mmol的硫粉和15ml的超纯水混合，在25℃下在超声频率为50W超声波清洗仪中处理0.5h，然后磁力搅拌4h，得到混合液； (2) Mix 0.1 mmol of MXene (Ti 3 C 2 T x ) nanosheets, suspension, 0.06 mmol of sulfur powder and 15 ml of ultrapure water, and process at 25°C in an ultrasonic cleaner with an ultrasonic frequency of 50W 0.5h, then magnetic stirring for 4h to obtain a mixed solution;
(3)将搅拌后的混合液移入容量为60ml的反应釜中，并在微波加热箱中加热至150℃，反应10h，并自然冷却至室温；把产物移至离心管中，在7000r/min条件下离心5min，去除上清液的滤渣用去离子水和无水乙醇分别洗涤3次，然后在真空干燥箱中进行烘干，得到粗产物，其中干燥温度为65℃，干燥时间为10h；(3) Transfer the stirred mixture into a reaction kettle with a capacity of 60ml, heat it to 150°C in a microwave oven, react for 10h, and naturally cool to room temperature; move the product to a centrifuge tube, at 7000r/min Centrifuge for 5 min under conditions, remove the filter residue of the supernatant, wash three times with deionized water and anhydrous ethanol, and then dry in a vacuum drying oven to obtain a crude product, wherein the drying temperature is 65 °C, and the drying time is 10h;
(4)将步骤(3)得到的粗产物研磨至分布均匀，并放入刚玉方舟中，在通入氩气的管式炉中加热至250℃，煅烧3h，自然冷却至室温，收集产物，得到硫掺杂ReSe 2/MXene复合材料。 (4) Grind the crude product obtained in step (3) to a uniform distribution, put it into a corundum ark, heat it to 250° C. in a tube furnace fed with argon, calcine for 3 hours, naturally cool to room temperature, and collect the product, A sulfur-doped ReSe 2 /MXene composite was obtained.
将硫掺杂ReSe 2/MXene复合材料、导电剂超级P碳和聚偏氟乙烯粘结剂，按质量比为8:1:1的比例混合均匀，加入适量N-甲基吡咯烷酮，搅拌形成均匀浆料涂在铜箔上，经干燥裁片后作为钾离子电池工作电极，以1M KFSI EC(碳酸乙烯酯)，PC(碳酸丙烯酯)(1:1)为电解液、金属钾片为对电极和玻璃纤维为隔膜，组装成2032型纽扣半电池；所有组装都在惰性气氛手套箱中进行。 The sulfur-doped ReSe 2 /MXene composite material, the conductive agent super P carbon and the polyvinylidene fluoride binder were mixed uniformly in a mass ratio of 8:1:1, and an appropriate amount of N-methylpyrrolidone was added, and stirred to form a uniform The slurry was coated on the copper foil, dried and cut as the working electrode of the potassium ion battery, 1M KFSI EC (ethylene carbonate), PC (propylene carbonate) (1:1) was used as the electrolyte, and potassium metal sheet was used as the countermeasure. Electrodes and glass fibers were used as separators and assembled into 2032 type coin half cells; all assembly was performed in an inert atmosphere glove box.
本实施例的硫掺杂ReSe 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圈后的可逆容量为326.6mA h/g，是未掺杂MXene负极材料组装钾离子电池可 逆容量(61.1mA h/g)的5.3倍，是单纯ReSe 2负极材料(102.4mA h/g)的3.18倍，是ReSe 2/MXene负极材料(286.2mA h/g)的1.14倍，本实施例的硫掺杂ReSe 2/MXene复合负极材料具有良好的储钾性能和充放电循环性能。 The potassium ion battery assembled with the sulfur-doped ReSe 2 /MXene composite negative electrode material in this example has a reversible capacity of 326.6 mA h/g after 100 cycles at a current density of 100 mA/g, which is the best solution for the potassium ion battery assembled with the undoped MXene negative electrode material. The reversible capacity of the ion battery is 5.3 times (61.1 mA h/g), 3.18 times that of the pure ReSe 2 anode material (102.4 mA h/g), and 1.14 times that of the ReSe 2 /MXene anode material (286.2 mA h/g), The sulfur-doped ReSe 2 /MXene composite anode material in this example has good potassium storage performance and charge-discharge cycle performance.
