WO2020147294A1 - 一种硒掺杂MXene材料及其制备方法和应用 - Google Patents

一种硒掺杂MXene材料及其制备方法和应用 Download PDF

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WO2020147294A1
WO2020147294A1 PCT/CN2019/098136 CN2019098136W WO2020147294A1 WO 2020147294 A1 WO2020147294 A1 WO 2020147294A1 CN 2019098136 W CN2019098136 W CN 2019098136W WO 2020147294 A1 WO2020147294 A1 WO 2020147294A1
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selenium
mxene material
doped mxene
doped
preparation
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张业龙
徐晓丹
孙宏阳
陈浩
汪达
张弛
宋伟东
郭月
刘争
陈梅
温锦秀
曾庆光
彭章泉
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Wuyi University Fujian
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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
    • H01M4/58—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
    • 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

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  • the invention belongs to the technical field of nanomaterials, and relates to a selenium-doped MXene material and a preparation method and application thereof, especially its application as an electrode material in a potassium ion battery.
  • lithium-ion batteries have been widely used in people's daily lives, and the massive consumption of metal lithium has also begun to cause people's concerns. Therefore, finding an alternative to lithium-ion batteries has become the current research focus.
  • Potassium resources are rich in reserves on the earth, accounting for 2.09% of the earth's crust, which is more than 1,000 times that of lithium resources (0.0017%), and the price is relatively low.
  • Potassium ion batteries can meet the needs of the energy storage field because of their low cost, long cycle life, high energy density, and good rate performance. They are potential secondary batteries. Based on the above advantages, potassium ion secondary battery technology is considered to be a promising large-scale electrochemical energy storage technology in the future. Therefore, the development of low-cost potassium ion batteries with good cycle performance has great commercial value.
  • one of the objectives of the present invention is to provide a selenium-doped MXene material.
  • Another object of the present invention is to provide a method for preparing the above-mentioned selenium-doped MXene material.
  • the present invention provides an application of selenium-doped MXene material, which is used as a negative electrode of a potassium ion battery.
  • a preparation method of selenium-doped MXene material is a solvothermal method and includes the following steps:
  • step (3) Wash the product obtained in step (2) with a cleaning agent and centrifuge, collect the precipitate, and vacuum dry for 8-24 h, for example, 16 h, to obtain the selenium-doped MXene material.
  • the organic selenium source is at least one of dimethyl selenium, dibenzyl diselenol, and selenophenol, preferably dimethyl selenium or selenophenol, preferably with a mass ratio of 3 to 5:1 Dimethyl selenium and dibenzyl diselenide.
  • the MXene is Ti 2 NT x, Mo 2 NT x, V 2 NT x, Ti 2 CT x, Mo 2 CT x, V 2 CT x of one or more, alternatively V 2 CT x , Optional Mo 2 NT x , optional V 2 NT x , optional Ti 2 CT x and V 2 NT x with a mass ratio of 4-6:1, Ti 2 CT with a mass ratio of 4-6:1 x and Mo 2 CT x , Ti 2 CT x , Mo 2 CT x and V 2 CT x are optional (for example, the mass ratio is 5 ⁇ 8:2:1), T x is the surface functional group -O, -F or -OH .
  • the dispersant is at least one of N,N-dimethylformamide and ethanol.
  • the cleaning agent is at least one of water and ethanol.
  • the precipitate is thoroughly washed with deionized water and absolute ethanol, and the precipitate can be washed alternately with deionized water and absolute ethanol 2-15 times, preferably 3-8 times.
  • the amount of selenium doped in the selenium-doped MXene material is 0.3-8wt% (for example, 1, 2, 3, 4, 5, 6, 7, 8wt%).
  • stirring time in step (1) is 1-6h, and 2, 3, 4, 5, 6h can be selected.
  • the dispersion liquid in step (2) is heated to 110-200°C, preferably 130-180°C, optionally 140°C, 150°C, 160°C, 170°C, and reacted for 12-30 hours, optionally 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28h.
  • the rotating speed used for centrifugation in step (3) is 4000-6000 revolutions per minute, preferably 5000 revolutions per minute.
  • the temperature of vacuum drying is 50-70°C, preferably 60°C, and the vacuum degree does not exceed 133 Pa, for example, does not exceed 130, 120, 110, 100, 90 Pa.
