WO2022032750A1 - Method for preparing array-shaped sns2/mxene composite material - Google Patents

Method for preparing array-shaped sns2/mxene composite material Download PDF

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WO2022032750A1
WO2022032750A1 PCT/CN2020/112571 CN2020112571W WO2022032750A1 WO 2022032750 A1 WO2022032750 A1 WO 2022032750A1 CN 2020112571 W CN2020112571 W CN 2020112571W WO 2022032750 A1 WO2022032750 A1 WO 2022032750A1
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sns
composite material
mxene
arrayed
mxene composite
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French (fr)
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张业龙
孙宏阳
周健文
徐晓丹
汤伟健
曾庆光
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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
    • 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 field of new energy materials, in particular to a preparation method of an array SnS 2 /MXene composite material.
  • Potassium-ion batteries have the advantages of low cost and wide source of raw materials, and have become a strong candidate for large-scale energy storage devices.
  • potassium ions will produce huge volume changes when they are inserted into and extracted from the electrode, which will destroy the structure of the electrode material and cause poor cycle stability.
  • the theoretical potassium storage specific capacity of graphite is only 278mAh/g, which is far from meeting the commercial requirements for potassium-ion batteries to be used as large-scale energy storage. Therefore, the development of potassium-ion anode materials with high specific capacity and high cycle stability has the advantages of great commercial value.
  • SnS 2 shows great potential in energy storage due to its good redox reversibility, high theoretical specific capacity (733 mAh/g), and low cost and easy availability.
  • pure SnS has a huge volume expansion during charging and discharging, and is prone to "pulverization" and agglomeration during long - term cycling, resulting in a sharp decline in battery capacity, which severely limits the practical application of SnS .
  • MXene materials are a series of new two-dimensional metal carbides and nitrides.
  • the general chemical formula is: M n+1 X n T x , where M represents transition metal, X represents carbon or nitrogen, and T represents functional groups -OH, -F, - O et al.
  • M represents transition metal
  • X represents carbon or nitrogen
  • T represents functional groups -OH, -F, - O et al.
  • the unique accordion-like structure endows MXene with distinctive electrochemical properties, such as high electrical conductivity, large specific surface area, abundant active sites, diverse surface functional groups, etc., thus showing good application in the field of energy storage. potential.
  • its interlayer spacing is small, and the surface functional groups have certain adsorption properties, so it cannot achieve the ideal rapid ion migration effect when used alone.
  • one of the objectives of the present invention is to provide an arrayed SnS 2 /MXene composite material.
  • Another object of the present invention is to provide a method for preparing the above-mentioned arrayed SnS 2 /MXene composite material.
  • the present invention provides the application of the arrayed SnS 2 /MXene composite material, and the arrayed SnS 2 /MXene composite material is used as the negative electrode of potassium ion battery.
  • a preparation method of an arrayed SnS 2 /MXene composite material belongs to a solvothermal method, and includes the following steps:
  • the tin atoms and sulfur atoms in the tin source material and the sulfur source material are in a molar ratio of 1:(2-5), preferably 1:(2-4), and more preferably 1:(2.5-3.5 ), more preferably 1:(3-5), adding the dispersion liquid obtained in step (1), and stirring for 1-5 hours, optional 1, 2, 3, 4, and 5 hours to obtain a mixed solution;
  • step (3) The mixed solution obtained in step (2) is transferred into a stainless steel reactor and heated to 120-200°C, such as 120°C, 150°C, 180°C, 200°C, and kept for 8-24 hours, such as 8 hours, 12 hours, 15 hours, 18 hours, and 20 hours, cooled to room temperature, centrifuged, washed with detergent for several times, and dried in vacuum to obtain an arrayed SnS 2 /MXene composite;
  • 120-200°C such as 120°C, 150°C, 180°C, 200°C
  • 8-24 hours such as 8 hours, 12 hours, 15 hours, 18 hours, and 20 hours
  • the tin source material is one or more of SnCl 4 , SnCl 4 ⁇ 5H 2 O, and C 12 H 10 Cl 2 Sn.
  • the sulfur source material is one or more of thioacetamide and thiourea.
  • the MXene is one or more of Ti 3 C 2 T x , V 3 C 2 T x , Mo 3 N 2 T x , such as Ti 3 C 2 T x , V 3 C 2 T x , Mo 3 N 2 T x ; preferably Ti 3 C 2 T x and V 3 C 2 T x with a mass ratio of 2-4:1, and more preferably Ti 3 with a mass ratio of 2-4: 1: 1 C 2 T x , V 3 C 2 T x , and Mo 3 N 2 T x .
  • the dispersant is a mixture of ethanol and ethylene glycol, preferably ethanol and ethylene glycol with a mass ratio of 3-8:1, more preferably ethanol and ethylene glycol with a mass ratio of 3:1 .
  • the cleaning agent is one or more of water and absolute ethanol.
  • the product obtained in step (2) is washed alternately with deionized water and absolute ethanol, for example, alternately washed with deionized water and absolute ethanol for 2-10 times, preferably 3-5 times.
  • the loading amount of SnS 2 in the arrayed SnS 2 /MXene composite material is 50-200wt%, preferably 50-100wt%, more preferably 60-150wt%, still more preferably 70-120wt% , such as 110-200wt%.
  • the mixed dispersion liquid is heated to 120-200°C, preferably 160°C, such as 140°C, 150°C, 160°C, 170°C in the reaction kettle, and reacts for 10-15 hours, preferably 12 hours , such as 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours.