实施例2Example 2
一种硫掺杂ReSe 2/MXene复合材料的制备方法，包括以下步骤： A preparation method of sulfur-doped ReSe 2 /MXene composite material, comprising the following steps:
(1)将0.1mmol的ReSe 2纳米颗粒、15ml的N,N-二甲基甲酰胺(DMF)和10ml的超纯水充分搅拌混匀，得到悬浊液； (1) Fully stirring and mixing 0.1 mmol of ReSe nanoparticles, 15 ml of N,N-dimethylformamide (DMF) and 10 ml of ultrapure water to obtain a suspension;
(2)将0.1mmol的MXene(Ti 3C 2T x)纳米片、悬浊液、0.07mmol的硫粉和20ml的超纯水混合，27℃下，在超声频率为50W超声波清洗仪中处理0.5h，然后磁力搅拌5h，得到混合液； (2) Mix 0.1 mmol of MXene (Ti 3 C 2 T x ) nanosheets, suspension, 0.07 mmol of sulfur powder and 20 ml of ultrapure water, at 27°C, in an ultrasonic cleaner with an ultrasonic frequency of 50W 0.5h, then magnetic stirring for 5h to obtain a mixed solution;
(3)将混合液移入容量为60ml的反应釜中，在微波加热箱中加热至180℃，反应12h，并自然冷却至室温，把产物移至离心管用离心机在7500r/min条件下离心5min，用去离子水和无水乙醇分别对滤渣洗涤3次，然后在真空干燥箱中进行烘干，得到粗产物，其中干燥温度为60℃，干燥时间为10h；(3) Transfer the mixed solution into a reaction kettle with a capacity of 60ml, heat it to 180°C in a microwave heating box, react for 12h, and naturally cool to room temperature, move the product to a centrifuge tube and centrifuge at 7500r/min for 5min , the filter residue was washed 3 times with deionized water and absolute ethanol, and then dried in a vacuum drying oven to obtain a crude product, wherein the drying temperature was 60 °C, and the drying time was 10 h;
(4)将步骤(3)得到的粗产物研磨至分布均匀，并放入刚玉方舟中，在通入氩气的管式炉中加热至280℃煅烧3h，自然冷却至室温，收集产物，得到硫掺杂ReSe 2/MXene复合材料。 (4) Grind the crude product obtained in step (3) to a uniform distribution, put it into a corundum ark, heat it to 280° C. for 3 hours in a tube furnace fed with argon, cool it naturally to room temperature, and collect the product to obtain Sulfur-doped ReSe 2 /MXene composites.
将硫掺杂ReSe 2/MXene复合材料、导电剂超级P碳和聚偏氟乙烯粘结剂，按质量比为8:1:1的比例混合均匀，加入适量N-甲基吡咯烷酮，搅拌形成均匀浆料涂在铜箔上，经干燥裁片后作为钾离子电池工作电极，以1M KFSI EC(碳酸乙烯酯)，PC(碳酸丙烯酯)(1:1)为电解液、金属钾片为对电极和玻璃纤维为隔膜，组装成2032型纽扣半电池；所有组装都在惰性气氛手套箱中进行。 The sulfur-doped ReSe 2 /MXene composite material, the conductive agent super P carbon and the polyvinylidene fluoride binder were mixed uniformly in a mass ratio of 8:1:1, and an appropriate amount of N-methylpyrrolidone was added, and stirred to form a uniform The slurry was coated on the copper foil, dried and cut as the working electrode of the potassium ion battery, 1M KFSI EC (ethylene carbonate), PC (propylene carbonate) (1:1) was used as the electrolyte, and potassium metal sheet was used as the countermeasure. Electrodes and glass fibers were used as separators and assembled into 2032 type coin half cells; all assembly was performed in an inert atmosphere glove box.
本实施例的硫掺杂ReSe 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圈后的可逆容量为335.2mA h/g，是未掺杂MXene负极材料组装钾离子电池可逆容量(61.1mA h/g)的5.4倍，是单纯ReSe 2负极材料(102.4mA h/g)的3.27倍，是ReSe 2/MXene负极材料(286.2mA h/g)的1.17倍，本实施例的硫掺杂ReSe 2/MXene复合负极材料具有良好的储钾性能和充放电循环性能。 The potassium ion battery assembled with the sulfur-doped ReSe 2 /MXene composite negative electrode material in this example has a reversible capacity of 335.2 mA h/g after 100 cycles at a current density of 100 mA/g, which is the best solution for the potassium ion battery assembled with the undoped MXene negative electrode material. The reversible capacity of the ion battery is 5.4 times (61.1 mA h/g), 3.27 times that of the pure ReSe 2 anode material (102.4 mA h/g), and 1.17 times that of the ReSe 2 /MXene anode material (286.2 mA h/g), The sulfur-doped ReSe 2 /MXene composite anode material in this example has good potassium storage performance and charge-discharge cycle performance.