  • a selenium-doped MXene material is prepared by a method for preparing a selenium-doped MXene material.
  • the selenium-doped MXene material is used as a negative electrode of a potassium ion battery.
  • MXene is a new type of transition metal carbide or carbonitride two-dimensional layered crystal. This type of material has a structure similar to graphene. MXene material has good conductivity, high specific surface area, low ion diffusion resistance, low open circuit voltage and high storage capacity. At the same time, it can well combine battery behavior with pseudocapacitance behavior, thereby further increasing capacity . After selenium doping, part of the C and N atoms in MXene are replaced by Se atoms, and the surface has a large number of defects, which further improves the specific capacity, rate performance, cycle stability, etc., and is more suitable for use as a potassium ion battery anode material.
  • the composite material prepared by the present invention has a higher specific surface area, good conductivity, cycle stability, rate performance and higher theoretical specific capacity, and the preparation method is simple, the cost is low, and it is suitable for large potassium ion batteries. Scale development and application;
  • the preparation device of the present invention is mature, simple in process, readily available in raw materials, high in production efficiency, and convenient for large-scale industrial production applications.
  • 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 selenium-doped MXene material in Example 1;
  • Example 3 is a graph showing the cycle performance of the negative electrode of the selenium-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;
  • Example 5 is a graph showing the cycle performance of the negative electrode of the selenium-doped MXene potassium ion battery in Example 2;
  • Example 6 is a graph showing the cycle performance of the negative electrode of the selenium-doped MXene potassium ion battery in Example 3.
  • a preparation method of selenium-doped MXene material includes the following steps:
  • step (2) Transfer the dispersion obtained in step (1) to a 100ml reactor, and put it in an oven, react at 110°C for 12 hours, and cool to room temperature naturally;
  • step (3) Collect the product obtained in step (2), wash thoroughly with deionized water and absolute ethanol, centrifuge, and then vacuum dry at 60° C. for 8 hours to obtain the selenium-doped MXene material.
  • the specific surface area of the doped MXene in this embodiment is 210.2m 2 /g, the interlayer spacing is 0.72nm, and the selenium atom content is 0.3%, which is much larger than the specific surface area (50.8m 2 /g) and interlayer spacing ( 0.60nm);
  • the negative electrode of the selenium-doped MXene potassium ion battery shown in Figure 3 has a reversible capacity of 215mAh/g after 100 cycles at a current density of 100mA/g, which is the undoped potassium MXene shown in Figure 4
  • the negative electrode (116.3mAh/g) of the ion battery is 1.85 times, and the doped MXene material of this embodiment has very stable charge-discharge cycle characteristics.
  • a method for preparing a selenium-doped MXene material is to prepare the selenium-doped MXene material at a mass ratio of 0.5:1 between the MXene material and dimethyl selenium, including the following steps:
  • step (2) Transfer the dispersion obtained in step (1) to a 50ml reactor, and put it in an oven, react at 180°C for 18h, and cool to room temperature naturally;
  • step (3) Collect the product obtained in step (2), wash thoroughly with deionized water and absolute ethanol, centrifuge, and then vacuum dry at 60° C. for 16 hours to obtain the selenium-doped MXene material.
  • the specific surface area of the doped MXene in this embodiment is 350.5m 2 /g, the interlayer spacing is 0.76nm, and the selenium atom content is 5%, which is much larger than the specific surface area (50.8m 2 /g) and interlayer spacing ( 0.60nm);
  • the negative electrode of the selenium-doped MXene potassium ion battery shown in Figure 5 has a reversible capacity of 341mAh/g after 100 cycles at a current density of 100mA/g, which is an undoped MXene potassium ion battery negative electrode (116.3 mAh/g) is 2.7 times, and the doped MXene material of this embodiment has very stable charge-discharge cycle characteristics.
  • a preparation method of selenium-doped MXene material includes the following steps:
  • step (2) Transfer the dispersion obtained in step (1) to a 50ml reactor, and put it in an oven, react at 230°C for 30h, and cool to room temperature naturally;
  • step (3) Collect the product obtained in step (2), wash it thoroughly with deionized water and absolute ethanol, centrifuge, and then vacuum dry at 60° C. for 24 hours to obtain the selenium-doped MXene material.