  • the centrifugal rotation speed is 3000-8000r/min, preferably 6000r/min, and the centrifugation time is 5-10min, such as 5min, 6min, 7min, 8min, 9min, 10min.
  • the temperature of vacuum drying in step (3) is 50-100°C, preferably 80°C, and the drying time is 6-15 hours, preferably 8 hours, such as 8 hours, 9 hours, 10 hours, 11 hours, 12 hours; vacuum
  • the degree does not exceed 135Pa, for example, it does not exceed 133Pa, 130Pa, 120Pa, 110Pa, 100Pa, 90Pa.
  • a potassium ion battery negative electrode comprising the arrayed SnS 2 /MXene composite material prepared by the above preparation method.
  • a potassium ion battery comprising the above-mentioned battery negative electrode.
  • the arrayed SnS 2 /MXene composites prepared in the present invention relieve the SnS 2 in cycling by anchoring the SnS 2 nanosheets with high specific capacity on the MXene surface with good electrical conductivity.
  • the huge volume expansion of the process greatly improves the agglomeration and pulverization of SnS 2 during the cycle, so as to solve the problem of SnS 2 capacity decay.
  • Fig. 1 is the scanning electron microscope image of pure SnS material in comparative example 1 ;
  • Fig. 2 is the scanning electron microscope image of MXene material in comparative example 2;
  • Example 3 is a scanning electron microscope image of the arrayed SnS 2 /MXene composite material in Example 1;
  • Example 4 is a graph showing the cycle performance of pure SnS 2 in Comparative Example 1, MXene in Comparative Example 2, and the arrayed SnS 2 /MXene composite in Example 1.
  • the Ti 3 C 2 T x particles were purchased from Beijing Beike New Material Technology Co., Ltd., number BK2020011814, lamellar stacking thickness: 1-5 ⁇ m, purity: 99%, product application fields: energy storage, catalysis, analytical chemistry, etc.
  • SnS2 loading X-ray energy dispersive analysis (EDS).
  • Battery performance test Mix the active materials (SnS2, MXene, SnS2/MXene) with conductive carbon black and polyvinylidene fluoride binder in a mass ratio of 8:1:1, and add an appropriate amount of N-methyl fluoride. pyrrolidone, stir evenly, coat on copper foil, vacuum dry at 80° C. and slice to obtain a potassium ion battery negative electrode sheet with a diameter of 18 mm. The negative electrode, potassium metal foil, and separator (Whatman, GF/F) were assembled into a 2032 button battery in a glove box, and the battery performance was tested by using the Wuhan Blue Electric Battery Test System.
  • the invention prepares an arrayed SnS 2 /MXene composite material.
  • SnS 2 material please refer to: "Li Xin. Research on the synthesis and properties of tin disulfide-based composite materials [D]. Northeastern University, 2011.”
  • a preparation method of an arrayed SnS 2 /MXene composite material comprising the following steps:
  • step (3) the mixed solution obtained in step (2) is transferred into a stainless steel reaction kettle and heated to 160° C. and kept warm for 12 hours, and then cooled to room temperature;
  • step (3) centrifuging the target product obtained in step (3) at 6000 r/min for 5 minutes, and alternately washing with deionized water and absolute ethanol for 3 times;
  • step (4) drying the product obtained in step (4) in a vacuum drying oven at a drying temperature of 80° C. and a drying time of 10 hours to obtain an arrayed SnS2/MXene composite material.
  • the reversible capacity of the arrayed SnS 2 /MXene composite prepared in this example was 272.7 mAh/g after 200 cycles.
  • a preparation method of an arrayed SnS 2 /MXene composite material comprising the following steps:
  • step (3) The mixed dispersion liquid obtained in step (2) is transferred into a stainless steel reactor, heated to 120° C. and kept for 18h, and then cooled to room temperature;
  • step (3) the target product of step (3) gained is centrifuged 3 minutes under 8000r/min conditions, with deionized water and absolute ethanol alternately wash three times;
  • step (4) drying the product obtained in step (4) in a vacuum drying oven at a drying temperature of 70° C. and a drying time of 12 hours to obtain an arrayed SnS2/MXene composite material.
  • the reversible capacity of the arrayed SnS 2 /MXene composite prepared in this example was 302.7 mAh/g after 200 cycles.
  • a preparation method of an arrayed SnS 2 /MXene composite material comprising the following steps:
  • step (3) the mixed solution obtained in step (2) is moved into a stainless steel reaction kettle and heated to 180° C. and kept warm for 10 hours, and then cooled to room temperature;
  • step (3) centrifuging the target product obtained in step (3) at 4000 r/min for 5 minutes, and alternately washing three times with deionized water and absolute ethanol;
  • step (4) drying the product obtained in step (4) in a vacuum drying oven at a drying temperature of 60° C. and a drying time of 16 hours to obtain an arrayed SnS2/MXene composite material.
  • the reversible capacity of the arrayed SnS 2 /MXene composite prepared in this example after 200 cycles is 215.3 mAh/g.
  • the reversible capacity of the SnS 2 material prepared in this comparative example was only 5.3 mAh/g after 50 cycles.
  • the reversible capacity of the MXene material of this comparative example was 43 mAh/g after 50 cycles.
  • the pure SnS 2 material is spherical and has obvious agglomeration; the pure MXene material is sheet-like, but the interlayer spacing is small ; 2 The material is uniformly loaded on MXene without agglomeration.
