WO2020147302A1 - 碲掺杂MXene复合材料及其制备方法和应用 - Google Patents

碲掺杂MXene复合材料及其制备方法和应用 Download PDF

Info

Publication number
WO2020147302A1
WO2020147302A1 PCT/CN2019/098954 CN2019098954W WO2020147302A1 WO 2020147302 A1 WO2020147302 A1 WO 2020147302A1 CN 2019098954 W CN2019098954 W CN 2019098954W WO 2020147302 A1 WO2020147302 A1 WO 2020147302A1
Authority
WO
WIPO (PCT)
Prior art keywords
tellurium
composite material
mxene composite
doped mxene
doped
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2019/098954
Other languages
English (en)
French (fr)
Inventor
张业龙
孙宏阳
徐晓丹
凡雨渲
汪达
张弛
宋伟东
陈梅
温锦秀
郭月
曾庆光
彭章泉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuyi University Fujian
Original Assignee
Wuyi University Fujian
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuyi University Fujian filed Critical Wuyi University Fujian
Publication of WO2020147302A1 publication Critical patent/WO2020147302A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/36—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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 specifically relates to a method for preparing a tellurium-doped MXene composite material and its application in a potassium ion battery.
  • Lithium-ion batteries have been the core direction in the field of rechargeable batteries since their birth due to their good chemical stability and electrochemical performance. However, the storage of lithium is limited and mining is difficult, and it is difficult to be widely used. In order to find alternatives to lithium-ion batteries, potassium with similar chemical properties and a larger storage capacity began to arouse researchers' interest. The research on the anode of high-performance potassium ion batteries has important scientific significance.
  • the potassium ion radius is larger than the lithium ion radius.
  • the traditional commercial graphite electrode layer has a small spacing and cannot meet the rapid deintercalation of potassium ions.
  • the MXene material is shaped like a "book page. The material has good electrical conductivity and a high specific surface area, and is suitable as a negative electrode material for potassium ion batteries.
  • the pure MXene material used as a negative electrode material for potassium ion batteries has still not satisfactory performance. Tellurium doping on MXene can increase the interlayer spacing and optimize the potassium ion diffusion channel, thereby improving the electrochemical performance of the potassium ion battery.
  • one of the objectives of the present invention is to provide a tellurium-doped MXene composite material.
  • Another object of the present invention is to provide a method for preparing the aforementioned tellurium-doped MXene composite material.
  • the present invention provides an application of tellurium-doped MXene composite material, and the tellurium-doped MXene composite material is used as a potassium ion battery.
  • a preparation method of tellurium-doped MXene composite material includes the following steps:
  • step (3) Wash the product obtained in step (2) with detergent, centrifuge, and then vacuum dry;
  • step (3) Place the dried product obtained in step (3) in a corundum ark, then transfer it to a tube furnace, under the protection of inert gas, heat to 300-500°C, keep it for 3-5 hours and then cool to room temperature, that is The tellurium doped MXene composite material is obtained.
  • the tellurium source is at least one of biphenyl ditellurium, sodium tellurite, and tellurium powder (with a particle size of 80-120 mesh, such as 100 mesh).
  • the MXene is one of Ti 3 C 2 T x , Ti 2 CT x , Ti 3 N 2 T x , V 3 C 2 T x , V 3 N 2 T x , Mo 3 N 2 T x Or more, optional Ti 3 N 2 T x , optional V 3 C 2 T x , optional V 3 N 2 T x , preferably Ti 3 C 2 T x and V 3 with a mass ratio of 4-9:1 C 2 T x , Ti 3 C 2 T x , V 3 N 2 T x and V 3 C 2 T x are optional (for example, the mass ratio is 4-9:1:1), T x is the surface functional group -O,- F or -OH.
  • the tellurium doping amount in the tellurium-doped MXene composite material is 0.5wt%-15wt%, for example, 1-13wt%, 3-11wt%, 5-12wt%, 6-10wt%.
  • the dispersant is at least one of ethanol and N,N-dimethylformamide; the detergent is water and ethanol.
  • the inert gas is Ar or N 2 .
  • the rotating speed used for centrifugation in step (3) is 4000-6000 r/min, preferably 5000 r/min, and centrifugation is 5-10 min.
