WO2020147290A1 - Tellurium-doped mxene material, preparation method therefor and use thereof - Google Patents

Tellurium-doped mxene material, preparation method therefor and use thereof Download PDF

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WO2020147290A1
WO2020147290A1 PCT/CN2019/097437 CN2019097437W WO2020147290A1 WO 2020147290 A1 WO2020147290 A1 WO 2020147290A1 CN 2019097437 W CN2019097437 W CN 2019097437W WO 2020147290 A1 WO2020147290 A1 WO 2020147290A1
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tellurium
mxene material
doped
quartz
doped mxene
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Chinese (zh)
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张业龙
孙宏阳
徐晓丹
王炳春
宋伟东
汪达
张弛
刘争
郭月
温锦秀
陈梅
曾庆光
彭章泉
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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
    • 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
    • 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
    • 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 new energy, and specifically relates to a preparation method of tellurium-doped MXene and its application in sodium ion batteries.
  • the first commercially successful lithium-ion battery has always occupied a dominant position in the field of energy storage.
  • the inherent defects of lithium-ion batteries such as limited lithium resource reserves, uneven resource distribution, and high costs
  • Such issues gradually arouse people's concerns.
  • it is increasingly urgent to find alternatives with lower cost and richer content.
  • Sodium is rich in storage.
  • Sodium ion batteries (SIB) are expected to replace lithium ion batteries (LIB) and become a new generation of secondary batteries due to their low cost and suitable redox potential (2.71V compared to standard hydrogen electrodes).
  • the sodium ion radius is larger than the lithium ion radius, the graphite material widely used in lithium ion batteries has a small interlayer spacing, and has poor Na + intercalation ability, which is not suitable for sodium ion batteries.
  • MXene material is a new series of two-dimensional metal carbides and carbonitrides, where M is a transition metal, A is group IIIA or group IVA and X is C and/or N. It can be etched by hydrofluoric acid to form a hydroxyl group.
  • the nano flake materials with functional groups of, oxygen and fluorine, a variety of chemical components and abundant functional groups give MXenes excellent hydrophilic surface and good electrical conductivity, thus showing great potential in the field of energy storage. Compared with traditional carbon materials, the electrochemical performance of sodium ion batteries still has huge room for improvement.
  • one of the objectives of the present invention is to provide a tellurium-doped MXene material.
  • Another object of the present invention is to provide a method for preparing the aforementioned tellurium-doped MXene material.
  • the present invention provides an application of tellurium-doped MXene material, which is used as a negative electrode of a sodium ion battery.
  • a preparation method of tellurium-doped MXene material includes the following steps:
  • the quartz ark containing the tellurium source is on the inlet side
  • the quartz ark containing MXene is on the outlet side.
  • the two arks are separated by 1-5cm (for example, 2, 3). , 4cm);
  • the tellurium source is at least one of tellurium powder and sodium tellurite.
  • the tellurium powder with a particle size of 50-150 mesh (for example, 80, 100, 120 mesh) is preferred, and the purity is preferably 99.99%.
  • the MXene is Ti 3 C 2 T x , Mo 3 C 2 T x , V 3 C 2 T x , Ti 3 N 2 T x , Mo 3 N 2 T x , V 3 N 2 T x , Ti 2 CT x
  • Ti 3 C 2 T x , V 3 N 2 T x and V 3 C 2 T x can be selected (for example, the mass ratio is 4-9:1:1)
  • T x is the surface functional group -O, -F or -OH.
  • the doping amount of tellurium in the tellurium-doped MXene material is 0.5 wt% to 15 wt%.
  • the doping amount of tellurium in the tellurium-doped MXene material is 1.5wt%-10wt%, for example 1.5wt%-5wt%, for example 5wt%-9wt%.
  • the inert gas is Ar.
  • step (3) under the protection of an inert gas with a gas flow rate of 220-300 ml/min (for example, 250 ml/min), heating to 350-350 °C at a temperature increase rate of 4 to 6 °C/min (for example, 5 °C/min) 450°C, keep for 3-5 hours and then cool to room temperature.
  • an inert gas with a gas flow rate of 220-300 ml/min (for example, 250 ml/min)
  • heating to 350-350 °C at a temperature increase rate of 4 to 6 °C/min (for example, 5 °C/min) 450°C keep for 3-5 hours and then cool to room temperature.