  • the array-like SnS 2 /MXene composites prepared in the present invention can alleviate the problem by anchoring the SnS 2 nanosheets with high specific capacity on the MXene surface with good electrical conductivity.
  • the huge volume expansion of SnS 2 during the cycling process is eliminated, and the agglomeration and pulverization phenomena of SnS 2 during the cycling process are greatly improved, so as to solve the problem of SnS 2 capacity decay.

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Abstract

A method for preparing an array-shaped SnS2/MXene composite material for the negative electrode of a potassium ion battery. The method comprises the following steps: (1) adding an MXene material to a dispersing agent, and fully stirring same to formulate a dispersion with a concentration of 0.1-10mg/ml; (2) adding a tin source material and a sulfur source material in a molar ratio of 1:(2-4) into the dispersion obtained in step (1), and fully stirring same to obtain a mixed solution; and (3) heating the mixed solution obtained in step (2) to 120-200°C, maintaining the temperature for 8-24 hours, and cooling, centrifuging, washing and drying same to obtain the array-shaped SnS2/MXene composite material. In comparison with pure SnS2, in the array-shaped SnS2/MXene composite material prepared above, SnS2 nanosheets with a high specific capacity are anchored to an MXene surface having a good conductivity. When the obtained array-shaped SnS2/MXene composite material is used for the negative electrode of a potassium ion battery, same exhibits a high specific capacity and good cycle stability.

Description

一种阵列状SnS 2/MXene复合材料的制备方法 An array of SnS Preparation method of 2/MXene composites 技术领域technical field
本发明属于新能源材料领域，具体涉及一种阵列状SnS 2/MXene复合材料的制备方法。 The invention belongs to the field of new energy materials, in particular to a preparation method of an array SnS 2 /MXene composite material.
背景技术Background technique
钾离子电池具有成本低，原料来源广的优点，已经成为大规模储能器件的有力候选者。然而，由于钾离子半径
Figure PCTCN2020112571-appb-000001
较大，这导致钾离子在体相材料中扩散动力学缓慢，造成容量低下，同时钾离子在嵌入与脱出电极时会产生巨大的体积变化，从而破坏电极材料结构，造成循环稳定性差，目前商用的石墨理论储钾比容量仅为278mAh/g，这远不能满足商业上对钾离子电池用作大规模储能的要求，因此，开发具有高比容量且循环稳定性高的钾离子负极材料具有巨大的商业价值。 Potassium-ion batteries have the advantages of low cost and wide source of raw materials, and have become a strong candidate for large-scale energy storage devices. However, due to the potassium ion radius
Figure PCTCN2020112571-appb-000001
This leads to slow diffusion kinetics of potassium ions in bulk materials, resulting in low capacity. At the same time, potassium ions will produce huge volume changes when they are inserted into and extracted from the electrode, which will destroy the structure of the electrode material and cause poor cycle stability. The theoretical potassium storage specific capacity of graphite is only 278mAh/g, which is far from meeting the commercial requirements for potassium-ion batteries to be used as large-scale energy storage. Therefore, the development of potassium-ion anode materials with high specific capacity and high cycle stability has the advantages of great commercial value.
SnS 2因具有良好的氧化还原可逆性，高的理论比容量(733mAh/g)，以及廉价易得等优点，在能源存储方面表现出极大地潜力。然而，单纯的SnS 2在充放电过程中体积膨胀巨大，并且在长期循环期间易出现“粉化”和团聚现象，从而使得电池容量急剧衰减，这严重限制了SnS 2的实际应用。 SnS 2 shows great potential in energy storage due to its good redox reversibility, high theoretical specific capacity (733 mAh/g), and low cost and easy availability. However, pure SnS has a huge volume expansion during charging and discharging, and is prone to "pulverization" and agglomeration during long - term cycling, resulting in a sharp decline in battery capacity, which severely limits the practical application of SnS .
MXene材料是新型二维金属碳化物和氮化物系列，其化学通式为：M n+1X nT x，M代表过渡金属，X代表碳或者氮，T代表官能团-OH、-F、-O等。独特的手风琴状结构赋予了MXene与众不同的电化学性能，如：高的导电性、大的比表面积、丰富的活性位点、多样的表面官能团等，从而在储能领域表现出良好的应用潜力。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 materials are a series of new two-dimensional metal carbides and nitrides. The general chemical formula is: M n+1 X n T x , where M represents transition metal, X represents carbon or nitrogen, and T represents functional groups -OH, -F, - O et al. The unique accordion-like structure endows MXene with distinctive electrochemical properties, such as high electrical conductivity, large specific surface area, abundant active sites, diverse surface functional groups, etc., thus showing good application in the field of energy storage. potential. However, its interlayer spacing is small, and the surface functional groups have certain adsorption properties, so it cannot achieve the ideal rapid ion migration effect when used alone.
发明内容SUMMARY OF THE INVENTION
针对目前钾离子电池负极材料存在的问题，本发明的目的之一在于提供一种阵列状SnS 2/MXene复合材料。本发明的另一目的在于提供上述阵列状SnS 2/MXene复合材料的制备方法。进一步的，本发明提供阵列状SnS 2/MXene复合材料的应用，将所述阵列状SnS 2/MXene复合材料用作钾离子电池负极。 Aiming at the problems existing in the current negative electrode materials for potassium ion batteries, one of the objectives of the present invention is to provide an arrayed SnS 2 /MXene composite material. Another object of the present invention is to provide a method for preparing the above-mentioned arrayed SnS 2 /MXene composite material. Further, the present invention provides the application of the arrayed SnS 2 /MXene composite material, and the arrayed SnS 2 /MXene composite material is used as the negative electrode of potassium ion battery.
