WO2021237377A1 - 一种新型过渡金属碳化物二维纳米材料的制备方法 - Google Patents

一种新型过渡金属碳化物二维纳米材料的制备方法 Download PDF

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WO2021237377A1
WO2021237377A1 PCT/CN2020/091945 CN2020091945W WO2021237377A1 WO 2021237377 A1 WO2021237377 A1 WO 2021237377A1 CN 2020091945 W CN2020091945 W CN 2020091945W WO 2021237377 A1 WO2021237377 A1 WO 2021237377A1
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覃华贤
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Nantong Duoqian New Material Science And Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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 relates to a method for preparing a novel transition metal carbide two-dimensional nano material.
  • MXenes (M: element in the first half of transition metal; X: C or N; ene: two-dimensional structure similar to graphene) is a type of two-dimensional nanocrystals with only a few layers of atoms, generally composed of its precursor MAX (A : Ga, Si, P, S, Ge, As and other elements) are prepared.
  • MAX A : Ga, Si, P, S, Ge, As and other elements
  • the structure of MAX is similar, belongs to the hexagonal crystal structure, and the space group is P63/mmc.
  • 1 C atom and 6 M atoms form a close-packed common edge M6C octahedron.
  • the C atom is located in the center of the octahedral gap, and the alternate M6C is formed by connecting the plane layers of A atoms.
  • the bond between the C atom and the M atom is a covalent bond, and the bond between the A element atom and the M atom in the middle layer is a metal bond, which is relatively weak.
  • the element A atoms can be selectively etched away by liquid-phase chemical etching, thereby obtaining MXenes two-dimensional nanocrystals with a thickness of only a few atoms.
  • MXenes prepared by liquid-phase chemical etching not only have a large specific surface area, but also have excellent photoelectric properties, mechanical properties, and adjustable chemical composition.
  • MXenes has metal conductivity, and the electronic structure of the MXT phase is related to the type of T and its orientation on a two-dimensional plane, showing semiconductor properties.
  • MXenes has shown great application potential in energy storage, catalysis, adsorption, and biomedicine.
  • MXenes has shown great application potential in energy storage, catalysis, adsorption, and biomedicine.
  • the method is divided into two steps: first, the synthesis of the precursor MAX, and then the etching process of MAX.
  • the precursor MAX is a ceramic material with excellent performance.
  • the synthesis methods mainly include cold/hot pressing sintering, hot isostatic pressing sintering, pulse discharge sintering, high-energy ball milling, and combustion synthesis.
  • the etching process of MAX mainly includes liquid phase chemical etching and high temperature fluorine salt melting method.
  • the purpose of the present invention is to provide a method for preparing a novel transition metal carbide two-dimensional nano material.
  • a method for preparing a new type of transition metal carbide two-dimensional nanomaterial including the following steps: placing 10-20 parts of Mo, 25-35 parts of Al and 7-9 parts of graphite in 60-70 parts of absolute ethanol at room temperature Perform magnetic stirring. After the absolute ethanol is completely volatilized, the obtained mixture is put into an agate mortar for grinding, and then sieved with a sieve several times to discard large particles, and finally the mixed raw material powder is placed in In a stainless steel mold, use a hydraulic press to cold press into a wafer; put the pressed wafer into a graphite crucible, put it in a radio frequency induction furnace, evacuate the radio frequency furnace, and then fill it with argon as a protective atmosphere to maintain the argon in the furnace The pressure is 11-13Pa, slowly increase the working voltage to 145-155V and keep it for 40-50min, then slowly increase the voltage to 205-215V, after the reaction for 3.5-4.5h, reduce the working voltage to 0V, and cool to room temperature naturally
  • the argon pressure in the furnace is maintained at 12 Pa.
  • the working voltage is slowly increased to 150V and maintained for 45 minutes.
  • the voltage is slowly increased to 210V, and the working voltage is reduced to 0V after 4 hours of reaction.
  • the reaction is carried out with magnetic stirring at 45° C. for 48 hours.
  • deionized water is added for centrifugal washing to pH 6.0.
  • the preparation method it is placed in a vacuum drying oven at 55° C. and dried for 26 hours.
  • the method is simple, fast, and easy to operate, and the prepared high-purity two-dimensional nanomaterial has good conductivity and stability, has a huge market prospect, and can be prepared on a large scale.
  • a new type of transition metal carbide two-dimensional nanomaterial preparation method including the following steps: put 15 parts of Mo, 30 parts of Al and 8 parts of graphite in 65 parts of absolute ethanol, magnetically stirred at room temperature, and wait for the absolute ethanol After being completely volatilized, put the obtained mixture in an agate mortar for grinding, then sieving with a sieve several times to discard large particles, and finally put the uniformly mixed raw material powder in a stainless steel mold and press it with a hydraulic press.
  • a method for preparing a new type of transition metal carbide two-dimensional nanomaterial including the following steps: placing 10 parts of Mo, 25 parts of Al, and 7 parts of graphite in 60 parts of absolute ethanol, magnetically stirring at room temperature, and waiting for the absolute ethanol After being completely volatilized, put the obtained mixture in an agate mortar for grinding, then sieving with a sieve several times to discard large particles, and finally put the uniformly mixed raw material powder in a stainless steel mold and press it with a hydraulic press.
  • a method for preparing a new type of transition metal carbide two-dimensional nanomaterial including the following steps: placing 20 parts of Mo, 35 parts of Al and 9 parts of graphite in 70 parts of absolute ethanol, magnetically stirring at room temperature, and waiting for the absolute ethanol After being completely volatilized, put the obtained mixture in an agate mortar for grinding, then sieving with a sieve several times to discard large particles, and finally put the uniformly mixed raw material powder in a stainless steel mold and press it with a hydraulic press.
  • the method is simple, fast, and easy to operate, and the prepared high-purity two-dimensional nanomaterial has good conductivity and stability, has a huge market prospect, and can be prepared on a large scale.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