实施例3Example 3
一种硫掺杂ReSe 2/MXene复合材料的制备方法，包括以下步骤： A preparation method of sulfur-doped ReSe 2 /MXene composite material, comprising the following steps:
(1)将0.2mmol的ReSe 2纳米颗粒、15ml的N,N-二甲基甲酰胺(DMF)和10ml的超纯水充分搅拌混匀，得到悬浊液； (1) fully stirring and mixing 0.2 mmol of ReSe nanoparticles, 15 ml of N,N-dimethylformamide (DMF) and 10 ml of ultrapure water to obtain a suspension;
(2)将0.2mmol的MXene(Ti 3C 2T x)纳米片、悬浊液、0.13mmol的硫脲和20ml的超纯水混合，在27℃，超声频率为50W超声波清洗仪中处理0.5h，然后磁力搅拌4h，得到混合液； (2) Mix 0.2 mmol of MXene (Ti 3 C 2 T x ) nanosheets, the suspension, 0.13 mmol of thiourea and 20 ml of ultrapure water, and process it in an ultrasonic cleaner at 27°C with an ultrasonic frequency of 50W for 0.5 h, then magnetic stirring for 4h to obtain a mixed solution;
(3)将混合液移入容量为60ml的反应釜中，在微波加热箱中加热至180℃，反应12h，并自然冷却至室温，把产物移至离心管用离心机在7500r/min条件下离心5min，用去离子水和无水乙醇分别对滤渣洗涤3次，然后在真空干燥箱中进行烘干，得到粗产物，其中干燥温度为60℃，干燥时间为10h；(3) Transfer the mixed solution into a reaction kettle with a capacity of 60ml, heat it to 180°C in a microwave heating box, react for 12h, and naturally cool to room temperature, move the product to a centrifuge tube and centrifuge at 7500r/min for 5min , the filter residue was washed 3 times with deionized water and absolute ethanol, and then dried in a vacuum drying oven to obtain a crude product, wherein the drying temperature was 60 °C, and the drying time was 10 h;
(4)将步骤(3)得到的粗产物进行研磨至分布均匀，放入刚玉方舟中，在通入氩气的管式炉中加热至280℃，煅烧3h，自然冷却至室温，收集产物，得到硫掺杂ReSe 2/MXene复合材料。 (4) Grind the crude product obtained in step (3) to a uniform distribution, put it into a corundum ark, heat it to 280° C. in a tubular furnace fed with argon, calcine for 3 hours, naturally cool to room temperature, and collect the product, A sulfur-doped ReSe 2 /MXene composite was obtained.
将硫掺杂ReSe 2/MXene复合材料、导电剂超级P碳和聚偏氟乙烯粘结剂，按质量比为8:1:1的比例混合均匀，加入适量N-甲基吡咯烷酮，搅拌形成均匀浆料涂在铜箔上，经干燥裁片后作为钾离子电池工作电极，以1M KFSI EC(碳酸乙烯酯),PC(碳酸丙烯酯)(1:1)为电解液、金属钾片为对电极和玻璃纤维为隔膜，组装成2032型纽扣半电池；所有组装都在惰性气氛手套箱中进行。 The sulfur-doped ReSe 2 /MXene composite material, the conductive agent super P carbon and the polyvinylidene fluoride binder were mixed uniformly in a mass ratio of 8:1:1, and an appropriate amount of N-methylpyrrolidone was added, and stirred to form a uniform The slurry was coated on the copper foil, dried and cut as the working electrode of the potassium ion battery, with 1M KFSI EC (ethylene carbonate), PC (propylene carbonate) (1:1) as the electrolyte and metal potassium sheet as the countermeasure. Electrodes and glass fibers were used as separators and assembled into 2032 type coin half cells; all assembly was performed in an inert atmosphere glove box.