  • the vacuum drying temperature in step (3) is 50-70°C, preferably 60°C, and the drying time is 5-20 hours, optionally 5, 6, 7, 8, 9, 10, 11, 12, 13, and 14. , 15, 16, 17, 18, 19, 20h, the vacuum degree does not exceed 135Pa, for example, does not exceed 133, 130, 120, 110, 100, 90Pa.
  • a tellurium-doped MXene composite material prepared by a method for preparing a tellurium-doped MXene composite material.
  • the invention uses the MXene nano material as the matrix, and prepares the tellurium-doped MXene material by a method combining hydrothermal method and heat treatment.
  • the tellurium is first doped into MXene by hydrothermal method, and then high-temperature annealing is used to uniformly diffuse the tellurium atoms and reduce the crystal stress caused by doping.
  • the hydrothermal method and heat treatment are easy to operate and can be produced on a large scale.
  • the combination of the two methods can obtain MXene materials with large lattice distortion, more uniform defect concentration, wider interlayer spacing, and richer active sites, which has broad application prospects in the field of energy storage devices.
  • the composite material prepared by the present invention can be used as a negative electrode of a potassium ion battery, increasing the interlayer spacing, optimizing ion diffusion channels, thereby improving the electrochemical performance of the potassium ion battery;
  • the preparation process of the present invention is simple, low in cost, and can be applied on a large scale.
  • Figure 1 is a scanning electron microscope image of the undoped MXene material in Comparative Example 1;
  • Example 2 is a scanning electron micrograph of the tellurium-doped MXene composite material in Example 1;
  • Example 3 is a graph showing the cycle performance of the negative electrode of the tellurium-doped MXene potassium ion battery in Example 1;
  • Figure 4 is a graph showing the cycle performance of the negative electrode of an undoped MXene potassium ion battery in Comparative Example 1;
  • Figure 5 is a graph showing the cycle performance of the negative electrode of the tellurium-doped MXene potassium ion battery in Example 2;
  • Example 6 is a graph showing the cycle performance of the negative electrode of the tellurium-doped MXene potassium ion battery in Example 3.
  • a preparation method of tellurium-doped MXene composite material includes the following steps:
  • step (2) Transfer the dispersion obtained in step (1) to a reactor with a capacity of 100ml and seal it, place it in an oven, keep it at 100°C for 10 hours, and cool to room temperature;
  • step (3) After centrifuging the product obtained in step (2) at 5000r/min for 5 minutes, it is washed with ultrapure water and absolute ethanol for 3 times and then moved to a vacuum drying oven; the drying temperature is 60°C, Drying time 5 hours;
  • step (3) Place the product obtained in step (3) in a corundum ark, transfer it to a tube furnace, heat it to 300°C at a heating rate of 5°C/min under the protection of Ar gas, keep it warm for 3 hours and then cool to room temperature , That is, tellurium doped MXene material.
  • the specific surface area of the doped MXene in this embodiment is 170.8m 2 /g, the interlayer spacing is 0.74nm, and the content of tellurium atoms is 0.2%, which is much larger than the specific surface area (38.2m 2 /g) and interlayer spacing ( 0.62nm);
  • the negative electrode of the doped MXene potassium ion battery shown in Figure 3 has a reversible capacity of 234mAh/g after 100 cycles at a current density of 100mA/g, which is the negative electrode of the undoped MXene potassium ion battery shown in Figure 4. (91.7mAh/g) 2.6 times.
  • a preparation method of tellurium-doped MXene composite material includes the following steps:
  • step (2) Transfer the dispersion obtained in step (1) to a reactor with a capacity of 50 ml and seal it and place it in an oven, keep it at 150°C for 15 hours, and cool to room temperature;
  • step (3) After centrifuging the product obtained in step (2) at 5000r/min for 5 minutes, it is washed with ultrapure water and absolute ethanol for 3 times and then moved to a vacuum drying oven; the drying temperature is 60°C, Drying time 15 hours;