  • a tellurium-doped MXene material is prepared by a method for preparing tellurium-doped MXene material.
  • tellurium-doped MXene material using the tellurium-doped MXene material for the negative electrode of a sodium ion battery.
  • the preparation method of the material is simple, safe and environmentally friendly, and suitable for large-scale applications.
  • the radius of tellurium atoms is larger than that of S atoms. After MXene is incorporated, the interlayer spacing is wider and the active sites are more, which significantly improves the performance of sodium ion batteries.
  • the tellurium-doped MXene material prepared by the present invention can greatly improve the specific capacity and cycle stability of sodium ion batteries;
  • the preparation method of the present invention is simple, safe and environmentally friendly, and is suitable for large-scale 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 tellurium-doped MXene material in Example 2;
  • Figure 3 is a graph showing the cycle performance of the negative electrode of an undoped MXene sodium ion battery in Comparative Example 1;
  • Example 4 is a graph showing the cycle performance of the negative electrode of the tellurium-doped MXene sodium ion battery in Example 2.
  • a preparation method of tellurium-doped MXene material includes the following steps:
  • the specific surface area of the doped MXene in this embodiment is 141.3m 2 /g, the interlayer spacing is 0.71nm, and the content of tellurium atoms is 0.7%, which is much larger than the specific surface area (33.7m 2 /g) and interlayer spacing ( 0.64nm), the reversible capacity of the doped MXene sodium ion battery negative electrode at a current density of 100mA/g after 100 cycles is 198.1mAh/g, which is an undoped MXene sodium ion battery negative electrode (107.2mAh/g) 1.85 times.
  • a preparation method of tellurium-doped MXene material includes the following steps:
  • the specific surface area of doped MXene in this embodiment is 327.8m 2 /g, the interlayer spacing is 0.79nm, and the content of tellurium atoms is 3.1%, which is much larger than the specific surface area (33.7m 2 /g) and interlayer spacing ( 0.64nm), the negative electrode of the doped MXene sodium ion battery shown in Figure 4 has a reversible capacity of 332.5mAh/g after 100 cycles at a current density of 100mA/g, which is the undoped MXene sodium ion battery shown in Figure 3. 3.1 times the negative electrode (107.2mAh/g).
  • a preparation method of tellurium-doped MXene material includes the following steps:
  • the specific surface area of doped MXene in this embodiment is 289.1m 2 /g, the interlayer spacing is 0.78nm, and the content of tellurium atoms is 9.6%, which is much larger than the specific surface area (33.7m 2 /g) and interlayer spacing ( 0.64nm), the doped MXene sodium ion battery negative electrode has a reversible capacity of 289.4mAh/g after 100 cycles at a current density of 100mA/g, which is the negative electrode of the undoped MXene sodium ion battery (107.2mAh/g) 2.7 times.
  • a preparation method of tellurium-doped MXene material includes the following steps:
  • the negative electrode of the doped MXene sodium ion battery in this example has a reversible capacity of 370.1mAh/g after 100 cycles at a current density of 100mA/g, which is 3.5 of that of the undoped MXene sodium ion battery negative electrode (107.2mAh/g). Times.
  • a preparation method of tellurium-doped MXene material includes the following steps:
  • the negative electrode of the doped MXene sodium ion battery in this example has a reversible capacity of 353.1mAh/g after 100 cycles at a current density of 100mA/g, which is 3.3 of that of the undoped MXene sodium ion battery negative electrode (107.2mAh/g). Times.
  • Comparative Example 1 Undoped MXene sodium ion battery negative electrode, the process of using undoped MXene to prepare the sodium ion battery negative electrode is the same as in Example 2.