本发明采用以下技术方案：The present invention adopts the following technical solutions:
一种阵列状SnS 2/MXene复合材料的制备方法，所述制备方法属于溶剂热法，包括以下步骤： A preparation method of an arrayed SnS 2 /MXene composite material, the preparation method belongs to a solvothermal method, and includes the following steps:
(1)将MXene材料先加入分散剂中，搅拌3-12小时，例如3小时，5小时，8小时，12小时，配制成浓度为0.1-10mg/ml的分散液，优选的为0.1-9mg/ml，进一步优选的为0.2-8mg/ml，更进一步优选的为0.4-0.6mg/ml；(1) Add the MXene material to the dispersant first, stir for 3-12 hours, such as 3 hours, 5 hours, 8 hours, 12 hours, and prepare a dispersion liquid with a concentration of 0.1-10 mg/ml, preferably 0.1-9 mg /ml, more preferably 0.2-8mg/ml, still more preferably 0.4-0.6mg/ml;
(2)将锡源材料与硫源材料中的锡原子和硫原子按照摩尔比例1:(2-5)，优选的为1:(2-4)，进一步优选的为1:(2.5-3.5)，更进一步优选的为1:(3-5)，加入步骤(1)所得分散液，并搅拌1-5小时，可选1、2、3、4、5小时，得到混合液；(2) The tin atoms and sulfur atoms in the tin source material and the sulfur source material are in a molar ratio of 1:(2-5), preferably 1:(2-4), and more preferably 1:(2.5-3.5 ), more preferably 1:(3-5), adding the dispersion liquid obtained in step (1), and stirring for 1-5 hours, optional 1, 2, 3, 4, and 5 hours to obtain a mixed solution;
(3)将步骤(2)所得混合液移入不锈钢反应釜加热至120-200℃，例如120℃，150℃，180℃，200℃，并保温8-24小时，例如8小时、12小时、15小时、18小时、20小时，冷却至室温，离心，用清洗剂进行多次清洗，真空干燥，得到阵列状SnS 2/MXene复合材料； (3) The mixed solution obtained in step (2) is transferred into a stainless steel reactor and heated to 120-200°C, such as 120°C, 150°C, 180°C, 200°C, and kept for 8-24 hours, such as 8 hours, 12 hours, 15 hours, 18 hours, and 20 hours, cooled to room temperature, centrifuged, washed with detergent for several times, and dried in vacuum to obtain an arrayed SnS 2 /MXene composite;
进一步地，所述锡源材料为SnCl 4、SnCl 4·5H 2O、C 12H 10Cl 2Sn中的一种或多种。 Further, the tin source material is one or more of SnCl 4 , SnCl 4 ·5H 2 O, and C 12 H 10 Cl 2 Sn.
进一步地，所述硫源材料为硫代乙酰胺、硫脲中的一种或多种。Further, the sulfur source material is one or more of thioacetamide and thiourea.
进一步地，所述MXene为Ti 3C 2T x、V 3C 2T x、Mo 3N 2T x中的一种或多种，例如Ti 3C 2T x，V 3C 2T x，Mo 3N 2T x；优选的为质量比为2～4:1的Ti 3C 2T x和V 3C 2T x，进一步优选的为质量比为2～4:1:1的Ti 3C 2T x、V 3C 2T x、和Mo 3N 2T x。 Further, the MXene is one or more of Ti 3 C 2 T x , V 3 C 2 T x , Mo 3 N 2 T x , such as Ti 3 C 2 T x , V 3 C 2 T x , Mo 3 N 2 T x ; preferably Ti 3 C 2 T x and V 3 C 2 T x with a mass ratio of 2-4:1, and more preferably Ti 3 with a mass ratio of 2-4: 1: 1 C 2 T x , V 3 C 2 T x , and Mo 3 N 2 T x .
进一步地，所述分散剂为乙醇与乙二醇的混合物，优选的为质量比为3-8:1的乙醇和乙二醇，进一步优选的为质量比为3:1的乙醇和乙二醇。Further, the dispersant is a mixture of ethanol and ethylene glycol, preferably ethanol and ethylene glycol with a mass ratio of 3-8:1, more preferably ethanol and ethylene glycol with a mass ratio of 3:1 .
进一步地，所述清洗剂为水、无水乙醇中的一种或多种。优选用去离子水和无水乙醇交替清洗步骤(2)所得的产物，例如用去离子水和无水乙醇交替清洗2-10次，优选3-5次。Further, the cleaning agent is one or more of water and absolute ethanol. Preferably, the product obtained in step (2) is washed alternately with deionized water and absolute ethanol, for example, alternately washed with deionized water and absolute ethanol for 2-10 times, preferably 3-5 times.
进一步地，所述阵列状SnS 2/MXene复合材料中SnS 2负载量为50-200wt％，优选的为50-100wt％，进一步优选的为60-150wt％，更进一步优选的为70-120wt％，例如110-200wt％。 Further, the loading amount of SnS 2 in the arrayed SnS 2 /MXene composite material is 50-200wt%, preferably 50-100wt%, more preferably 60-150wt%, still more preferably 70-120wt% , such as 110-200wt%.