  • the specific surface area of the doped MXene in this embodiment is 301.7m 2 /g, the interlayer spacing is 0.79nm, and the selenium atom content is 8%, which is much larger than the specific surface area (50.8m 2 /g) and interlayer spacing ( 0.60nm);
  • the negative electrode of the selenium-doped MXene potassium ion battery has a reversible capacity of 300mAh/g after 100 cycles at a current density of 100mA/g, which is an undoped MXene potassium ion battery negative electrode ( 116.3 mAh/g), and the doped MXene material of this embodiment has very stable charge-discharge cycle characteristics.
  • a preparation method of selenium-doped MXene material is prepared by the MXene material and the organic selenium source at a mass ratio of 0.4:1, including the following steps:
  • step (2) Transfer the dispersion obtained in step (1) to a 50ml reactor, and place it in an oven, react at 190°C for 10 hours, and cool to room temperature naturally;
  • step (3) Collect the product obtained in step (2), wash thoroughly with deionized water and absolute ethanol, centrifuge, and then vacuum dry at 60° C. for 16 hours to finally obtain the selenium-doped MXene material.
  • the reversible capacity of the negative electrode of the doped MXene potassium ion battery in this embodiment at a current density of 100 mA/g after 100 cycles is 401 mAh/g, which is 3.5 of that of the non-doped MXene potassium ion battery negative electrode (116.3 mAh/g).
  • the doped MXene material of this embodiment has very stable charge-discharge cycle performance.
  • a preparation method of selenium-doped MXene material includes the following steps:
  • step (2) Transfer the dispersion obtained in step (1) to a 50ml reactor, and place it in an oven, react at 170°C for 13 hours, and cool to room temperature naturally;
  • step (3) Collect the product obtained in step (2), wash thoroughly with deionized water and absolute ethanol, centrifuge, and then vacuum dry at 60° C. for 16 hours to obtain the selenium-doped MXene material.
  • the reversible capacity of the negative electrode of the doped MXene potassium ion battery in this embodiment after 100 cycles is 387mAh/g, which is 3.3 of the negative electrode of the undoped MXene potassium ion battery (116.3mAh/g).