  • step (3) Place the product obtained in step (3) in a corundum ark, transfer it to a tube furnace, under the protection of Ar gas, heat to 300°C at a heating rate of 5°C/min, keep it warm for 3 hours and then cool to room temperature , That is, tellurium doped MXene material.
  • the specific surface area of doped MXene in this embodiment is 300.5m 2 /g, the interlayer spacing is 0.78nm, and the content of tellurium atoms is 4%, which is much larger than the specific surface area (38.2m 2 /g) and interlayer spacing ( 0.62nm);
  • the negative electrode of the doped MXene potassium ion battery shown in Figure 5 has a reversible capacity of 312mAh/g after 100 cycles at a current density of 100mA/g, which is an undoped MXene potassium ion battery negative electrode (91.7mAh/g). g) 3.4 times.
  • a preparation method of tellurium-doped MXene composite material includes the following steps:
  • step (2) Transfer the dispersion obtained in step (1) to a reactor with a capacity of 50 ml and seal it, then place it in an oven, keep it at 220°C for 24 hours, and cool to room temperature;
  • step (3) After centrifuging the product obtained in step (2) at 5000r/min for 5 minutes, it is washed with ultrapure water and absolute ethanol for 3 times and then moved to a vacuum drying oven; the drying temperature is 60°C, Drying time 20 hours;
  • step (3) Place the product obtained in step (3) in a corundum ark, transfer it to a tube furnace, under the protection of Ar gas, heat to 300°C at a heating rate of 5°C/min, keep it warm for 3 hours and then cool to room temperature , That is, tellurium doped MXene material.
  • the specific surface area of the doped MXene in this embodiment is 254.4m 2 /g, the interlayer spacing is 0.77nm, and the tellurium atom content is 7%, which is much larger than the specific surface area (38.2m 2 /g) and interlayer spacing ( 0.62nm);
  • the negative electrode of the doped MXene potassium ion battery shown in Figure 6 has a reversible capacity of 308mAh/g after 100 cycles at a current density of 100mA/g, which is an undoped MXene potassium ion battery negative electrode (91.7mAh/g). g) 3.3 times.
  • a preparation method of tellurium-doped MXene composite material includes the following steps:
  • step (2) Transfer the dispersion obtained in step (1) to a reactor with a capacity of 50 ml and seal it, then place it in an oven, keep it at 180°C for 16 hours, and cool to room temperature;
  • step (3) After centrifuging the product obtained in step (2) at 5000r/min for 5 minutes, it is washed with ultrapure water and absolute ethanol for 3 times and then moved to a vacuum drying oven; the drying temperature is 60°C, Drying time 5 hours;
  • step (3) Place the product obtained in step (3) in a corundum ark, transfer it to a tube furnace, under the protection of Ar gas, heat to 300°C at a heating rate of 4°C/min, keep it warm for 3 hours and then cool to room temperature , That is, tellurium doped MXene material.
  • the reversible capacity of the doped MXene potassium ion battery negative electrode in this embodiment at a current density of 100mA/g after 100 cycles is 334mAh/g, which is 3.6 of that of the undoped MXene potassium ion battery negative electrode (91.7mAh/g) Times.
  • step (2) Transfer the dispersion obtained in step (1) to a reactor with a capacity of 50 ml and seal it, then place it in an oven, keep it at 120°C for 11 hours, and cool to room temperature;
  • step (3) After centrifuging the product obtained in step (2) at 5000r/min for 5 minutes, it is washed with ultrapure water and absolute ethanol for 3 times and then moved to a vacuum drying oven; the drying temperature is 60°C, Drying time is 6 hours;
  • step (3) Place the product obtained in step (3) in a corundum ark, transfer it to a tube furnace, heat it to 300°C at a heating rate of 6°C/min under the protection of Ar gas, keep it warm for 3 hours and then cool to room temperature , That is, tellurium doped MXene material.
  • the reversible capacity of the doped MXene potassium ion battery negative electrode in this example after 100 cycles is 347mAh/g, which is 3.8 of that of the undoped MXene potassium ion battery negative electrode (91.7mAh/g). Times.
  • Comparative Example 1 The anode of MXene potassium ion battery was not doped, and the process of preparing the anode of potassium ion battery was the same as that in Example 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