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Abstract

Disclosed are a tellurium-doped MXene material and a preparation method therefor. The method comprises the following steps: (1) adding MXene and a tellurium source according to a mass ratio of 1 : 1-5 in two quartz arks, respectively; (2) placing the two quartz arks in a tube furnace, in which a quartz ark filled with the tellurium source is located on an intake side, a quartz ark filled with the MXene is located on an outlet side, and the interval between the two quartz arks is 1-5 cm; (3) under the protection of an inert gas with a gas flow rate of 70-300 ml/min, heating to 300-500ºC at a heating rate of 3-8ºC/min, maintaining the temperature for 3-5 hours, and then cooling same to room temperature; and (4) collecting a solid in the quartz ark located on the outlet side, so as to obtain the tellurium-doped MXene material. The tellurium-doped MXene material prepared in the present invention can greatly improve the specific capacity and cycle stability performance of a sodium ion battery, and the preparation method is simple, safe and environmentally friendly, which is suitable for large-scale application.

Description

一种碲掺杂MXene材料及其制备方法和应用Tellurium doped MXene material and its preparation method and application 技术领域Technical field
本发明属于新能源技术领域，具体涉及一种碲掺杂MXene的制备方法及其在钠离子电池中的应用。The invention belongs to the technical field of new energy, and specifically relates to a preparation method of tellurium-doped MXene and its application in sodium ion batteries.
背景技术Background technique
最早商用成功的锂离子电池在储能领域一直占据着主导地位，但随着二次电池使用越加广泛，锂离子电池的固有缺陷，如锂资源储量有限、资源分布不均衡、成本居高不下等问题逐渐引起人们的担忧。随着新能源行业的发展，寻找成本更低、含量更丰富的替代品越发紧迫。The first commercially successful lithium-ion battery has always occupied a dominant position in the field of energy storage. However, as the use of secondary batteries becomes more widespread, the inherent defects of lithium-ion batteries, such as limited lithium resource reserves, uneven resource distribution, and high costs Such issues gradually arouse people's concerns. With the development of the new energy industry, it is increasingly urgent to find alternatives with lower cost and richer content.
钠存储丰富，钠离子电池(SIB)因其低成本和合适的氧化还原电位(相对于标准氢电极为2.71V)的显著优点而有望取代锂离子电池(LIB)，成为新一代二次电池。钠离子半径大于锂离子半径，在锂离子电池得到广泛应用的石墨材料的层间距较小，Na +插嵌能力差，并不适用于钠离子电池。 Sodium is rich in storage. Sodium ion batteries (SIB) are expected to replace lithium ion batteries (LIB) and become a new generation of secondary batteries due to their low cost and suitable redox potential (2.71V compared to standard hydrogen electrodes). The sodium ion radius is larger than the lithium ion radius, the graphite material widely used in lithium ion batteries has a small interlayer spacing, and has poor Na + intercalation ability, which is not suitable for sodium ion batteries.
MXene材料是一个新的二维金属碳化物和碳氮化物系列，其中M是过渡金属，A是IIIA族或IVA族并且X是C和/或N，经氢氟酸刻蚀，可形成含有羟基、氧和氟的官能团的纳米片状材料，多种化学成分和丰富的官能团赋予MXenes优异的亲水表面和良好的导电性能，因而在储能领域表现出巨大的潜力。与传统碳材料相比，钠离子电池的电化学性能仍存在巨大提升空间。MXene material is a new series of two-dimensional metal carbides and carbonitrides, where M is a transition metal, A is group IIIA or group IVA and X is C and/or N. It can be etched by hydrofluoric acid to form a hydroxyl group. The nano flake materials with functional groups of, oxygen and fluorine, a variety of chemical components and abundant functional groups give MXenes excellent hydrophilic surface and good electrical conductivity, thus showing great potential in the field of energy storage. Compared with traditional carbon materials, the electrochemical performance of sodium ion batteries still has huge room for improvement.
此外在现有电池行业中，制备钠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H 2S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、更安全环保的碲掺杂MXene材料及其钠离子电池具有重要的现实意义。 In addition, in the existing battery industry, there are many methods or process steps for preparing sodium batteries, which easily increase the cost, and if some process steps are simply omitted, the performance will decrease. In addition, the widely used sulfur-doped MXene technology uses H 2 S as the sulfur source, which is highly toxic, highly polluting, and difficult to follow up. Therefore, it is of great practical significance to prepare low-cost, safer and environmentally friendly tellurium-doped MXene materials and sodium ion batteries through simple methods.