  • the doped MXene material of this embodiment has very stable charge-discharge cycle characteristics.
  • Comparative Example 1 Undoped MXene potassium ion battery negative electrode.
  • Comparative Example 2 Use inorganic selenium source (such as selenium powder) to dope MXene potassium ion battery negative electrode, and the doping process is the same as in Example 2.
  • inorganic selenium source such as selenium powder

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Abstract

一种硒掺杂MXene材料及其制备方法，包括以下步骤：(1)将MXene和有机硒源按照质量比为0.1～1∶1加入分散剂中，搅拌配制成浓度为10-100mg/ml的分散液；(2)将所述分散液转移至反应釜，升温至110-230℃，反应10-30h，然后冷却至室温；(3)将步骤(2)所得产物用清洗剂洗涤后离心，收集沉淀物，真空干燥8-24h，得到所述硒掺杂MXene材料。制备得到的复合材料具有较高的比表面积，良好的导电性、循环稳定性能、倍率性能以及较高的理论比容量，且制备方法简单，成本低廉，适用于钾离子电池的大规模开发和应用。

Description

一种硒掺杂MXene材料及其制备方法和应用 技术领域
本发明属于纳米材料技术领域，涉及一种硒掺杂MXene材料及其制备方法和应用，特别是在钾离子电池中作为电极材料的应用。
背景技术
随着现代社会对能源需求量的不断提高，化石类能源不断消耗衰竭，生态环境问题日趋严重，为此，开发新型绿色能源已经成为人们的研究热点。
目前，锂离子电池已经广泛应用到人们的日常生活中，同时金属锂的大量消耗也开始引起了人们的担忧。因此，寻找一种锂离子电池的替代品成为目前的研究重点。
钾资源在地球上的储量丰富，占地壳的2.09％，是锂资源(0.0017％)的1000多倍，价格相对低廉。钾离子电池由于具有较低的成本、长的循环使用寿命、能量密度高及良好的倍率性能等优势，可满足储能领域的需要，是富有潜力的二次电池。基于以上优点，钾离子二次电池技术被认为是未来极具前景的大规模电化学储能技术。因此，发展价格低廉且具良好循环性能的钾离子电池具有巨大的商业价值。
由于钾离子的半径比锂离子大，在锂离子电池中达到商业应用的石墨碳负极材料，由于其层间距较小(0.335nm)而不能满足钾离子的快速脱嵌，探究高容量且循环性能优异的钾离子电池负极材料是该领域的研究热点。
而现有电池行业中，制备钾电池的方法或工艺步骤较多，这样容易增加成本，而如果简单的省略一些工艺步骤又会导致性能下降。此外，广泛使用的硫掺杂MXene的技术采用H2S作为硫源，毒性大，有很强的污染性，后续处理困难。因而，通过简单的方法制备低成本、更安全环保的硒掺杂MXene材料及其钾离子电池具有重要的现实意义。
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硒掺杂MXene材料。本发明的另一目的在于提供上述硒掺杂MXene材料的制备方法。进一步的，本发明提供一种硒掺杂MXene材料的应用，将所述硒掺杂MXene材料用作钾离子电池负极。
本发明采用以下技术方案：
一种硒掺杂MXene材料的制备方法，所述制备方法为溶剂热法，包括以下步骤：
(1)将MXene和有机硒源按照质量比为(0.1～1)∶1，可选(0.2～0.8)∶1，可选(0.4～0.6)∶1加入分散剂中，搅拌(可选磁力搅拌)配制成浓度为10-100mg/ml，可选20-80mg/ml，可 选40-60mg/ml的分散液；
(2)将所述分散液转移至反应釜中，升温至110-230℃，反应10-30h，优选反应在反应釜中进行(反应釜密封)，然后自然冷却至室温；
(3)将步骤(2)所得产物用清洗剂洗涤后离心，收集沉淀物，真空干燥8-24h，例如16h，得到所述硒掺杂MXene材料。
进一步地，所述有机硒源为二甲基硒、二苄基二硒醚、苯硒酚中的至少一种，优选二甲基硒或苯硒酚，优选质量比为3～5∶1的二甲基硒和二苄基二硒醚。
进一步地，所述MXene为Ti 2NT x、Mo 2NT x、V 2NT x、Ti 2CT x、Mo 2CT x、V 2CT x中的一种或多种，可选V 2CT x，可选Mo 2NT x，可选V 2NT x，可选质量比为4～6∶1的Ti 2CT x和V 2NT x，可选质量比为4～6∶1的Ti 2CT x和Mo 2CT x，可选Ti 2CT x、Mo 2CT x和V 2CT x(例如质量比为5～8∶2∶1)，T x为表面官能团-O、-F或-OH。
进一步地，所述分散剂为N，N-二甲基甲酰胺、乙醇中的至少一种。
进一步地，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彻底清洗沉淀物，可以用去离子水和无水乙醇交替清洗沉淀物2-15次，优选3-8次。
进一步地，所述硒掺杂MXene材料中硒掺杂量为0.3-8wt％(例如1、2、3、4、5、6、7、8wt％)。