本发明公开了一种碲掺杂MXene复合材料及其制备方法，包括以下步骤：(1)将MXene和碲源按照质量比为1：0.01～1加入分散剂中，配制成浓度为1-100mg/ml的分散液，然后搅拌1-5小时；(2)将所述分散液升温至100-220℃，反应10-24h，然后冷却至室温；(3)将步骤(2)所得的产物离心后，用洗涤剂进行洗涤，然后真空干燥；(4)将步骤(3)得到的干燥产物放置在刚玉方舟中，然后转移到管式炉中，在惰性气体保护下，加热至300-500℃，保温3-5小时后冷至室温，即得到碲掺杂MXene复合材料。本发明制备的复合材料可用作钾离子电池负极，增大层间距，优化离子扩散通道，从而提高钾离子电池的电化学性能。

Description

碲掺杂MXene复合材料及其制备方法和应用 技术领域
本发明属于新能源技术领域，具体涉及一种碲掺杂MXene复合材料的制备方法及其在钾离子电池中的应用。
背景技术
随着工业水平的不断提高，能源问题日益突出，一方面，传统化石能源存储量有限，能源利用率低下，另一方面，人们环保意识的不断提高，传统化石燃料带来的污染越发难以忍受，人们迫切需要新型绿色能源来代替传统能源，在这一历史背景下，各国纷纷发力发展新型绿色能源，争夺新能源技术领域高地。
锂离子电池因其良好的化学稳定性及电化学性能，自诞生开始就是可充放电池领域核心方向，然而锂的存储有限，开采难度较大，难以广泛应用。为寻找锂离子电池的替代品，化学性质相近，储存量更大的钾开始引起研究者的兴趣。对于高性能钾离子电池负极的研究具有重要的科学意义。
钾离子半径大于锂离子半径，传统的商用石墨电极层间距较小而不能满足钾离子的快速脱嵌，MXene材料作为一种新型二维层状材料，形似“书页状”。该材料具有良好的导电性，较高的比表面积，适合作为钾离子电池负极材料。但单纯的MXene材料用作钾离子电池负极材料，性能仍不能令人满意。通过对MXene进行碲掺杂可增大层间距，优化钾离子扩散通道，从而提高钾离子电池的电化学性能。
发明内容
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碲掺杂MXene复合材料。本发明的另一目的在于提供上述碲掺杂MXene复合材料的制备方法。进一步的，本发明提供一种碲掺杂MXene复合材料的应用，将所述碲掺杂MXene复合材料用作钾离子电池。
本发明采用以下技术方案：
一种碲掺杂MXene复合材料的制备方法，包括以下步骤：
(1)将MXene和碲源按照质量比为1：(0.01～1)，可选1：(0.1～0.9)，可选1：(0.2～0.8)，可选1：(0.4～0.6)加入分散剂中，配制成浓度为1-100mg/ml，可选10-90mg/ml，可选20-80mg/ml，可选40-60mg/ml的分散液，然后搅拌1-5小时，可选1、2、3、4、5h；
(2)将所述分散液移入反应釜中密封后放置烘箱升温至100-220℃，反应10-24h，然后冷却至室温；
(3)将步骤(2)所得的产物用洗涤剂洗涤后离心，然后真空干燥；
(4)将步骤(3)得到的干燥产物放置在刚玉方舟中，然后转移到管式炉中，在惰性气体保护下，加热至300-500℃，保温3-5小时后冷至室温，即得到碲掺杂MXene复合材料。
进一步地，所述碲源为联苯二碲、亚碲酸钠、碲粉(粒径为80-120目，例如100目)中的至少一种。
进一步地，所述MXene为Ti 3C 2T x、Ti 2CT x、Ti 3N 2T x、V 3C 2T x、V 3N 2T x、Mo 3N 2T x中的一种或多种，可选Ti 3N 2T x，可选V 3C 2T x，可选V 3N 2T x，优选质量比为4～9：1的Ti 3C 2T x和V 3C 2T x，可选Ti 3C 2T x、V 3N 2T x和V 3C 2T x(例如质量比为4～9：1：1)，T x为表面官能团-O、-F或-OH。
进一步地，所述碲掺杂MXene复合材料中碲掺杂量为0.5wt％-15wt％，例如1-13wt％，3-11wt％，5-12wt％，6-10wt％。
进一步地，所述分散剂为乙醇、N,N-二甲基甲酰胺中的至少一种；所述洗涤剂为水和乙醇。
进一步地，所述惰性气体为Ar或N 2。
进一步地，步骤(3)中所述离心使用的转速为4000-6000r/min，优选5000r/min，离心5-10min。