一种过渡金属碳化物二维纳米材料的制备方法，步骤如下：将Mo、Al和石墨置于乙醇中，搅拌，待乙醇挥发后，放入玛瑙研钵中研磨，筛分，弃掉大的颗粒，置于不锈钢模具中，用液压机冷压成圆片；将压好的圆片装入石墨坩埚放入射频感应炉中，抽成真空后充入氩气，缓慢升高工作电压至145-155V保持40-50min，升高到205-215V，反应3.5-4.5h后将工作电压降低到0V，冷却到室温；将冷却后的胚体用玛瑙研钵研碎，加入的氢氟酸中，搅拌反应47-49h，取出反应液，离心清洗，干燥即得。该方法简便、易操作，制备得到的高纯二维纳米材料具有良好的导电性和稳定性。

Description

一种新型过渡金属碳化物二维纳米材料的制备方法 技术领域
本发明涉及一种新型过渡金属碳化物二维纳米材料的制备方法。
背景技术
MXenes(M：过渡金属前半区的元素；X：C或N；ene：与石墨烯有类似的二维结构)是一类只有几层原子的二维纳米晶体，一般由其前驱物MAX(A：Ga，Si，P，S，Ge，As等元素)制备而得。MAX的通式为M n+1AX n(n＝1，2，3)，根据n的取值不同，可以将MAX分为211、312和413相。MAX的结构相似，属于六方晶体结构，空间群为P63/mmc。在碳化物MAX中，1个C原子与6个M原子之间形成紧密堆积的共棱M6C八面体，C原子位于八面体间隙中心，交替出现的M6C由A原子平面层连接而成。C原子与M原子间的键合为共价键，处于中间层的A元素原子与M原子间的键合为金属键，相对较弱。利用A元素原子反应活性高、键能低的特点，可以采用液相化学刻蚀的方法将A元素原子选择性地刻蚀掉，从而得到只有几个原子厚度的MXenes二维纳米晶体。研究表明，通过液相化学刻蚀法制备的MXenes不仅具有大的比表面积，还具有优异的光电特性、力学性能和化学组成可调等性质。在制备过程中，MXenes的表面容易修饰多种官能团，形成MXT相(T代表-OH、＝O或F +离子)，表现出亲水性。密度泛函理论研究表明，纯的MXene相具有金属导电性，而MXT相的电子结构与T的种类及其在二维平面上的定向排列有关，表现出半导体性质。目前，MXenes在储能、催化、吸附、生物医疗等方面展现出巨大的应用潜力。然而，成功合成、剥离单层MXenes纳米材料仍然存在很多挑战。现有的MXenes合成方法主要有两类：直接合成和通过前驱物MAX刻蚀合成。通过MAX刻蚀得到MXenes是目前采用较多的方法。该方法分成两步：首先是前驱物MAX的合成，然后是MAX的刻蚀过程。前驱物MAX是一种性能优异的陶瓷材料，合成方法主要有冷/热压烧结、热等静压烧结、脉冲放电烧结、高能球磨以及燃烧合成等。MAX的刻蚀过程主要有液相化学刻蚀和高温氟盐熔融法等。在前驱物MAX的合成过程中，一般需要将原料粉体球磨数小时以上，不仅能耗高而且容易在球磨过程中发生固相反应，产生大量的杂质；而高温氟盐熔融法，容易破坏二维M n+1C n的晶体结构从而产生缺陷，适合刻蚀结合能更低的M n+1XN n。
发明内容
本发明的目的在于提供一种新型过渡金属碳化物二维纳米材料的制备方法。
本发明通过下面技术方案实现：
一种新型过渡金属碳化物二维纳米材料的制备方法，包括如下步骤：将10-20份Mo、25-35 份Al和7-9份石墨置于60-70份无水乙醇中，室温下进行磁力搅拌，待无水乙醇完全挥发后，将获得的混合物放入玛瑙研钵中进行研磨，然后用筛网多次筛分，弃掉大的颗粒，最后将混合均匀的原料粉体置于不锈钢模具中，用液压机冷压成圆片；将压好的圆片装入石墨坩埚，放入射频感应炉中，将射频炉抽成真空后，充入氩气作为保护气氛，维持炉内氩气压强为11-13Pa，缓慢升高工作电压至145-155V并保持40-50min，随后将电压缓慢升高到205-215V，反应3.5-4.5h后将工作电压降低到0V，自然冷却到室温；将冷却后的胚体用玛瑙研钵研碎，过300目的不锈钢筛，剔除较大的颗粒，缓慢加入20-30份质量浓度为50％的氢氟酸中，42-48℃下磁力搅拌反应47-49h，取出反应液，加去离子水离心清洗至pH为5.8-6.2，放入真空干燥箱中50-60℃干燥25-27h，冷却即得；各原料均为重量份。