进一步地，步骤(1)中搅拌时间为1-6h，可选2、3、4、5、6h。
进一步地，步骤(2)中所述分散液在反应釜中升温至110-200℃，优选130-180℃，可选140℃、150℃、160℃、170℃，反应12-30h，可选13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28h。
进一步地，步骤(3)中所述离心使用的转速为4000-6000转/分，优选5000转/分。
进一步地，真空干燥的温度为50-70℃，优选60℃，真空度不超过133Pa，例如不超过130、120、110、100、90Pa。
一种硒掺杂MXene材料的制备方法制备得到的硒掺杂MXene材料。
一种硒掺杂MXene材料的应用，将所述硒掺杂MXene材料用作钾离子电池负极。
MXene是一种新型过渡金属碳化物或碳氮化物二维层状晶体，这类材料具有和石墨烯类似的结构。MXene材料具有良好的导电性，较高的比表面积，较低的离子扩散阻力，低的开路电压和高的存储容量，同时，能够很好地将电池行为与赝电容行为结合，从而进一步提高容量。通过硒掺杂后，MXene中部分C、N原子被Se原子取代，表面具有大量的缺陷，使其比容量、倍率性能、循环稳定性能等进一步提高，更适合用作钾离子电池负极材料。
本发明的有益效果：
(1)本发明制备的复合材料具有较高的比表面积，良好的导电性、循环稳定性能、倍率性能以及较高的理论比容量，且制备方法简单，成本低，适用于钾离子电池的大规模开发和应用；
(2)本发明的制备装置成熟，工艺简单，原料易得，生产效率高，方便大规模工业生产应用。
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中硒掺杂MXene材料的扫描电镜图；
图3是实施例1中硒掺杂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为实施例2中硒掺杂MXene钾离子电池负极循环性能图；
图6为实施例3中硒掺杂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
一种硒掺杂MXene材料的制备方法，将MXene材料与二甲基硒按质量比0.1∶1制备硒掺杂MXene材料，包括以下步骤：
(1)取50mg MXene材料(Ti 2CT x)和500mg二甲基硒加入到N，N-二甲基甲酰胺中，配制成10mg/ml的分散液，在室温下，磁力搅拌1h；
(2)将步骤(1)中得到的分散液移至100ml反应釜中，并放于烘箱中，在110℃下反应12h，自然冷却至室温；
(3)收集步骤(2)所得产物，并用去离子水和无水乙醇彻底清洗，离心，然后在60℃下真空干燥8h，得到硒掺杂MXene材料。
(4)钾离子电池负极制备：将(3)所得的硒掺杂MXene材料与聚偏氟乙烯粘结剂、碳黑，按质量比为8∶1∶1的比例混合，加入适量的N-甲基吡咯烷酮溶液搅拌分散，搅拌均匀后形成浆料涂覆在集流体上，经真空干燥、切片后，制得钾离子电池负极片。
本实施例掺杂后的MXene比表面积为210.2m 2/g，层间距为0.72nm，硒原子含量为0.3％，远大于未掺杂MXene的比表面积(50.8m 2/g)、层间距(0.60nm)；图3所示的硒掺杂MXene钾离子电池负极的在100mA/g的电流密度下，循环100圈后的可逆容量为215mAh/g，是图4所示的未掺杂MXene钾离子电池负极(116.3mAh/g)的1.85倍，且本实施例掺杂的MXene 材料具有非常稳定的充放电循环特性。
实施例2
一种硒掺杂MXene材料的制备方法，将MXene材料与二甲基硒按质量比0.5∶1制备硒掺杂MXene材料，包括以下步骤：
(1)取500mg MXene材料(Ti 2CT x)和1000mg二甲基硒加入到N，N-二甲基甲酰胺中，配制成50mg/ml的分散液，在室温下，磁力搅拌3h；
(2)将步骤(1)中得到的分散液移至50ml反应釜中，并放于烘箱中，在180℃下反应18h，自然冷却至室温；
(3)收集步骤(2)所得产物，并用去离子水和无水乙醇彻底清洗，离心，然后在60℃下真空干燥16h，得到硒掺杂MXene材料。
(4)钾离子电池负极制备：将(3)所得的硒掺杂MXene与聚偏氟乙烯粘结剂、碳黑，按质量比为8∶1∶1的比例混合，加入适量N-甲基吡咯烷酮，搅拌均匀后形成浆料涂覆在集流体上，经真空干燥、切片后，制得钾离子电池负极片。
本实施例掺杂后的MXene比表面积为350.5m 2/g，层间距为0.76nm，硒原子含量为5％，远大于未掺杂MXene的比表面积(50.8m 2/g)、层间距(0.60nm)；图5所示的硒掺杂MXene钾离子电池负极的在100mA/g的电流密度下，循环100圈后的可逆容量为341mAh/g，是未掺杂MXene钾离子电池负极(116.3mAh/g)的2.7倍，且本实施例掺杂的MXene材料具有非常稳定的充放电循环特性。
实施例3
一种硒掺杂MXene材料的制备方法，将MXene材料与二甲基硒按质量比1∶1制备硒掺杂MXene材料，包括以下步骤：
(1)取1500mg MXene材料(Ti 2CT x)和1500mg二甲基硒加入到N，N-二甲基甲酰胺中，配制成100mg/ml的分散液，在室温下，磁力搅拌6h；
(2)将步骤(1)中得到的分散液移至50ml反应釜中，并放于烘箱中，在230℃下反应30h，自然冷却至室温；