进一步地，步骤(3)中真空干燥的温度为50-70℃，优选60℃，干燥时间5-20小时，可选5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20h，真空度不超过135Pa，例如不超过133、130、120、110、100、90Pa。
一种碲掺杂MXene复合材料的制备方法制备得到的碲掺杂MXene复合材料。
一种碲掺杂MXene复合材料的应用，将所述碲掺杂MXene复合材料用于钾离子电池。
本发明以MXene纳米材料为基体，通过水热法和热处理相结合的方法制备碲掺杂的MXene材料。相比所报道其它方法掺杂元素，先通过水热法使碲元素掺入MXene，然后通过高温退火，使碲原子均匀扩散，同时减少因掺杂带来的晶体应力。水热法和热处理操作简单，可大规模生产。通过两种方法相结合方法能得到晶格畸变更大，缺陷浓度更均匀、层间距更宽、活性位点更丰富的MXene材料，在储能器件领域应用前景广阔。
本发明的有益效果：
(1)本发明制备的复合材料可用作钾离子电池负极，增大层间距，优化离子扩散通道，从而提高钾离子电池的电化学性能；
(2)本发明的制备工艺简单、成本低，可以大规模应用。
附图说明
图1是对比例1中未掺杂MXene材料的扫描电镜图；
图2是实施例1中碲掺杂MXene复合材料的扫描电镜图；
图3是实施例1中碲掺杂MXene钾离子电池负极循环性能图；
图4是对比例1中未掺杂MXene钾离子电池负极循环性能图；
图5为实施列2中碲掺杂MXene钾离子电池负极循环性能图；
图6为实施列3中碲掺杂MXene钾离子电池负极循环性能图。
具体实施方式
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。
实施例1
一种碲掺杂MXene复合材料的制备方法，包括以下步骤：
(1)取50mg MXene(Ti 3C 2T x)和0.5mg的联苯二碲加入到乙醇中，配置成1mg/ml的乙醇分散液，磁力搅拌1小时；
(2)将步骤(1)得到的分散液移至容量为100ml反应釜中密封后放置在烘箱中，于100℃下保温10小时，冷却至室温；
(3)将步骤(2)得到的产物用离心机在5000r/min条件下离心5分钟后，用超纯水和无水乙醇分别洗涤3次后移至真空干燥箱；干燥温度为60℃，干燥时间5小时；
(4)将步骤(3)得到的产物放置在刚玉方舟中，转移到管式炉中，在Ar气体保护下，以5℃/min的升温速率加热至300℃，保温3小时后冷至室温，即得到碲掺杂MXene材料。
(5)将(4)所得的碲掺杂MXene与碳黑、粘结剂按8:1:1的比例(质量比)混合，均匀涂覆在集流体上，经真空干燥、切片后，用于钾离子电池负极；
本实施例掺杂后的MXene比表面积为170.8m 2/g，层间距为0.74nm，碲原子含量为0.2％，远大于未掺杂MXene的比表面积(38.2m 2/g)、层间距(0.62nm)；图3所示掺杂的MXene钾离子电池负极在100mA/g的电流密度下，循环100圈后的可逆容量为234mAh/g，是图4所示未掺杂MXene钾离子电池负极(91.7mAh/g)的2.6倍。
实施例2
一种碲掺杂MXene复合材料的制备方法，包括以下步骤：
(1)取1000mg MXene(Ti 3C 2T x)和500mg的联苯二碲加入到乙醇中，配置成50mg/ml的乙醇分散液，磁力搅拌3小时；
(2)将步骤(1)得到的分散液移至容量为50ml反应釜中密封后放置在烘箱中，于150℃下保温15小时，冷却至室温；
(3)将步骤(2)得到的产物用离心机在5000r/min条件下离心5分钟后，用超纯水和无水乙醇分别洗涤3次后移至真空干燥箱；干燥温度为60℃，干燥时间15小时；
(4)将步骤(3)得到的产物放置在刚玉方舟中，转移到管式炉中，在Ar气体保护下，以5℃/min的升温速率加热至300℃，保温3小时后冷至室温，即得到碲掺杂MXene材料。
(5)将(4)所得的碲掺杂MXene与碳黑、粘结剂按8:1:1的比例(质量比)混合，均匀涂覆在集流体上，经真空干燥、切片后，用于钾离子电池负极；