本实施例的硫掺杂ReSe 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圈后的可逆容量为313.4mA h/g，是未掺杂MXene钾离子电池负极可逆容量(61.1mA h/g)的5.1倍，是单纯ReSe 2负极材料(102.4mA h/g)的3.06倍，是ReSe 2/MXene负极材料(286.2mA h/g)的1.09倍，且本实施例的硫掺杂ReSe 2/MXene复合负极材料具有非常稳定的充放电循环性能。 The potassium ion battery assembled with the sulfur-doped ReSe 2 /MXene composite negative electrode material in this example has a reversible capacity of 313.4 mA h/g after 100 cycles at a current density of 100 mA/g, which is the negative electrode of an undoped MXene potassium ion battery. The reversible capacity (61.1mA h/g) is 5.1 times, which is 3.06 times that of pure ReSe 2 anode material (102.4 mA h/g), and 1.09 times that of ReSe 2 /MXene anode material (286.2 mA h/g). The sulfur-doped ReSe 2 /MXene composite anode material of the embodiment has very stable charge-discharge cycle performance.
实施例4Example 4
一种硫掺杂ReSe 2/MXene复合材料的制备方法，包括以下步骤： A preparation method of sulfur-doped ReSe 2 /MXene composite material, comprising the following steps:
(1)将0.2mmol的ReSe 2纳米颗粒、15ml的N,N-二甲基甲酰胺(DMF)和10ml的超纯水充分搅拌混匀，得到悬浊液； (1) fully stirring and mixing 0.2 mmol of ReSe nanoparticles, 15 ml of N,N-dimethylformamide (DMF) and 10 ml of ultrapure water to obtain a suspension;
(2)将0.2mmol的MXene(Ti 3C 2T x)纳米片、悬浊液、0.16mmol的硫脲和20ml的超纯水混合，27℃下，在超声频率为50W超声波清洗仪中处理0.5h，然后磁力搅拌4h，得到混合液； (2) Mix 0.2 mmol of MXene (Ti 3 C 2 T x ) nanosheets, suspension, 0.16 mmol of thiourea and 20 ml of ultrapure water, at 27°C, in an ultrasonic cleaner with an ultrasonic frequency of 50W 0.5h, then magnetic stirring for 4h to obtain a mixed solution;
(3)将混合液移入容量为60ml的反应釜中，在微波加热箱中加热至180℃，反应12h，并自然冷却至室温，把产物移至离心管用离心机在7500r/min条件下离心5min，用去离子水和无水乙醇分别对滤渣洗涤3次，然后在真空干燥箱中进行烘干，得到粗产物，其中干燥温度为60℃，干燥时间为10h；(3) Transfer the mixed solution into a reaction kettle with a capacity of 60ml, heat it to 180°C in a microwave heating box, react for 12h, and naturally cool to room temperature, move the product to a centrifuge tube and centrifuge at 7500r/min for 5min , the filter residue was washed 3 times with deionized water and absolute ethanol, and then dried in a vacuum drying oven to obtain a crude product, wherein the drying temperature was 60 °C, and the drying time was 10 h;
(4)将步骤(3)得到的粗产物进行研磨至分布均匀，并放入刚玉方舟中，在通入氩气的管式炉中加热至300℃，煅烧3h，自然冷却至室温，收集产物，得到硫掺杂ReSe 2/MXene复合材料。 (4) Grind the crude product obtained in step (3) to a uniform distribution, put it into a corundum ark, heat it to 300° C. in a tube furnace fed with argon, calcine for 3 hours, naturally cool to room temperature, and collect the product , the sulfur-doped ReSe 2 /MXene composites were obtained.
将硫掺杂ReSe 2/MXene复合材料、导电剂超级P碳和聚偏氟乙烯粘结剂，按质量比为8:1:1的比例混合均匀，加入适量N-甲基吡咯烷酮，搅拌形成均匀浆料涂在铜箔上，经干燥裁片后作为钾离子电池工作电极，以1M KFSI EC(碳酸乙烯酯)，PC(碳酸丙烯酯)(1:1)为电解液、金属钾片为对电极和玻璃纤维为隔膜，组装成2032型纽扣半电池；所有组装都在惰性气氛手套箱中进行。 The sulfur-doped ReSe 2 /MXene composite material, the conductive agent super P carbon and the polyvinylidene fluoride binder were mixed uniformly in a mass ratio of 8:1:1, and an appropriate amount of N-methylpyrrolidone was added, and stirred to form a uniform The slurry was coated on the copper foil, dried and cut as the working electrode of the potassium ion battery, 1M KFSI EC (ethylene carbonate), PC (propylene carbonate) (1:1) was used as the electrolyte, and potassium metal sheet was used as the countermeasure. Electrodes and glass fibers were used as separators and assembled into 2032 type coin half cells; all assembly was performed in an inert atmosphere glove box.