(3)收集步骤(2)所得产物，并用去离子水和无水乙醇彻底清洗，离心，然后在60℃下真空干燥24h，得到硒掺杂MXene材料。
(4)钾离子电池负极制备：将(3)所得的硒掺杂MXene与聚偏氟乙烯粘结剂、碳黑，按质量比为8∶1∶1的比例混合，加入适量N-甲基吡咯烷酮，搅拌均匀后形成浆料涂覆在集流体上，经真空干燥、切片后，制得钾离子电池负极片，且本实施例掺杂的MXene材料具有非常稳定的充放电循环特性。
本实施例掺杂后的MXene比表面积为301.7m 2/g，层间距为0.79nm，硒原子含量为8％，远大于未掺杂MXene的比表面积(50.8m 2/g)、层间距(0.60nm)；如图6所示，硒掺杂MXene钾离子电池负极的在100mA/g的电流密度下，循环100圈后的可逆容量为300mAh/g，是未掺杂MXene钾离子电池负极(116.3mAh/g)的2.6倍，且本实施例掺杂的MXene材料具有非常稳定的充放电循环特性。
实施例4
一种硒掺杂MXene材料的制备方法，将MXene材料与有机硒源按质量比为0.4∶1制备硒掺杂MXene材料，包括以下步骤：
(1)取400mg MXene材料(V 2CT x)和1000mg有机硒源(800mg二甲基硒和200mg二苄基二硒醚混合均匀)加入到N，N-二甲基甲酰胺中，配制成40mg/ml的分散液，在室温下，磁力搅拌3h；
(2)将步骤(1)中得到的分散液移至50ml反应釜中，并放于烘箱中，在190℃下反应10h，自然冷却至室温；
(3)收集步骤(2)所得产物，并用去离子水和无水乙醇彻底清洗，离心，然后在60℃下真空干燥16h，最终得到硒掺杂MXene材料。
(4)钾离子电池负极制备：将(3)所得的硒掺杂MXene与聚偏氟乙烯粘结剂、碳黑，按质量比为8∶1∶1的比例混合，加入适量N-甲基吡咯烷酮，搅拌均匀后形成浆料涂覆在集流体上，经真空干燥、切片后，制得钾离子电池负极片。
本实施例掺杂的MXene钾离子电池负极的在100mA/g的电流密度下，循环100圈后的可逆容量为401mAh/g，是未掺杂MXene钾离子电池负极(116.3mAh/g)的3.5倍，且本实施例掺杂的MXene材料具有非常稳定的充放电循环性能。
实施例5
一种硒掺杂MXene材料的制备方法，将MXene材料与二甲基硒按质量比为0.6∶1制备硒掺杂MXene材料，包括以下步骤：
(1)取600mg MXene材料(500mg Ti 2CT x和100mg Mo 2CT x)和1000mg二甲基硒加入到N，N-二甲基甲酰胺中，配制成60mg/ml的分散液，在室温下，磁力搅拌3h；
(2)将步骤(1)中得到的分散液移至50ml反应釜中，并放于烘箱中，在170℃下反应13h，自然冷却至室温；
(3)收集步骤(2)所得产物，并用去离子水和无水乙醇彻底清洗，离心，然后在60℃下真空干燥16h，得到硒掺杂MXene材料。
(4)钾离子电池负极制备：将(3)所得的硒掺杂MXene与聚偏氟乙烯粘结剂、碳黑， 按质量比为8∶1∶1的比例混合，加入适量N-甲基吡咯烷酮，搅拌均匀后形成浆料涂覆在集流体上，经真空干燥、切片后，制得钾离子电池负极片。
本实施例掺杂的MXene钾离子电池负极的在100mA/g的电流密度下，循环100圈后的可逆容量为387mAh/g，是未掺杂MXene钾离子电池负极(116.3mAh/g)的3.3倍，且本实施例掺杂的MXene材料具有非常稳定的充放电循环特性。
对比例1：未掺杂MXene钾离子电池负极。
对比例2：使用无机硒源(例如硒粉)掺杂MXene的钾离子电池负极，掺杂过程同实施例2。
表1：性能测试
Figure PCTCN2019098136-appb-000001
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. 一种硒掺杂MXene材料的制备方法，其特征在于，包括以下步骤：
    (1)将MXene和有机硒源按照质量比为0.1～1∶1加入分散剂中，搅拌配制成浓度为10-100mg/ml的分散液；
    (2)将所述分散液转移至反应釜后升温至110-230℃，反应10-30h，之后自然冷却至室温；
    (3)将步骤(2)所得产物用清洗剂洗涤后离心，收集沉淀物，真空干燥8-24h，得到所述硒掺杂MXene材料。
  2. 根据权利要求1所述的硒掺杂MXene材料的制备方法，其特征在于，所述有机硒源为二甲基硒、二苄基二硒醚、苯硒酚中的至少一种。
  3. 根据权利要求1所述的硒掺杂MXene材料的制备方法，其特征在于，所述MXene为Ti 2NT x、Mo 2NT x、V 2NT x、Ti 2CT x、Mo 2CT x、V 2CT x中的一种或多种。
  4. 根据权利要求1所述的硒掺杂MXene材料的制备方法，其特征在于，所述分散剂为N，N-二甲基甲酰胺、乙醇中的至少一种；所述清洗剂为水、乙醇中的至少一种。
  5. 根据权利要求1所述的硒掺杂MXene材料的制备方法，其特征在于，所述硒掺杂MXene材料中硒掺杂量为0.3-8wt％。
  6. 根据权利要求1所述的硒掺杂MXene材料的制备方法，其特征在于，步骤(1)中搅拌时间为1-6h。
  7. 根据权利要求1所述的硒掺杂MXene材料的制备方法，其特征在于，步骤(2)中所述分散液在反应釜中升温至110-200℃，反应12-30h。