本实施例掺杂后的MXene比表面积为300.5m 2/g，层间距为0.78nm，碲原子含量为4％，远大于未掺杂MXene的比表面积(38.2m 2/g)、层间距(0.62nm)；图5所示掺杂的MXene钾离子电池负极在100mA/g的电流密度下，循环100圈后的可逆容量为312mAh/g，是未掺杂MXene钾离子电池负极(91.7mAh/g)的3.4倍。
实施例3
一种碲掺杂MXene复合材料的制备方法，包括以下步骤：
(1)取2000mg MXene(Ti 3C 2T x)和2000mg的亚碲酸钠加入到乙醇中，配置成100mg/ml的乙醇分散液，磁力搅拌5小时；
(2)将步骤(1)得到的分散液移至容量为50ml反应釜中密封后放置在烘箱中，于220℃下保温24小时，冷却至室温；
(3)将步骤(2)得到的产物用离心机在5000r/min条件下离心5分钟后，用超纯水和无水乙醇分别洗涤3次后移至真空干燥箱；干燥温度为60℃，干燥时间20小时；
(4)将步骤(3)得到的产物放置在刚玉方舟中，转移到管式炉中，在Ar气体保护下，以5℃/min的升温速率加热至300℃，保温3小时后冷至室温，即得到碲掺杂MXene材料。
(5)将(3)所得的碲掺杂MXene与碳黑、粘结剂按8:1:1的比例(质量比)混合，均匀涂覆在集流体上，经真空干燥、切片后，用于钾离子电池负极；
本实施例掺杂后的MXene比表面积为254.4m 2/g，层间距为0.77nm，碲原子含量为7％，远大于未掺杂MXene的比表面积(38.2m 2/g)、层间距(0.62nm)；图6所示掺杂的MXene钾离子电池负极在100mA/g的电流密度下，循环100圈后的可逆容量为308mAh/g，是未掺杂MXene钾离子电池负极(91.7mAh/g)的3.3倍。
实施例4
一种碲掺杂MXene复合材料的制备方法，包括以下步骤：
(1)取1000mg MXene(900mg Ti 3C 2T x和100mg V 3C 2T x)和500mg的联苯二碲加入到乙醇中，配置成50mg/ml的乙醇分散液，磁力搅拌3小时；
(2)将步骤(1)得到的分散液移至容量为50ml反应釜中密封后放置在烘箱中，于180℃ 下保温16小时，冷却至室温；
(3)将步骤(2)得到的产物用离心机在5000r/min条件下离心5分钟后，用超纯水和无水乙醇分别洗涤3次后移至真空干燥箱；干燥温度为60℃，干燥时间5小时；
(4)将步骤(3)得到的产物放置在刚玉方舟中，转移到管式炉中，在Ar气体保护下，以4℃/min的升温速率加热至300℃，保温3小时后冷至室温，即得到碲掺杂MXene材料。
(5)将(4)所得的碲掺杂MXene与碳黑、粘结剂按8:1:1的比例(质量比)混合，均匀涂覆在集流体上，经真空干燥、切片后，用于钾离子电池负极；
本实施例掺杂后的MXene钾离子电池负极在100mA/g的电流密度下，循环100圈后的可逆容量为334mAh/g，是未掺杂MXene钾离子电池负极(91.7mAh/g)的3.6倍。
实施例5
(1)取1000mg MXene(V 3C 2T x)和400mg的联苯二碲加入到乙醇中，配置成50mg/ml的乙醇分散液，磁力搅拌3小时；
(2)将步骤(1)得到的分散液移至容量为50ml反应釜中密封后放置在烘箱中，于120℃下保温11小时，冷却至室温；
(3)将步骤(2)得到的产物用离心机在5000r/min条件下离心5分钟后，用超纯水和无水乙醇分别洗涤3次后移至真空干燥箱；干燥温度为60℃，干燥时间6小时；
(4)将步骤(3)得到的产物放置在刚玉方舟中，转移到管式炉中，在Ar气体保护下，以6℃/min的升温速率加热至300℃，保温3小时后冷至室温，即得到碲掺杂MXene材料。
(5)将(4)所得的碲掺杂MXene与碳黑、粘结剂按8:1:1的比例(质量比)混合，均匀涂覆在集流体上，经真空干燥、切片后，用于钾离子电池负极；
本实施例掺杂后的MXene钾离子电池负极在100mA/g的电流密度下，循环100圈后的可逆容量为347mAh/g，是未掺杂MXene钾离子电池负极(91.7mAh/g)的3.8倍。
对比例1：未掺杂MXene钾离子电池负极，制备钾离子电池负极的过程同实施例2。
表1：性能测试
Figure PCTCN2019098954-appb-000001
Figure PCTCN2019098954-appb-000002
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。