进一步地，步骤(3)中所述混合分散液在反应釜中升温至120-200℃，优选160℃，例如140℃、150℃、160℃、170℃，反应10-15小时，优选12小时，例如10小时、11小时、12小时、13小时、14小时、15小时。Further, in the step (3), the mixed dispersion liquid is heated to 120-200°C, preferably 160°C, such as 140°C, 150°C, 160°C, 170°C in the reaction kettle, and reacts for 10-15 hours, preferably 12 hours , such as 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours.
进一步地，步骤(3)中所述离心转速为3000-8000r/min，优选6000r/min，离心时间为5-10min，例如5min，6min，7min，8min，9min，10min。Further, in step (3), the centrifugal rotation speed is 3000-8000r/min, preferably 6000r/min, and the centrifugation time is 5-10min, such as 5min, 6min, 7min, 8min, 9min, 10min.
进一步地，步骤(3)中真空干燥的温度为50-100℃，优选80℃，干燥时间6-15小时，优选8小时，例如8小时、9小时、10小时、11小时、12小时；真空度不超过135Pa，例如不超过133Pa、130Pa、120Pa、110Pa、100Pa、90Pa。Further, the temperature of vacuum drying in step (3) is 50-100°C, preferably 80°C, and the drying time is 6-15 hours, preferably 8 hours, such as 8 hours, 9 hours, 10 hours, 11 hours, 12 hours; vacuum The degree does not exceed 135Pa, for example, it does not exceed 133Pa, 130Pa, 120Pa, 110Pa, 100Pa, 90Pa.
一种钾离子电池负极，其包括上述制备方法制备得到的阵列状SnS 2/MXene复合材料。 A potassium ion battery negative electrode, comprising the arrayed SnS 2 /MXene composite material prepared by the above preparation method.
一种钾离子电池，其包括上述电池负极。A potassium ion battery, comprising the above-mentioned battery negative electrode.
本发明的有益效果：Beneficial effects of the present invention:
(1)与纯SnS 2材料相比，本发明制备的阵列状SnS 2/MXene复合材料通过将高比容量的SnS 2纳米片锚定在具有良好导电性的MXene表面，缓解了SnS 2在循环过程的巨大体积膨胀，并极大改善了SnS 2在循环过程中出现的团聚以及粉化现象，以解决SnS 2容量衰减问题。 (1) Compared with pure SnS 2 materials, the arrayed SnS 2 /MXene composites prepared in the present invention relieve the SnS 2 in cycling by anchoring the SnS 2 nanosheets with high specific capacity on the MXene surface with good electrical conductivity. The huge volume expansion of the process greatly improves the agglomeration and pulverization of SnS 2 during the cycle, so as to solve the problem of SnS 2 capacity decay.
(2)所述阵列状SnS 2/MXene复合材料用作钾离子负极材料时，具有高的比容量及良好的循环稳定性，是极具发展前途的钾离子负极材料。 (2) When the arrayed SnS 2 /MXene composite material is used as a potassium ion anode material, it has high specific capacity and good cycle stability, and is a promising potassium ion anode material.
(3)本发明提供的阵列状SnS 2/MXene复合材料的制备方法简单，操作难度低，适合大规模应用。 (3) The preparation method of the arrayed SnS 2 /MXene composite material provided by the present invention is simple, the operation difficulty is low, and it is suitable for large-scale application.
附图说明Description of drawings
图1是对比例1中纯SnS 2材料的扫描电镜图； Fig. 1 is the scanning electron microscope image of pure SnS material in comparative example 1 ;
图2是对比例2中MXene材料的扫描电镜图；Fig. 2 is the scanning electron microscope image of MXene material in comparative example 2;
图3是实施例1中阵列状SnS 2/MXene复合材料的扫描电镜图； 3 is a scanning electron microscope image of the arrayed SnS 2 /MXene composite material in Example 1;
图4是对比例1中纯SnS 2，对比例2中MXene，实施例1中阵列状SnS 2/MXene复合材料的循环性能图。 4 is a graph showing the cycle performance of pure SnS 2 in Comparative Example 1, MXene in Comparative Example 2, and the arrayed SnS 2 /MXene composite in Example 1.
具体实施方式detailed description
为了更好的解释本发明，现结合以下具体实施例作进一步说明，但是本发明不限于具体实施例。In order to better explain the present invention, further description will now be made in conjunction with the following specific embodiments, but the present invention is not limited to the specific embodiments.
其中，所述材料如无特别说明均可以在商业途径可得；Wherein, the materials can be commercially available unless otherwise specified;
所述Ti 3C 2T x颗粒购自北京北科新材科技有限公司，编号BK2020011814，片层堆积厚度：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 particles were purchased from Beijing Beike New Material Technology Co., Ltd., number BK2020011814, lamellar stacking thickness: 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.
比表面积测试：通过ASAP2460比表面积分析仪对所获样品进行N 2吸附脱附测试，并基于BET理论计算出比表面积。 Specific surface area test: The obtained samples were tested for N adsorption and desorption by ASAP2460 specific surface area analyzer, and the specific surface area was calculated based on BET theory.
SnS2负载量：X射线能谱分析(EDS)。SnS2 loading: X-ray energy dispersive analysis (EDS).