优选地，所述的制备方法中，维持炉内氩气压强为12Pa。
优选地，所述的制备方法中，缓慢升高工作电压至150V并保持45min。
优选地，所述的制备方法中，将电压缓慢升高到210V，反应4h后将工作电压降低到0V。
优选地，所述的制备方法中，45℃下磁力搅拌反应48h。
优选地，所述的制备方法中，加去离子水离心清洗至pH为6.0。
优选地，所述的制备方法中，放入真空干燥箱中55℃干燥26h。
本发明技术效果：
该方法简便、快捷、易操作，制备得到的高纯二维纳米材料具有良好的导电性和稳定性，具有巨大的市场前景，可大规模制备。
具体实施方式
下面结合实施例具体介绍本发明的实质性内容。
实施例1
一种新型过渡金属碳化物二维纳米材料的制备方法，包括如下步骤：将15份Mo、30份Al和8份石墨置于65份无水乙醇中，室温下进行磁力搅拌，待无水乙醇完全挥发后，将获得的混合物放入玛瑙研钵中进行研磨，然后用筛网多次筛分，弃掉大的颗粒，最后将混合均匀的原料粉体置于不锈钢模具中，用液压机冷压成圆片；将压好的圆片装入石墨坩埚，放入射频感应炉中，将射频炉抽成真空后，充入氩气作为保护气氛，维持炉内氩气压强为12Pa，缓慢升高工作电压至150V并保持45min，随后将电压缓慢升高到210V，反应4h后将工作电压降低到0V，自然冷却到室温；将冷却后的胚体用玛瑙研钵研碎，过300目的不锈钢筛，剔除较大的颗粒，缓慢加入25份质量浓度为50％的氢氟酸中，45℃下磁力搅拌反应48h，取出反应液，加去离子水离心清洗至pH为6.0，放入真空干燥箱中55℃干燥26h，冷却即得；各原料均为重量份。
实施例2
一种新型过渡金属碳化物二维纳米材料的制备方法，包括如下步骤：将10份Mo、25份Al和7份石墨置于60份无水乙醇中，室温下进行磁力搅拌，待无水乙醇完全挥发后，将获得的混合物放入玛瑙研钵中进行研磨，然后用筛网多次筛分，弃掉大的颗粒，最后将混合均匀的原料粉体置于不锈钢模具中，用液压机冷压成圆片；将压好的圆片装入石墨坩埚，放入射频感应炉中，将射频炉抽成真空后，充入氩气作为保护气氛，维持炉内氩气压强为11Pa，缓慢升高工作电压至145V并保持40min，随后将电压缓慢升高到205V，反应3.5h后将工作电压降低到0V，自然冷却到室温；将冷却后的胚体用玛瑙研钵研碎，过300目的不锈钢筛，剔除较大的颗粒，缓慢加入20份质量浓度为50％的氢氟酸中，42℃下磁力搅拌反应47h，取出反应液，加去离子水离心清洗至pH为5.8，放入真空干燥箱中50℃干燥25h，冷却即得；各原料均为重量份。
实施例3
一种新型过渡金属碳化物二维纳米材料的制备方法，包括如下步骤：将20份Mo、35份Al和9份石墨置于70份无水乙醇中，室温下进行磁力搅拌，待无水乙醇完全挥发后，将获得的混合物放入玛瑙研钵中进行研磨，然后用筛网多次筛分，弃掉大的颗粒，最后将混合均匀的原料粉体置于不锈钢模具中，用液压机冷压成圆片；将压好的圆片装入石墨坩埚，放入射频感应炉中，将射频炉抽成真空后，充入氩气作为保护气氛，维持炉内氩气压强为13Pa，缓慢升高工作电压至155V并保持50min，随后将电压缓慢升高到215V，反应4.5h后将工作电压降低到0V，自然冷却到室温；将冷却后的胚体用玛瑙研钵研碎，过300目的不锈钢筛，剔除较大的颗粒，缓慢加入30份质量浓度为50％的氢氟酸中，48℃下磁力搅拌反应49h，取出反应液，加去离子水离心清洗至pH为6.2，放入真空干燥箱中60℃干燥27h，冷却即得；各原料均为重量份。
该方法简便、快捷、易操作，制备得到的高纯二维纳米材料具有良好的导电性和稳定性，具有巨大的市场前景，可大规模制备。