发明内容Summary of the invention
针对现有技术存在的问题，本发明的目的之一在于提供一种碲掺杂MXene材料。本发明的另一目的在于提供上述碲掺杂MXene材料的制备方法。进一步的，本发明提供一种碲掺杂MXene材料的应用，将所述碲掺杂MXene材料用作钠离子电池负极。In view of the problems in the prior art, one of the objectives of the present invention is to provide a tellurium-doped MXene material. Another object of the present invention is to provide a method for preparing the aforementioned tellurium-doped MXene material. Further, the present invention provides an application of tellurium-doped MXene material, which is used as a negative electrode of a sodium ion battery.
本发明采用以下技术方案：The present invention adopts the following technical solutions:
一种碲掺杂MXene材料的制备方法，包括以下步骤：A preparation method of tellurium-doped MXene material includes the following steps:
(1)将MXene和碲源按照质量比为1∶1～5(例如1∶2、1∶3、1∶4)分别加入两个石 英方舟中；(1) Add MXene and tellurium source into two Shiying Ark according to the mass ratio of 1:1～5 (e.g. 1:2, 1:3, 1:4);
(2)将两个石英舟放置在管式炉中，其中，盛放碲源的石英方舟位于进气侧，盛放MXene的石英方舟位于出气侧，两方舟间隔1-5cm(例如2、3、4cm)；(2) Place two quartz boats in the tube furnace. Among them, the quartz ark containing the tellurium source is on the inlet side, and the quartz ark containing MXene is on the outlet side. The two arks are separated by 1-5cm (for example, 2, 3). , 4cm);
(3)在气体流速为70-300ml/min(例如80、90、100、110、120、130、140、150、160、170、180、190、200、210、220、230、240、250、260、270、280、290、300ml/min)的惰性气体保护下，以3～8℃/min的升温速度加热至300-500℃，保温3-5小时后冷至室温；(3) When the gas flow rate is 70-300ml/min (e.g. 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, Under the protection of inert gas of 260, 270, 280, 290, 300ml/min), heat to 300-500℃ at a heating rate of 3～8℃/min, keep it for 3-5 hours and then cool to room temperature;
(4)收集位于出气侧的石英方舟中的固体，即得到碲掺杂MXene材料。(4) Collect the solids in the quartz ark on the outlet side to obtain the tellurium-doped MXene material.
进一步地，所述碲源为碲粉、亚碲酸钠中的至少一种。优选粒径为50-150目(例如80、100、120目)的碲粉，优选纯度为99.99％。Further, the tellurium source is at least one of tellurium powder and sodium tellurite. The tellurium powder with a particle size of 50-150 mesh (for example, 80, 100, 120 mesh) is preferred, and the purity is preferably 99.99%.
所述MXene为Ti 3C 2T x、Mo 3C 2T x、V 3C 2T x、Ti 3N 2T x、Mo 3N 2T x、V 3N 2T x、Ti 2CT 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。 The MXene is Ti 3 C 2 T x , Mo 3 C 2 T x , V 3 C 2 T x , Ti 3 N 2 T x , Mo 3 N 2 T x , V 3 N 2 T x , Ti 2 CT x One or more of them, Ti 3 N 2 T x , V 3 C 2 T x , V 3 N 2 T x , Ti 3 C 2 T with a mass ratio of 4-9:1 x and V 3 C 2 T x , Ti 3 C 2 T x , V 3 N 2 T x and V 3 C 2 T x can be selected (for example, the mass ratio is 4-9:1:1), T x is the surface functional group -O, -F or -OH.
进一步地，所述碲掺杂MXene材料中碲掺杂量为0.5wt％-15wt％。Further, the doping amount of tellurium in the tellurium-doped MXene material is 0.5 wt% to 15 wt%.
进一步优选地，所述碲掺杂MXene材料中碲掺杂量为1.5wt％-10wt％，例如1.5wt％-5wt％，例如5wt％-9wt％。Further preferably, the doping amount of tellurium in the tellurium-doped MXene material is 1.5wt%-10wt%, for example 1.5wt%-5wt%, for example 5wt%-9wt%.
进一步地，所述惰性气体为Ar。Further, the inert gas is Ar.