本实施例的硫掺杂ReSe 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圈后的可逆容量为344.1mA h/g，是未掺杂MXene钾离子电池负极可逆容量(61.1mA h/g)的5.6倍，是单纯ReSe 2负极材料(102.4mA h/g)的3.36倍，是ReSe 2/MXene负极材料(286.2mA h/g)的1.2倍，且本实施例的硫掺杂ReSe 2/MXene复合负极材料具有非常稳定的充放电循环性能。 The potassium ion battery assembled with the sulfur-doped ReSe 2 /MXene composite negative electrode material in this example has a reversible capacity of 344.1 mA h/g after 100 cycles at a current density of 100 mA/g, which is the negative electrode of an undoped MXene potassium ion battery. The reversible capacity (61.1mA h/g) is 5.6 times, which is 3.36 times that of pure ReSe 2 anode material (102.4 mA h/g), and 1.2 times that of ReSe 2 /MXene anode material (286.2 mA h/g). The sulfur-doped ReSe 2 /MXene composite anode material of the embodiment has very stable charge-discharge cycle 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 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 type button battery was assembled with a metal potassium sheet as the counter electrode and glass fiber as the separator.
对比例2Comparative Example 2
称取80mg的ReSe 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 ReSe 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, and 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.
对比例3Comparative Example 3
(1)将0.1mmol的ReSe 2纳米颗粒、15ml的N,N-二甲基甲酰胺(DMF)和10ml的超 纯水充分搅拌混匀，得到悬浊液； (1) Fully stirring and mixing 0.1 mmol of ReSe nanoparticles, 15 ml of N,N-dimethylformamide (DMF) and 10 ml of ultrapure water to obtain a suspension;
(2)将0.1mmol的MXene(Ti 3C 2T x)纳米片、悬浊液和20ml的超纯水混合，27℃下，在超声频率为50W超声波清洗仪中处理0.5h，然后磁力搅拌5h，得到混合液； (2) Mix 0.1 mmol of MXene (Ti 3 C 2 T x ) nanosheets, the suspension and 20 ml of ultrapure water, at 27°C, treat in an ultrasonic cleaner with an ultrasonic frequency of 50 W for 0.5 h, and then magnetically stir 5h to obtain a mixed solution;
(3)将混合液移入容量为60ml的反应釜中，在微波加热箱中加热至180℃，反应12h，并自然冷却至室温，把产物移至离心管用离心机在7500r/min条件下离心5min，用去离子水和无水乙醇分别洗涤3次，然后在真空干燥箱中进行烘干，得到粗产物，其中干燥温度为60℃，干燥时间为10h；(3) Transfer the mixed solution into a reaction kettle with a capacity of 60ml, heat it to 180°C in a microwave heating box, react for 12h, and naturally cool to room temperature, move the product to a centrifuge tube and centrifuge at 7500r/min for 5min , washed 3 times with deionized water and absolute ethanol respectively, and then dried in a vacuum drying oven to obtain a crude product, wherein the drying temperature was 60 °C, and the drying time was 10 h;
(4)将步骤(3)得到的粗产物研磨至分布均匀，并放入刚玉方舟中，在通入氩气的管式炉中加热至280℃煅烧3h，自然冷却至室温，收集产物，得到ReSe 2/MXene复合材料。 (4) Grind the crude product obtained in step (3) to a uniform distribution, put it into a corundum ark, heat it to 280° C. for 3 hours in a tube furnace fed with argon, cool it naturally to room temperature, and collect the product to obtain ReSe 2 /MXene composites.
将ReSe 2/MXene复合材料、导电剂超级P碳和聚偏氟乙烯粘结剂，按质量比为8:1:1的比例混合均匀，加入适量N-甲基吡咯烷酮，搅拌形成均匀浆料涂在铜箔上，经干燥裁片后作为钾离子电池工作电极，以1M KFSI EC(碳酸乙烯酯)，PC(碳酸丙烯酯)(1:1)为电解液、金属钾片为对电极和玻璃纤维为隔膜，组装成2032型纽扣半电池；所有组装都在惰性气氛手套箱中进行。 Mix the ReSe 2 /MXene composite material, the conductive agent super P carbon and the polyvinylidene fluoride binder in a mass ratio of 8:1:1, add an appropriate amount of N-methylpyrrolidone, and stir to form a uniform slurry coating. On the copper foil, dried and cut as the working electrode of potassium ion battery, 1M KFSI EC (ethylene carbonate), PC (propylene carbonate) (1:1) as electrolyte, metal potassium sheet as counter electrode and glass Fibers as separators were assembled into 2032-type coin-half cells; all assembly was performed in an inert atmosphere glove box.