Claims (7)

  1. 一种新型过渡金属碳化物二维纳米材料的制备方法，其特征在于包括如下步骤：将10-20份Mo、25-35份Al和7-9份石墨置于60-70份无水乙醇中，室温下进行磁力搅拌，待无水乙醇完全挥发后，将获得的混合物放入玛瑙研钵中进行研磨，然后用筛网多次筛分，弃掉大的颗粒，最后将混合均匀的原料粉体置于不锈钢模具中，用液压机冷压成圆片；将压好的圆片装入石墨坩埚，放入射频感应炉中，将射频炉抽成真空后，充入氩气作为保护气氛，维持炉内氩气压强为11-13Pa，缓慢升高工作电压至145-155V并保持40-50min，随后将电压缓慢升高到205-215V，反应3.5-4.5h后将工作电压降低到0V，自然冷却到室温；将冷却后的胚体用玛瑙研钵研碎，过300目的不锈钢筛，剔除较大的颗粒，缓慢加入20-30份质量浓度为50％的氢氟酸中，42-48℃下磁力搅拌反应47-49h，取出反应液，加去离子水离心清洗至pH为5.8-6.2，放入真空干燥箱中50-60℃干燥25-27h，冷却即得；各原料均为重量份。
  2. 根据权利要求1所述的制备方法，其特征在于：维持炉内氩气压强为12Pa。
  3. 根据权利要求1所述的制备方法，其特征在于：缓慢升高工作电压至150V并保持45min。
  4. 根据权利要求1所述的制备方法，其特征在于：将电压缓慢升高到210V，反应4h后将工作电压降低到0V。
  5. 根据权利要求1所述的制备方法，其特征在于：45℃下磁力搅拌反应48h。
  6. 根据权利要求1所述的制备方法，其特征在于：加去离子水离心清洗至pH为6.0。
  7. 根据权利要求1所述的制备方法，其特征在于：放入真空干燥箱中55℃干燥26h。
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CN115820183A (zh) * 2022-12-23 2023-03-21 深圳市道尔科技有限公司 一种耐高温高强度、高导热胶的制备方法
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