进一步地，步骤(3)中在气体流速为220-300ml/min(例如250ml/min)的惰性气体保护下，以4～6℃/min(例如5℃/min)的升温速度加热至350-450℃，保温3-5小时后冷至室温。Further, in step (3), under the protection of an inert gas with a gas flow rate of 220-300 ml/min (for example, 250 ml/min), heating to 350-350 °C at a temperature increase rate of 4 to 6 °C/min (for example, 5 °C/min) 450°C, keep for 3-5 hours and then cool to room temperature.
一种碲掺杂MXene材料的制备方法制备得到的碲掺杂MXene材料。A tellurium-doped MXene material is prepared by a method for preparing tellurium-doped MXene material.
一种碲掺杂MXene材料的应用，将所述碲掺杂MXene材料用于钠离子电池负极。将碲掺杂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，用于钠离子电池负极，可极大提高钠离子电池的比容量、循环稳定性能。该材料制备方法简单，安全环保，适合大规模应用。An application of tellurium-doped MXene material, using the tellurium-doped MXene material for the negative electrode of a sodium ion battery. Mix the tellurium-doped MXene with carbon black and binder at a ratio of 8:1:1 (mass ratio), uniformly coat it on the current collector, vacuum dry and slice, and use it as the negative electrode of a sodium ion battery. Greatly improve the specific capacity and cycle stability of sodium ion batteries. The preparation method of the material is simple, safe and environmentally friendly, and suitable for large-scale applications.
碲原子半径大于S原子，在掺入MXene后，层间距更宽、活性位点更多，显著提高钠离子电池性能。The radius of tellurium atoms is larger than that of S atoms. After MXene is incorporated, the interlayer spacing is wider and the active sites are more, which significantly improves the performance of sodium ion batteries.
本发明的有益效果：The beneficial effects of the present invention:
(1)本发明制备的碲掺杂的MXene材料可极大提高钠离子电池的比容量、循环稳定性能；(1) The tellurium-doped MXene material prepared by the present invention can greatly improve the specific capacity and cycle stability of sodium ion batteries;
(2)本发明的制备方法简单，安全环保，适合大规模应用。(2) The preparation method of the present invention is simple, safe and environmentally friendly, and is suitable for large-scale applications.
附图说明BRIEF DESCRIPTION
图1是对比例1中未掺杂MXene材料的扫描电镜图；Figure 1 is a scanning electron microscope image of the undoped MXene material in Comparative Example 1;
图2是实施例2中碲掺杂MXene材料的扫描电镜图；2 is a scanning electron micrograph of the tellurium-doped MXene material in Example 2;
图3是对比例1中未掺杂MXene钠离子电池负极循环性能图；Figure 3 is a graph showing the cycle performance of the negative electrode of an undoped MXene sodium ion battery in Comparative Example 1;
图4是实施例2中碲掺杂MXene钠离子电池负极循环性能图。4 is a graph showing the cycle performance of the negative electrode of the tellurium-doped MXene sodium ion battery in Example 2.
具体实施方式detailed description
为了更好的解释本发明，现结合以下具体实施例做进一步说明，但是本发明不限于具体实施例。In order to better explain the present invention, a further description will be made with the following specific embodiments, but the present invention is not limited to the specific embodiments.
实施例1Example 1
一种碲掺杂MXene材料的制备方法，包括以下步骤：A preparation method of tellurium-doped MXene material includes the following steps:
(1)将50mg MXene材料(Ti 3C 2T x)和50mg碲粉分别加入两个石英方舟中，并将两个石英方舟放置在管式炉中间位置，其中盛放碲粉的方舟位于进气侧，盛放MXene的方舟位于出气侧，两方舟间隔1cm； (1) Add 50 mg of MXene material (Ti 3 C 2 T x ) and 50 mg of tellurium powder into two quartz arks respectively, and place the two quartz arks in the middle of the tube furnace, where the ark containing the tellurium powder is located in the inlet On the air side, the ark containing MXene is on the air outlet side, and the two arks are separated by 1 cm;
(2)在气体流速为70ml/min的惰性气体保护下，以5℃/min的升温速率加热至300℃，保温3小时后随炉冷至室温；(2) Under the protection of inert gas with a gas flow rate of 70ml/min, heat to 300°C at a heating rate of 5°C/min, keep it for 3 hours and then cool to room temperature with the furnace;
(3)收集位于出气侧的方舟中的固体，即得到碲掺杂MXene材料。(3) Collect the solids in the ark on the outlet side to obtain the tellurium-doped MXene material.