图1是对比例1中单独的MXene材料的扫描电镜图，图2是实施例1中硫掺杂ReSe 2/MXene复合材料的扫描电镜图。从图1-2可以看出，本发明所使用的MXene材料呈现多层状结构，表面无杂质，但是层间距较小，掺杂之后的MXene复合材料仍保留原来手风琴状层状结构，同时层间距有明显增大，而且MXene材料表面无团聚现象，表明本实施例成功制备了硫掺杂ReSe 2/MXene复合材料。 FIG. 1 is a scanning electron microscope image of the single MXene material in Comparative Example 1, and FIG. 2 is a scanning electron microscope image of the sulfur-doped ReSe 2 /MXene composite material in Example 1. It can be seen from Figures 1-2 that the MXene material used in the present invention presents a multi-layered structure with no impurities on the surface, but the interlayer spacing is small. The MXene composite material after doping still retains the original accordion-like layered structure, while the layered The spacing increases significantly, and there is no agglomeration on the surface of the MXene material, indicating that the sulfur-doped ReSe 2 /MXene composite material is successfully prepared in this example.
图3-6分别是实施例1中硫掺杂ReSe 2/MXene复合材料，对比例1中单纯的MXene负极材料，对比例2中单独的ReSe 2负极材料，对比例3中ReSe 2/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。从图3-6和表1中我们可以看出，本发明硫掺杂ReSe 2/MXene复合材料在循环100圈后的比容量，储钾性能和循环性能远远优于对比例1-3所述材料。见图4，对比例1中单纯的MXene负极材料，可逆容量很低，仅为61.1mA h/g；见图5，对比例2中单独的ReSe 2负极材料，比容量在循环10圈后衰退，这是因为单独的ReSe 2负极材料易团聚且结构不稳定，充放电性能较差；见图6，对比例3中ReSe 2/MXene材料，在充放电过程中良好的储钾性能，具有较高比容量和稳定的充放电性能，电池性能仍然不理想，需要进一步提高其电化学性能。 Figures 3-6 are respectively the sulfur-doped ReSe 2 /MXene composite material in Example 1, the pure MXene negative electrode material in Comparative Example 1, the single ReSe 2 negative electrode material in Comparative Example 2, and the ReSe 2 /MXene material in Comparative Example 3. Graph of the cycle performance of the assembled potassium-ion battery measured at a current density of 100 mA/g. From Figures 3-6 and Table 1, we can see that the specific capacity, potassium storage performance and cycle performance of the sulfur-doped ReSe 2 /MXene composite of the present invention after 100 cycles are far superior to those of Comparative Examples 1-3. mentioned materials. As shown in Figure 4, the pure MXene anode material in Comparative Example 1 has a very low reversible capacity of only 61.1 mA h/g; Figure 5, the single ReSe 2 anode material in Comparative Example 2, the specific capacity declines after 10 cycles , this is because the single ReSe 2 anode material is easy to agglomerate, has an unstable structure, and has poor charge and discharge performance; as shown in Figure 6, the ReSe 2 /MXene material in Comparative Example 3 has good potassium storage performance during the charge and discharge process, and has a relatively With high specific capacity and stable charge-discharge performance, the battery performance is still not ideal, and its electrochemical performance needs to be further improved.
见图3，本发明专利以MXene为主要基底，将合成的ReSe 2负载在MXene上，并将硫元 素掺杂到ReSe 2/MXene复合物中，经热处理反应制得硫掺杂ReSe 2/MXene复合材料。得到的硫掺杂ReSe2/MXene复合材料的导电性佳，层间距增大，比表面积大，MXene特殊的层状结构可以有效减缓在循环充放电过程中由于负极材料的团聚或体积膨胀而带来的电学性能下降、结构塌陷等问题；ReSe 2的负载有效提高了层间距，增大比表面积；进一步地，硫元素的掺杂使ReSe 2/MXene复合材料暴露更多活性位点与空位，进而提高材料的储钾性能。因此，MXene，ReSe 2，硫原子之间可以弥补各自的缺陷和不足，具有协同增效作用，最大程度地提高了复合材料的储钾性能，比容量、充放电稳定性、电子转移速率等性能。同时，制备工艺简单，性能可控。 As shown in Figure 3, the patent of the present invention uses MXene as the main substrate, the synthesized ReSe 2 is supported on MXene, and sulfur is doped into the ReSe 2 /MXene composite, and the sulfur-doped ReSe 2 /MXene is prepared by heat treatment reaction. composite material. The obtained sulfur-doped ReSe2/MXene composite has good conductivity, increased interlayer spacing, and large specific surface area. The special layered structure of MXene can effectively slow down the agglomeration or volume expansion of the negative electrode material during the cyclic charge-discharge process. The electrical performance decline and structural collapse of the ReSe 2 can effectively increase the interlayer spacing and increase the specific surface area; further, the doping of sulfur element exposes more active sites and vacancies in the ReSe 2 /MXene composite, and then Improve the potassium storage properties of the material. Therefore, MXene, ReSe 2 , and sulfur atoms can compensate for their respective defects and deficiencies, and have a synergistic effect, which maximizes the potassium storage performance, specific capacity, charge-discharge stability, electron transfer rate and other properties of the composite. . Meanwhile, the preparation process is simple and the performance is controllable.