Claims (10)

  1. 一种碲掺杂MXene复合材料的制备方法，其特征在于，包括以下步骤：
    (1)将MXene和碲源按照质量比为1：0.01～1加入分散剂中，配制成浓度为1-100mg/ml的分散液，然后搅拌1-5小时；
    (2)将所述分散液移入反应釜后升温至100-220℃，反应10-24h，然后冷却至室温；
    (3)将步骤(2)所得的产物用洗涤剂洗涤后离心，然后进行真空干燥；
    (4)将步骤(3)得到的干燥产物放置在刚玉方舟中，然后转移到管式炉中，在惰性气体保护下，加热至300-500℃，保温3-5小时后冷至室温，即得到碲掺杂MXene复合材料。
  2. 根据权利要求1所述的碲掺杂MXene复合材料的制备方法，其特征在于，所述碲源为联苯二碲、亚碲酸钠、碲粉中的至少一种。
  3. 根据权利要求1所述的碲掺杂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、Ti 3N 2T x、V 3C 2T x、V 3N 2T x、Mo 3N 2T x中的一种或多种。
  4. 根据权利要求1所述的碲掺杂MXene复合材料的制备方法，其特征在于，所述碲掺杂MXene复合材料中碲掺杂量为0.5wt％-15wt％。
  5. 根据权利要求1所述的碲掺杂MXene复合材料的制备方法，其特征在于，所述分散剂为乙醇、N,N-二甲基甲酰胺中的至少一种；所述洗涤剂为水和乙醇。
  6. 根据权利要求1所述的碲掺杂MXene复合材料的制备方法，其特征在于，所述惰性气体为Ar或N 2。
  7. 根据权利要求1所述的碲掺杂MXene复合材料的制备方法，其特征在于，步骤(3)中所述离心使用的转速为4000-6000r/min，离心5-10min。
  8. 根据权利要求1所述的碲掺杂MXene复合材料的制备方法，其特征在于，步骤(3)中真空干燥的温度为50-70℃，干燥时间5-20小时，真空度不超过135Pa。
  9. 一种碲掺杂MXene复合材料，其特征在于，所述碲掺杂MXene复合材料由权利要求1-8中任一项所述的制备方法制备得到。
  10. 一种根据权利要求9所述的碲掺杂MXene复合材料的应用，其特征在于，将所述碲掺杂MXene复合材料用于钾离子电池。
PCT/CN2019/098954 2019-01-16 2019-08-02 碲掺杂MXene复合材料及其制备方法和应用 Ceased WO2020147302A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910038426.9A CN109888203B (zh) 2019-01-16 2019-01-16 碲掺杂MXene复合材料及其制备方法和应用
CN201910038426.9 2019-01-16

Publications (1)

Publication Number Publication Date
WO2020147302A1 true WO2020147302A1 (zh) 2020-07-23

Family

ID=66926079

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/098954 Ceased WO2020147302A1 (zh) 2019-01-16 2019-08-02 碲掺杂MXene复合材料及其制备方法和应用

Country Status (3)

Country Link
US (1) US10847798B2 (zh)
CN (1) CN109888203B (zh)
WO (1) WO2020147302A1 (zh)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109830659B (zh) * 2019-01-15 2022-01-04 五邑大学 一种Te掺杂MXene材料及其制备方法
CN109888279B (zh) * 2019-01-15 2022-01-04 五邑大学 一种硒掺杂MXene材料及其制备方法和应用
CN109888203B (zh) * 2019-01-16 2022-01-04 五邑大学 碲掺杂MXene复合材料及其制备方法和应用
CN111740106A (zh) * 2020-07-02 2020-10-02 北京理工大学 一种碘修饰MXene材料及其制备方法与应用
CN112018346A (zh) * 2020-08-10 2020-12-01 五邑大学 一种磷掺杂CoSe2/Mxene复合材料及其制备方法
CN112018349B (zh) * 2020-08-12 2022-04-08 五邑大学 一种CoTe2/MXene复合材料及其制备方法
CN112072101A (zh) * 2020-08-14 2020-12-11 五邑大学 一种硼掺杂MXene材料及其制备方法
CN114644338A (zh) * 2020-12-21 2022-06-21 苏州北科纳米科技有限公司 一种MXene量子点药物负载体系制备方法
CN114838851B (zh) * 2021-01-30 2024-04-02 苏州北科纳米科技有限公司 一种MXene柔性微力传感器的制备方法
CN113277554A (zh) * 2021-05-21 2021-08-20 厦门理工学院 一种氧化铋/碳化钛复合材料及其制备方法
CN113488638B (zh) * 2021-06-30 2022-12-23 肇庆市华师大光电产业研究院 一种高导电强吸附的锂硫电池正极材料制备方法
CN114400340B (zh) * 2022-01-19 2023-12-22 中原工学院 氮硫共掺杂纳米碳管复合材料及其制备方法和应用
CN115282787A (zh) * 2022-01-21 2022-11-04 浙江师范大学 具有光催化自清洁功能的复合分离膜及其制备方法和应用
CN116190637A (zh) * 2023-02-15 2023-05-30 东南大学 一种钾离子电池负极复合材料的制备方法及其所得材料
CN116613318B (zh) * 2023-06-09 2024-02-20 广东格林赛福能源科技有限公司 CoSe/Te复合材料、制备方法及应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106025236A (zh) * 2016-07-21 2016-10-12 陕西科技大学 一种S-SnO2/Ti3C2二维纳米锂离子电池负极材料及其制备方法
CN107579235A (zh) * 2017-09-12 2018-01-12 哈尔滨工业大学 一种应用于锂硫电池正极的氧化Mxene /S复合物的制备方法
CN109830659A (zh) * 2019-01-15 2019-05-31 五邑大学 一种Te掺杂MXene材料及其制备方法
CN109888203A (zh) * 2019-01-16 2019-06-14 五邑大学 碲掺杂MXene复合材料及其制备方法和应用