(4)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，用于钠离子电池负极。(4) Mix the tellurium-doped MXene obtained in (3) with carbon black and binder at a ratio (mass ratio) of 8:1:1, uniformly coat it on the current collector, vacuum dry and slice, then use On the negative electrode of sodium ion battery.
本实施例掺杂后的MXene比表面积为141.3m 2/g，层间距为0.71nm，碲原子含量为0.7％，远大于未掺杂MXene的比表面积(33.7m 2/g)、层间距(0.64nm)，掺杂的MXene钠离子电池负极的在100mA/g的电流密度下，循环100圈后的可逆容量为198.1mAh/g，是未掺杂MXene钠离子电池负极(107.2mAh/g)的1.85倍。 The specific surface area of the doped MXene in this embodiment is 141.3m 2 /g, the interlayer spacing is 0.71nm, and the content of tellurium atoms is 0.7%, which is much larger than the specific surface area (33.7m 2 /g) and interlayer spacing ( 0.64nm), the reversible capacity of the doped MXene sodium ion battery negative electrode at a current density of 100mA/g after 100 cycles is 198.1mAh/g, which is an undoped MXene sodium ion battery negative electrode (107.2mAh/g) 1.85 times.
实施例2Example 2
一种碲掺杂MXene材料的制备方法，包括以下步骤：A preparation method of tellurium-doped MXene material includes the following steps:
(1)称取50mg的MXene材料(Ti 3C 2T x)和150mg碲粉分别加入两个石英方舟中，并将两个石英方舟放置在管式炉中间位置，其中盛放碲粉的方舟位于进气侧，盛放MXene的方舟位于出气侧，两方舟间隔3cm； (1) Weigh 50 mg of MXene material (Ti 3 C 2 T x ) and 150 mg of tellurium powder into two quartz arks respectively, and place the two quartz arks in the middle of the tube furnace, in which the ark containing the tellurium powder Located on the inlet side, the ark containing MXene is on the outlet side, and the two arks are separated by 3cm;
(2)在气体流速为180ml/min的惰性气体保护下，以5℃/min的升温速率加热至400℃，保温4小时后随炉冷至室温；(2) Under the protection of inert gas with a gas flow rate of 180ml/min, heat to 400°C at a heating rate of 5°C/min, keep it for 4 hours and then cool to room temperature with the furnace;
(3)收集位于出气侧的方舟中的固体，即得到碲掺杂MXene材料。(3) Collect the solids in the ark on the outlet side to obtain the tellurium-doped MXene material.
(4)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，用于钠离子电池负极。(4) Mix the tellurium-doped MXene obtained in (3) with carbon black and binder at a ratio (mass ratio) of 8:1:1, uniformly coat it on the current collector, vacuum dry and slice, then use On the negative electrode of sodium ion battery.
本实施例掺杂后的MXene比表面积为327.8m 2/g，层间距为0.79nm，碲原子含量为3.1％， 远大于未掺杂MXene的比表面积(33.7m 2/g)、层间距(0.64nm)，图4所示掺杂的MXene钠离子电池负极在100mA/g的电流密度下，循环100圈后的可逆容量为332.5mAh/g，是图3所示未掺杂MXene钠离子电池负极(107.2mAh/g)的3.1倍。 The specific surface area of doped MXene in this embodiment is 327.8m 2 /g, the interlayer spacing is 0.79nm, and the content of tellurium atoms is 3.1%, which is much larger than the specific surface area (33.7m 2 /g) and interlayer spacing ( 0.64nm), the negative electrode of the doped MXene sodium ion battery shown in Figure 4 has a reversible capacity of 332.5mAh/g after 100 cycles at a current density of 100mA/g, which is the undoped MXene sodium ion battery shown in Figure 3. 3.1 times the negative electrode (107.2mAh/g).