电池性能测试：将活性物质(SnS2，MXene，SnS2/MXene)分别与导电碳黑、聚偏氟乙烯粘结剂，按质量比为8:1:1的比例进行混合，并加入适量N-甲基吡咯烷酮，搅拌均匀后涂 覆在铜箔上，经80℃真空干燥后切片，得到直径为18mm的钾离子电池负极片。将该负极极片，金属钾箔，隔膜(Whatman,GF/F)在手套箱中组装成2032型纽扣电池，并利用武汉蓝电电池测试系统进行电池性能测试。Battery performance test: Mix the active materials (SnS2, MXene, SnS2/MXene) with conductive carbon black and polyvinylidene fluoride binder in a mass ratio of 8:1:1, and add an appropriate amount of N-methyl fluoride. pyrrolidone, stir evenly, coat on copper foil, vacuum dry at 80° C. and slice to obtain a potassium ion battery negative electrode sheet with a diameter of 18 mm. The negative electrode, potassium metal foil, and separator (Whatman, GF/F) were assembled into a 2032 button battery in a glove box, and the battery performance was tested by using the Wuhan Blue Electric Battery Test System.
本发明制备一种阵列状SnS 2/MXene复合材料，其中SnS 2材料的合成方法请参见：“李欣.二硫化锡基复合材料的合成及性能研究[D].东北大学,2011.” The invention prepares an arrayed SnS 2 /MXene composite material. For the synthesis method of the SnS 2 material, please refer to: "Li Xin. Research on the synthesis and properties of tin disulfide-based composite materials [D]. Northeastern University, 2011."
实施例1Example 1
一种阵列状SnS 2/MXene复合材料的制备方法，包括以下步骤： A preparation method of an arrayed SnS 2 /MXene composite material, comprising the following steps:
(1)取30mg MXene(Ti 3C 2T x)加入到21.5ml乙醇和7.5ml乙二醇的混合溶液中，磁力搅拌8小时，配置成1mg/ml的分散液； (1) Take 30mg of MXene (Ti 3 C 2 T x ) and add it to a mixed solution of 21.5ml of ethanol and 7.5ml of ethylene glycol, stir magnetically for 8 hours, and configure a dispersion of 1 mg/ml;
(2)将0.1mol SnCl 4·5H 2O与0.3mol硫代乙酰胺(TAA)加入(1)所述分散液，并搅拌3小时，得到混合液； (2) adding 0.1 mol SnCl 4 .5H 2 O and 0.3 mol thioacetamide (TAA) to the dispersion liquid described in (1), and stirring for 3 hours to obtain a mixed solution;
(3)将步骤(2)所得混合液移入不锈钢反应釜加热至160℃并保温12小时，然后冷却至室温；(3) the mixed solution obtained in step (2) is transferred into a stainless steel reaction kettle and heated to 160° C. and kept warm for 12 hours, and then cooled to room temperature;
(4)将步骤(3)所得的目标产物在6000r/min条件下离心5分钟，用去离子水和无水乙醇交替进行清洗3次；(4) centrifuging the target product obtained in step (3) at 6000 r/min for 5 minutes, and alternately washing with deionized water and absolute ethanol for 3 times;
(5)将步骤(4)得到的产物在真空干燥箱中进行干燥，干燥温度80℃，干燥时间10小时，得到阵列状SnS2/MXene复合材料。(5) drying the product obtained in step (4) in a vacuum drying oven at a drying temperature of 80° C. and a drying time of 10 hours to obtain an arrayed SnS2/MXene composite material.
本实施例所制的阵列状SnS 2/MXene复合材料在100mA/g的电流密度下，循环200圈后的可逆容量为272.7mAh/g。 At the current density of 100 mA/g, the reversible capacity of the arrayed SnS 2 /MXene composite prepared in this example was 272.7 mAh/g after 200 cycles.
实施例2Example 2
一种阵列状SnS 2/MXene复合材料的制备方法，包括以下步骤： A preparation method of an arrayed SnS 2 /MXene composite material, comprising the following steps:
(1)取240mg MXene(Ti 3C 2T x)加入到53.3ml乙醇和26.7ml乙二醇的混合溶液中，磁力搅拌12小时，配置成3mg/ml的分散液； (1) 240 mg of MXene (Ti 3 C 2 T x ) was added to a mixed solution of 53.3 ml of ethanol and 26.7 ml of ethylene glycol, and stirred magnetically for 12 hours to form a dispersion of 3 mg/ml;
(2)将0.3mol SnCl 4·5H 2O与1.2mol硫脲加入(1)所述分散液，并搅拌3小时，得到混合液； (2) 0.3 mol SnCl 4 ·5H 2 O and 1.2 mol thiourea were added to the dispersion liquid of (1), and stirred for 3 hours to obtain a mixed liquid;
(3)将步骤(2)所得混合分散液移入不锈钢反应釜加热至120℃并保温18h，然后冷却至室温；(3) The mixed dispersion liquid obtained in step (2) is transferred into a stainless steel reactor, heated to 120° C. and kept for 18h, and then cooled to room temperature;
(4)将步骤(3)所得的目标产物在8000r/min条件下离心3分钟，用去离子水和无水 乙醇交替进行清洗三次；(4) the target product of step (3) gained is centrifuged 3 minutes under 8000r/min conditions, with deionized water and absolute ethanol alternately wash three times;
(5)将步骤(4)得到的产物在真空干燥箱中进行干燥，干燥温度70℃，干燥时间12小时，得到阵列状SnS2/MXene复合材料。(5) drying the product obtained in step (4) in a vacuum drying oven at a drying temperature of 70° C. and a drying time of 12 hours to obtain an arrayed SnS2/MXene composite material.
本实施例所制的阵列状SnS 2/MXene复合材料在100mA/g的电流密度下，循环200圈后的可逆容量为302.7mAh/g。 At the current density of 100 mA/g, the reversible capacity of the arrayed SnS 2 /MXene composite prepared in this example was 302.7 mAh/g after 200 cycles.