  8. 根据权利要求1所述的硒掺杂MXene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4000-6000转/分；真空干燥的温度为50-70℃，真空度不超过133Pa。
  9. 一种硒掺杂MXene材料，其特征在于，所述硒掺杂MXene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所述的硒掺杂MXene材料的应用，其特征在于，将所述硒掺杂MXene材料用于钾离子电池负极。
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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
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
CN112018354A (zh) * 2020-08-14 2020-12-01 五邑大学 一种阵列状SnS2/MXene复合材料的制备方法
CN112038641B (zh) * 2020-09-09 2022-10-28 宁波富理电池材料科技有限公司 一种MXene硅碳复合材料、其制备方法、负极和锂离子电池
CN113593922B (zh) * 2021-07-27 2022-10-14 陕西君普新航科技有限公司 超级电容器电极粉体材料及其制备方法
CN113628890B (zh) * 2021-08-06 2022-08-26 西南大学 双金属硒化物复合Ti3C2材料的制备方法及其产品和超级电容器
CN114933286A (zh) * 2022-06-23 2022-08-23 山东大学 Se@MXene复合材料及其制备方法与全固态锂电池
CN116798782B (zh) * 2023-07-06 2026-03-20 浙江大学 一种碳骨架锚定的硒化钛复合材料的制备方法及其产品和应用

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106025200A (zh) * 2016-05-24 2016-10-12 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
CN107170587A (zh) * 2017-05-26 2017-09-15 中国石油大学(北京) 一种硫掺杂MXene材料及其制备方法与应用
KR20170106860A (ko) * 2016-03-14 2017-09-22 한국에너지기술연구원 황으로 표면이 변형된 Mxene 구조체
CN109817918A (zh) * 2019-01-22 2019-05-28 五邑大学 硫掺杂MXene复合材料及其制备方法和应用
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
CN109830661A (zh) * 2019-01-16 2019-05-31 五邑大学 硒掺杂MXene复合纳米材料及其制备方法和应用
CN109888280A (zh) * 2019-01-23 2019-06-14 五邑大学 钾离子电池硫掺杂MXene负极材料及其制备方法
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 (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106629678A (zh) * 2016-12-12 2017-05-10 天津师范大学 一种水热法制备多元共掺杂石墨烯的方法
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 (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170106860A (ko) * 2016-03-14 2017-09-22 한국에너지기술연구원 황으로 표면이 변형된 Mxene 구조체
CN106025200A (zh) * 2016-05-24 2016-10-12 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
CN107170587A (zh) * 2017-05-26 2017-09-15 中国石油大学(北京) 一种硫掺杂MXene材料及其制备方法与应用
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
CN109830661A (zh) * 2019-01-16 2019-05-31 五邑大学 硒掺杂MXene复合纳米材料及其制备方法和应用
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
CN109817918A (zh) * 2019-01-22 2019-05-28 五邑大学 硫掺杂MXene复合材料及其制备方法和应用
CN109888280A (zh) * 2019-01-23 2019-06-14 五邑大学 钾离子电池硫掺杂MXene负极材料及其制备方法

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