实施例3Example 3
一种碲掺杂MXene材料的制备方法，包括以下步骤：A preparation method of tellurium-doped MXene material includes the following steps:
(1)称取50mg的MXene材料(Ti 2CT x)和250mg碲粉分别加入两个石英方舟中，并将两个石英方舟放置在管式炉中间位置，其中盛放碲粉的方舟位于进气侧，盛放MXene的方舟位于出气侧，两方舟间隔5cm； (1) Weigh 50 mg of MXene material (Ti 2 CT x ) and 250 mg of tellurium powder into two quartz arks, and place the two quartz arks in the middle of the tube furnace, where the ark containing the tellurium powder is located in the inlet On the air side, the ark containing MXene is on the air outlet side, and the two arks are separated by 5 cm;
(2)在气体流速为300ml/min的惰性气体保护下，以5℃/min的升温速率加热至500℃，保温5小时后随炉冷至室温；(2) Under the protection of inert gas with a gas flow rate of 300ml/min, heat to 500°C at a heating rate of 5°C/min, keep it for 5 hours and then cool to room temperature with the furnace;
(3)收集位于出气侧的方舟中的固体，即得到碲掺杂MXene材料。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，用于钠离子电池负极。(3) Collect the solids in the ark on the outlet side to obtain the tellurium-doped MXene material. Mix the tellurium-doped MXene obtained in (3) with carbon black and binder at a ratio of 8:1:1 (mass ratio), uniformly coat it on the current collector, vacuum dry and slice, and use it for sodium ion Battery negative.
本实施例掺杂后的MXene比表面积为289.1m 2/g，层间距为0.78nm，碲原子含量为9.6％，远大于未掺杂MXene的比表面积(33.7m 2/g)、层间距(0.64nm)，掺杂的MXene钠离子电池负极在100mA/g的电流密度下，循环100圈后的可逆容量为289.4mAh/g，是未掺杂MXene钠离子电池负极(107.2mAh/g)的2.7倍。 The specific surface area of doped MXene in this embodiment is 289.1m 2 /g, the interlayer spacing is 0.78nm, and the content of tellurium atoms is 9.6%, which is much larger than the specific surface area (33.7m 2 /g) and interlayer spacing ( 0.64nm), the doped MXene sodium ion battery negative electrode has a reversible capacity of 289.4mAh/g after 100 cycles at a current density of 100mA/g, which is the negative electrode of the undoped MXene sodium ion battery (107.2mAh/g) 2.7 times.
实施例4Example 4
一种碲掺杂MXene材料的制备方法，包括以下步骤：A preparation method of tellurium-doped MXene material includes the following steps:
(1)称取50mg的MXene材料(40mg Ti 3C 2T x和10mgV 3C 2T x)和150mg碲粉分别加入两个石英方舟中，并将两个石英方舟放置在管式炉中间位置，其中盛放碲粉的方舟位于进气侧，盛放MXene的方舟位于出气侧，两方舟间隔2cm； (1) Weigh 50mg of MXene material (40mg Ti 3 C 2 T x and 10mgV 3 C 2 T x ) and 150mg tellurium powder into two quartz arks respectively, and place the two quartz arks in the middle of the tube furnace , Where the ark containing tellurium powder is on the inlet side, and the ark containing MXene is on the outlet side, and the two arks are separated by 2cm;
(2)在气体流速为230ml/min的惰性气体保护下，以4℃/min的升温速率加热至380℃，保温4小时后随炉冷至室温；(2) Under the protection of an inert gas with a gas flow rate of 230ml/min, heat to 380°C at a heating rate of 4°C/min, keep it for 4 hours and then cool to room temperature with the furnace;
(3)收集位于出气侧的方舟中的固体，即得到碲掺杂MXene材料。(3) Collect the solids in the ark on the outlet side to obtain the tellurium-doped MXene material.
(4)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，用于钠离子电池负极。(4) Mix the tellurium-doped MXene obtained in (3) with carbon black and binder at a ratio (mass ratio) of 8:1:1, uniformly coat it on the current collector, vacuum dry and slice, then use On the negative electrode of sodium ion battery.
本实施例掺杂的MXene钠离子电池负极在100mA/g的电流密度下，循环100圈后的可逆容量为370.1mAh/g，是未掺杂MXene钠离子电池负极(107.2mAh/g)的3.5倍。The negative electrode of the doped MXene sodium ion battery in this example has a reversible capacity of 370.1mAh/g after 100 cycles at a current density of 100mA/g, which is 3.5 of that of the undoped MXene sodium ion battery negative electrode (107.2mAh/g). Times.