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. 一种硫掺杂ReSe 2/MXene复合材料的制备方法，其特征在于，包括以下步骤： A preparation method of sulfur-doped ReSe 2 /MXene composite material, characterized in that it comprises the following steps:
    (1)将ReSe 2纳米颗粒、溶剂和水充分混合，得到分散液； (1) fully mixing ReSe nanoparticles, solvent and water to obtain dispersion;
    (2)将MXene纳米片、分散液、硫源和水混合，超声，配制成浓度为1-100mg/ml的混合液；(2) Mix the MXene nanosheets, dispersion liquid, sulfur source and water, ultrasonically, and prepare a mixed liquid with a concentration of 1-100 mg/ml;
    (3)将搅拌后的混合液加热至150-250℃，反应10-24h，得到悬浊液，离心，洗涤，干燥得到粗产物；(3) heating the stirred mixture to 150-250°C, reacting for 10-24h to obtain a suspension, centrifuging, washing, and drying to obtain a crude product;
    (4)将步骤(3)得到的粗产物在保护气氛中，加热至200-300℃，煅烧2-4h，冷却，收集，得到硫掺杂ReSe 2/MXene复合材料。 (4) The crude product obtained in step (3) is heated to 200-300° C. in a protective atmosphere, calcined for 2-4 hours, cooled and collected to obtain a sulfur-doped ReSe 2 /MXene composite material.
  2. 根据权利要求1所述的硫掺杂ReSe 2/MXene复合材料的制备方法，其特征在于，所述溶剂为N,N-二甲基甲酰胺、环己烷、二甲苯中的至少一种；优选的，所述清洗剂为水、乙醇中的至少一种。 The method for preparing a sulfur-doped ReSe 2 /MXene composite material according to claim 1, wherein the solvent is at least one of N,N-dimethylformamide, cyclohexane, and xylene; Preferably, the cleaning agent is at least one of water and ethanol.
  3. 根据权利要求1所述的硫掺杂ReSe 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、Nb 2CT x、Ta 4C 3T x、Ti 3CNT X中的一种或多种。 The preparation method of sulfur-doped ReSe 2 /MXene composite material according to claim 1, wherein the MXene is Ti 3 C 2 T x , Ti 2 CT x , Nb 2 CT x , Ta 4 C 3 T One or more of x and Ti 3 CNT X.
  4. 根据权利要求1所述的硫掺杂ReSe 2/MXene复合材料的制备方法，其特征在于，所述硫源为硫粉、硫脲、硫代乙酰胺中的一种或多种。 The method for preparing a sulfur-doped ReSe 2 /MXene composite material according to claim 1, wherein the sulfur source is one or more of sulfur powder, thiourea, and thioacetamide.
  5. 根据权利要求1所述的硫掺杂ReSe 2/MXene复合材料的制备方法，其特征在于，所述硫掺杂ReSe 2/MXene复合材料中的硫掺杂量为1-20wt％。 The method for preparing a sulfur-doped ReSe 2 /MXene composite material according to claim 1, wherein the sulfur-doped ReSe 2 /MXene composite material has a sulfur doping amount of 1-20 wt %.
  6. 根据权利要求1所述的硫掺杂ReSe 2/MXene复合材料的制备方法，其特征在于，MXene纳米片、ReSe 2纳米颗粒和硫源的摩尔为1：1：0.01-0.9。 The method for preparing a sulfur-doped ReSe 2 /MXene composite material according to claim 1, wherein the moles of the MXene nanosheets, the ReSe 2 nanoparticles and the sulfur source are 1:1:0.01-0.9.