实施例3Example 3
一种阵列状SnS 2/MXene复合材料的制备方法，包括以下步骤： A preparation method of an arrayed SnS 2 /MXene composite material, comprising the following steps:
(1)取500mg MXene(Ti 3C 2T x)加入到50ml乙醇和12.5ml乙二醇的混合溶液中，磁力搅拌10小时，配置成8mg/ml的分散液； (1) Take 500mg of MXene (Ti 3 C 2 T x ) and add it to a mixed solution of 50 ml of ethanol and 12.5 ml of ethylene glycol, stir magnetically for 10 hours, and configure it into a dispersion of 8 mg/ml;
(2)将0.5mol SnCl 4·5H 2O与2.0mol硫代乙酰胺(TAA)加入(1)所述分散液，并搅拌3小时，得到混合液； (2) 0.5mol SnCl 4 ·5H 2 O and 2.0mol thioacetamide (TAA) were added to the dispersion liquid of (1), and stirred for 3 hours to obtain a mixed solution;
(3)将步骤(2)所得混合液移入不锈钢反应釜加热至180℃并保温10小时，然后冷却至室温；(3) the mixed solution obtained in step (2) is moved into a stainless steel reaction kettle and heated to 180° C. and kept warm for 10 hours, and then cooled to room temperature;
(4)将步骤(3)所得的目标产物在4000r/min条件下离心5分钟，用去离子水和无水乙醇交替进行清洗三次；(4) centrifuging the target product obtained in step (3) at 4000 r/min for 5 minutes, and alternately washing three times with deionized water and absolute ethanol;
(5)将步骤(4)得到的产物在真空干燥箱中进行干燥，干燥温度60℃，干燥时间16小时，得到阵列状SnS2/MXene复合材料。(5) drying the product obtained in step (4) in a vacuum drying oven at a drying temperature of 60° C. and a drying time of 16 hours to obtain an arrayed SnS2/MXene composite material.
本实施例所制的阵列状SnS 2/MXene复合材料在100mA/g的电流密度下，循环200圈后的可逆容量为215.3mAh/g。 At the current density of 100 mA/g, the reversible capacity of the arrayed SnS 2 /MXene composite prepared in this example after 200 cycles is 215.3 mAh/g.
对比例1SnS 2 Comparative Example 1SnS 2
本对比例所制的SnS 2材料在100mA/g的电流密度下，循环50圈后的可逆容量为仅为5.3mAh/g。 At a current density of 100 mA/g, the reversible capacity of the SnS 2 material prepared in this comparative example was only 5.3 mAh/g after 50 cycles.
对比例2MXene。Comparative Example 2MXene.
本对比例MXene材料在100mA/g的电流密度下，循环50圈后的可逆容量为43mAh/g。At the current density of 100 mA/g, the reversible capacity of the MXene material of this comparative example was 43 mAh/g after 50 cycles.
各组的性能测试结果请参见表1。The performance test results of each group are shown in Table 1.
表1：性能测试Table 1: Performance Testing
Figure PCTCN2020112571-appb-000002
Figure PCTCN2020112571-appb-000002
Figure PCTCN2020112571-appb-000003
Figure PCTCN2020112571-appb-000003
由图1-3可见，纯SnS 2材料呈圆球状，团聚明显；单纯的MXene材料呈片状，但是层间距较小；本发明制备的阵列状SnS 2/MXene复合材料层间距较大，SnS 2材料均匀地负载在MXene上，无团聚现象。 It can be seen from Figures 1-3 that the pure SnS 2 material is spherical and has obvious agglomeration; the pure MXene material is sheet-like, but the interlayer spacing is small ; 2 The material is uniformly loaded on MXene without agglomeration.
由表1和图4可见，与纯SnS 2材料相比，本发明制备的阵列状SnS 2/MXene复合材料通过将高比容量的SnS 2纳米片锚定在具有良好导电性的MXene表面，缓解了SnS 2在循环过程的巨大体积膨胀，并极大改善了SnS 2在循环过程中出现的团聚以及粉化现象，以解决SnS 2容量衰减问题。 It can be seen from Table 1 and Fig. 4 that, compared with pure SnS 2 materials, the array-like SnS 2 /MXene composites prepared in the present invention can alleviate the problem by anchoring the SnS 2 nanosheets with high specific capacity on the MXene surface with good electrical conductivity. The huge volume expansion of SnS 2 during the cycling process is eliminated, and the agglomeration and pulverization phenomena of SnS 2 during the cycling process are greatly improved, so as to solve the problem of SnS 2 capacity decay.
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. 一种阵列状SnS 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 an arrayed SnS 2 /MXene composite material, characterized in that it comprises the following steps:
    (1)将MXene材料加入分散剂中，充分搅拌，配制成浓度为0.1-10mg/ml的分散液；(1) Add the MXene material into the dispersant, stir well, and prepare a dispersion with a concentration of 0.1-10 mg/ml;
    (2)将锡源材料与硫源材料按照1:(2-4)的摩尔比加入步骤(1)所得分散液，充分搅拌，得到混合液；(2) adding the tin source material and the sulfur source material to the obtained dispersion liquid of step (1) according to the molar ratio of 1:(2-4), fully stirring to obtain a mixed solution;
    (3)将步骤(2)所得混合液加热至120-200℃，保温8-24小时，冷却，离心，洗涤，干燥，得到阵列状SnS 2/MXene复合材料。 (3) heating the mixed solution obtained in step (2) to 120-200° C., maintaining the temperature for 8-24 hours, cooling, centrifuging, washing and drying to obtain an arrayed SnS 2 /MXene composite material.