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106025200B (zh) * 2016-05-24 2019-07-30 浙江大学 一种氮掺杂MXene电池负极材料的制备方法及其应用
CN106450205B (zh) * 2016-11-02 2020-02-21 南京工业大学 二维过渡族金属碳/氮化物与纳米硫颗粒复合材料及其制备和应用
CN107123800A (zh) * 2017-05-20 2017-09-01 西南大学 Ti3C2@SnSx（x=1、2）负极材料的制备方法
CN107200318A (zh) * 2017-06-02 2017-09-26 国家纳米科学中心 二维材料量子片及其制备方法
CN108516528B (zh) * 2018-04-12 2019-11-08 大连理工大学 一种基于三维MXene的三维复合结构及其通用合成方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106025236A (zh) * 2016-07-21 2016-10-12 陕西科技大学 一种S-SnO2/Ti3C2二维纳米锂离子电池负极材料及其制备方法
CN107579235A (zh) * 2017-09-12 2018-01-12 哈尔滨工业大学 一种应用于锂硫电池正极的氧化Mxene /S复合物的制备方法
CN109830659A (zh) * 2019-01-15 2019-05-31 五邑大学 一种Te掺杂MXene材料及其制备方法
CN109888203A (zh) * 2019-01-16 2019-06-14 五邑大学 碲掺杂MXene复合材料及其制备方法和应用

Also Published As

Publication number Publication date
US20200227745A1 (en) 2020-07-16
US10847798B2 (en) 2020-11-24
CN109888203B (zh) 2022-01-04
CN109888203A (zh) 2019-06-14

Similar Documents

Publication Publication Date Title
WO2020147302A1 (zh) 碲掺杂MXene复合材料及其制备方法和应用
WO2020147288A1 (zh) 硒掺杂MXene复合纳米材料及其制备方法和应用
CN108711611B (zh) 一种三维高密度的金属纳米颗粒/石墨烯多孔复合材料及其制备方法和应用
CN109817918B (zh) 硫掺杂MXene复合材料及其制备方法和应用
CN107706360A (zh) 一种锂离子电池复合负极材料的制备方法
WO2020147299A1 (zh) 一种Te掺杂MXene材料及其制备方法
CN108321378B (zh) 一种具有异质结界面效应的金属氧化物@金属复合物/石墨烯核壳半导体材料的制备方法
CN109888279B (zh) 一种硒掺杂MXene材料及其制备方法和应用
CN103700829B (zh) 二氧化钛(b)-石墨烯自卷绕纳米复合材料的制备方法
CN102983321B (zh) 一种一维壳核结构碳包覆MnOx纳米储能材料及其制备方法
CN106634855A (zh) 一种混杂石墨烯凝胶/相变导热复合材料的制备方法
WO2020147290A1 (zh) 一种碲掺杂MXene材料及其制备方法和应用
WO2020147295A1 (zh) 一种Se掺杂MXene电池负极材料及其制备方法和应用
CN115947336A (zh) 钠离子电池及其改性硬碳负极
CN108735983A (zh) 一种金属纳米颗粒负载于石墨烯水凝胶复合材料及其制备方法和应用
CN111048754A (zh) 一种锡掺杂金红石TiO2复合材料的制备方法及其应用
CN109003827B (zh) 一种海绵状石墨烯/镍钴硫化物复合材料的制备方法和应用
CN110061215A (zh) 一种用于锂离子电池负极的复合结构及其制备方法
CN110649258B (zh) 一种三维多孔氧化锡石墨烯复合电极材料的制备方法
CN115799518B (zh) 铋/氧化铋纳米点/碳片复合材料、制备方法及其应用
CN111180686A (zh) 一种柔性自支撑硅基锂离子电池负极材料的制备方法
CN108155374A (zh) 一种铝离子掺杂的介孔二氧化钛锂电池负极材料及其制备方法
CN110828796B (zh) 一种蛋黄壳结构钾离子电池负极材料及其制备方法
CN107394173A (zh) 石墨烯‑Co2V2O7复合材料及其制备方法和用途
CN108155356B (zh) 一种碳包裹二氧化钛气凝胶锂离子电池负极材料及其制备方法

Legal Events

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

Ref document number: 19909937

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19909937

Country of ref document: EP

Kind code of ref document: A1