  7. 根据权利要求1所述的硫掺杂ReSe 2/MXene复合材料的制备方法，其特征在于，步骤(3)中所述离心转速为6000-8000r/min，离心时间为5-10min；优选的，步骤(3)中所述干燥的温度为50-70℃，干燥时间8-12h。 The method for preparing a sulfur-doped ReSe 2 /MXene composite material according to claim 1, wherein the centrifugal rotation speed in step (3) is 6000-8000 r/min, and the centrifugal time is 5-10 min; preferably, The drying temperature in step (3) is 50-70° C., and the drying time is 8-12 h.
  8. 根据权利要求1所述的硫掺杂ReSe 2/MXene复合材料的制备方法，其特征在于，步骤(4)中的保护气体为氩气、氦气、氮气中的一种或多种。 The method for preparing a sulfur-doped ReSe 2 /MXene composite material according to claim 1, wherein the protective gas in step (4) is one or more of argon, helium, and nitrogen.
  9. 一种钾离子电池负极，其特征在于，其包括由权利要求1-8中任一项所述的制备方法制备得到硫掺杂ReSe 2/MXene复合材料。 A potassium ion battery negative electrode, characterized in that it comprises a sulfur-doped ReSe 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所述钾离子电池负极。A potassium ion battery, characterized in that it comprises the negative electrode of the potassium ion battery according to claim 9.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114614112A (en) * 2022-04-06 2022-06-10 吉林大学 Preparation method of solid-state energy storage device taking MXene as electrode and PVA-based hydrogel as electrolyte
CN115101733A (en) * 2022-06-30 2022-09-23 陕西科技大学 (NiCo) Se/(NiCo) Se 2 @ C heterostructure composite material and preparation method and application thereof
CN115678029A (en) * 2022-10-27 2023-02-03 陕西科技大学 Z-67/MXene nano composite material, preparation method and application

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160066966A (en) * 2014-12-03 2016-06-13 주식회사 엘지화학 Preparation method for nanosheet of layered strucutre compound
CN108423642A (en) * 2018-04-04 2018-08-21 南京邮电大学 A kind of preparation method of small size Transition-metal dichalcogenide two-dimensional nano piece
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
CN111180694A (en) * 2019-12-31 2020-05-19 广东工业大学 MXene/metal sulfide composite material, negative electrode material, preparation and application

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106207125B (en) * 2016-08-23 2018-10-26 东华大学 Sulfur doping selenizing molybdenum/graphene-graphene nanobelt aeroge and its preparation
CN109888280B (en) * 2019-01-23 2021-12-17 五邑大学 Sulfur-doped MXene negative electrode material of potassium ion battery and preparation method thereof
CN110534738B (en) * 2019-08-19 2021-02-09 中南大学 Double-anion cobalt-based selenium sulfide and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160066966A (en) * 2014-12-03 2016-06-13 주식회사 엘지화학 Preparation method for nanosheet of layered strucutre compound
CN108423642A (en) * 2018-04-04 2018-08-21 南京邮电大学 A kind of preparation method of small size Transition-metal dichalcogenide two-dimensional nano piece
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
CN111180694A (en) * 2019-12-31 2020-05-19 广东工业大学 MXene/metal sulfide composite material, negative electrode material, preparation and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WU MINGGUANG: "Study on the Novel Two-dimensional Layered Compounds as Anode Materials for Potassium Ion Batteries", MASTER THESIS, TIANJIN POLYTECHNIC UNIVERSITY, CN, no. 7, 15 July 2020 (2020-07-15), CN , XP055901005, ISSN: 1674-0246 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114614112A (en) * 2022-04-06 2022-06-10 吉林大学 Preparation method of solid-state energy storage device taking MXene as electrode and PVA-based hydrogel as electrolyte
CN114614112B (en) * 2022-04-06 2024-01-30 吉林大学 Preparation method of solid-state energy storage device with MXene as electrode PVA-based hydrogel as electrolyte
CN115101733A (en) * 2022-06-30 2022-09-23 陕西科技大学 (NiCo) Se/(NiCo) Se 2 @ C heterostructure composite material and preparation method and application thereof
CN115101733B (en) * 2022-06-30 2023-08-25 东莞市共和电子有限公司 (NiCo) Se/(NiCo) Se 2 Composite material with @ C heterostructure, and preparation method and application thereof
CN115678029A (en) * 2022-10-27 2023-02-03 陕西科技大学 Z-67/MXene nano composite material, preparation method and application
CN115678029B (en) * 2022-10-27 2023-11-24 陕西科技大学 Z-67/MXene nanocomposite, preparation method and application

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