  2. 根据权利要求1所述的阵列状SnS 2/MXene复合材料的制备方法，其特征在于，所述MXene为Ti 3C 2T x、V 3C 2T x、Mo 3N 2T x中的一种或多种。 The method for preparing an arrayed SnS 2 /MXene composite material according to claim 1, wherein the MXene is one of Ti 3 C 2 T x , V 3 C 2 T x , and Mo 3 N 2 T x . one or more.
  3. 根据权利要求1所述的阵列状SnS 2/MXene复合材料的制备方法，其特征在于，所述锡源材料为SnCl 4、SnCl 4·5H 2O、C 12H 10Cl 2Sn中的一种或多种。 The method for preparing an arrayed SnS 2 /MXene composite material according to claim 1, wherein the tin source material is one of SnCl 4 , SnCl 4 ·5H 2 O, and C 12 H 10 Cl 2 Sn or more.
  4. 根据权利要求1所述的阵列状SnS 2/MXene复合材料的制备方法，其特征在于，所述硫源材料为硫代乙酰胺、硫脲中的一种或多种。 The method for preparing an arrayed SnS 2 /MXene composite material according to claim 1, wherein the sulfur source material is one or more of thioacetamide and thiourea.
  5. 根据权利要求1所述的阵列状SnS 2/MXene复合材料的制备方法，其特征在于，步骤(1)中所述分散剂为乙醇与乙二醇的混合溶液。 The method for preparing an arrayed SnS 2 /MXene composite material according to claim 1, wherein the dispersant in step (1) is a mixed solution of ethanol and ethylene glycol.
  6. 根据权利要求1所述的阵列状SnS 2/MXene复合材料的制备方法，其特征在于，所述SnS 2/MXene复合材料中SnS 2负载量为50-200wt％。 The method for preparing an arrayed SnS 2 /MXene composite material according to claim 1, wherein the SnS 2 loading in the SnS 2 /MXene composite material is 50-200wt%.
  7. 根据权利要求1所述的阵列状SnS 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3000-8000r/min，离心时间为5-10min。 The method for preparing an arrayed SnS 2 /MXene composite material according to claim 1, wherein in step (3), the centrifugation speed is 3000-8000 r/min, and the centrifugation time is 5-10 min.
  8. 根据权利要求1所述的阵列状SnS 2/MXene复合材料的制备方法，其特征在于，步骤(5)中的干燥为真空干燥，干燥温度为60-90℃，干燥时间8-12小时，真空度不超过150Pa。 The method for preparing an arrayed SnS 2 /MXene composite material according to claim 1, wherein the drying in step (5) is vacuum drying, the drying temperature is 60-90° C., the drying time is 8-12 hours, and the vacuum The degree does not exceed 150Pa.
  9. 一种钾离子电池负极，其特征在于，其包括权利要求1-8中任一项所述的制备方法制备得到的阵列状SnS2/MXene复合材料。A potassium ion battery negative electrode, characterized in that it comprises an arrayed SnS2/MXene composite material prepared by the preparation method according to any one of claims 1-8.
  10. 一种钾离子电池，其特征在于，其包括权利要求9所述的电池负极。A potassium ion battery, characterized in that it comprises the battery negative electrode of claim 9 .
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114904040A (en) * 2022-05-18 2022-08-16 四川大学 Lactic acid-responsive light-activated antibacterial dressing

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106025200A (en) * 2016-05-24 2016-10-12 浙江大学 Preparation method and application of nitrogen-doped MXene battery anode material
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
CN109671949A (en) * 2018-12-12 2019-04-23 福建翔丰华新能源材料有限公司 A kind of MXene base flexible compound negative electrode material and preparation method thereof
CN109830659A (en) * 2019-01-15 2019-05-31 五邑大学 A kind of Te doping MXene material and preparation method thereof
CN109888279A (en) * 2019-01-15 2019-06-14 五邑大学 A kind of selenium doping MXene material and its preparation method and application
JP6564552B1 (en) * 2018-12-28 2019-08-21 株式会社アドマテックス MXene particulate material, slurry, secondary battery, transparent electrode, method for producing MXene particulate material

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107123800A (en) * 2017-05-20 2017-09-01 西南大学 Ti3C2@SnSx（x=1、2）The preparation method of negative material
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

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106025200A (en) * 2016-05-24 2016-10-12 浙江大学 Preparation method and application of nitrogen-doped MXene battery anode material
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
CN109671949A (en) * 2018-12-12 2019-04-23 福建翔丰华新能源材料有限公司 A kind of MXene base flexible compound negative electrode material and preparation method thereof
JP6564552B1 (en) * 2018-12-28 2019-08-21 株式会社アドマテックス MXene particulate material, slurry, secondary battery, transparent electrode, method for producing MXene particulate material
CN109830659A (en) * 2019-01-15 2019-05-31 五邑大学 A kind of Te doping MXene material and preparation method thereof
CN109888279A (en) * 2019-01-15 2019-06-14 五邑大学 A kind of selenium doping MXene material and its preparation method and application

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114904040A (en) * 2022-05-18 2022-08-16 四川大学 Lactic acid-responsive light-activated antibacterial dressing
CN114904040B (en) * 2022-05-18 2023-06-13 四川大学 Lactic acid response photo-activated antibacterial dressing

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