实施例5Example 5
一种碲掺杂MXene材料的制备方法，包括以下步骤：A preparation method of tellurium-doped MXene material includes the following steps:
(1)称取50mg的MXene材料(V 3C 2T x)和100mg碲粉分别加入两个石英方舟中，并将两个石英方舟放置在管式炉中间位置，其中盛放碲粉的方舟位于进气侧，盛放MXene的方舟位于出气侧，两方舟间隔3cm； (1) Weigh 50 mg of MXene material (V 3 C 2 T x ) and 100 mg of tellurium powder into two quartz arks, and place the two quartz arks in the middle of the tube furnace, which contains the tellurium powder. Located on the inlet side, the ark containing MXene is on the outlet side, and the two arks are separated by 3cm;
(2)在气体流速为260ml/min的惰性气体保护下，以6℃/min的升温速率加热至420℃，保温3小时后随炉冷至室温；(2) Under the protection of inert gas with a gas flow rate of 260ml/min, heat to 420°C at a heating rate of 6°C/min, keep it for 3 hours and then cool to room temperature with the furnace;
(3)收集位于出气侧的方舟中的固体，即得到碲掺杂MXene材料。(3) Collect the solids in the ark on the outlet side to obtain the tellurium-doped MXene material.
(4)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，用于钠离子电池负极。(4) Mix the tellurium-doped MXene obtained in (3) with carbon black and binder at a ratio (mass ratio) of 8:1:1, uniformly coat it on the current collector, vacuum dry and slice, then use On the negative electrode of sodium ion battery.
本实施例掺杂的MXene钠离子电池负极在100mA/g的电流密度下，循环100圈后的可逆容量为353.1mAh/g，是未掺杂MXene钠离子电池负极(107.2mAh/g)的3.3倍。The negative electrode of the doped MXene sodium ion battery in this example has a reversible capacity of 353.1mAh/g after 100 cycles at a current density of 100mA/g, which is 3.3 of that of the undoped MXene sodium ion battery negative electrode (107.2mAh/g). Times.
对比例1：未掺杂MXene钠离子电池负极，使用未掺杂MXene制备钠离子电池负极的过程同实施例2。Comparative Example 1: Undoped MXene sodium ion battery negative electrode, the process of using undoped MXene to prepare the sodium ion battery negative electrode is the same as in Example 2.
表1：性能测试Table 1: Performance test
Figure PCTCN2019097437-appb-000001
Figure PCTCN2019097437-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。The above are only specific embodiments of the present invention, and do not therefore limit the scope of the present invention. Any equivalent transformation made by the present invention, or directly or indirectly applied to other related technical fields, are included in the present invention in the same way. Within the scope of patent protection.

Claims (9)

  1. 一种碲掺杂MXene材料的制备方法，其特征在于，包括以下步骤：A preparation method of tellurium doped MXene material is characterized in that it comprises the following steps:
    (1)将MXene和碲源按照质量比为1∶1～5分别加入两个石英方舟中；(1) Add MXene and tellurium source to the two quartz arks according to the mass ratio of 1:1～5;
    (2)将两个石英舟放置在管式炉中，其中，盛放碲源的石英方舟位于进气侧，盛放MXene的石英方舟位于出气侧，两方舟间隔1-5cm；(2) Place two quartz boats in the tube furnace. Among them, the quartz ark containing the tellurium source is on the inlet side, and the quartz ark containing MXene is on the outlet side, and the two arks are separated by 1-5 cm;
    (3)在气体流速为70-300ml/min的惰性气体保护下，以3～8℃/min的升温速度加热至300-500℃，保温3-5小时后冷却至室温；(3) Under the protection of inert gas with a gas flow rate of 70-300ml/min, heat to 300-500°C at a heating rate of 3-8°C/min, keep it for 3-5 hours and then cool to room temperature;
    (4)收集位于出气侧的石英方舟中的固体，即得到碲掺杂MXene材料。(4) Collect the solids in the quartz ark on the outlet side to obtain the tellurium-doped MXene material.
  2. 根据权利要求1所述的碲掺杂MXene材料的制备方法，其特征在于，所述碲源为碲粉、亚碲酸钠中的至少一种。The method for preparing the tellurium-doped MXene material according to claim 1, wherein the tellurium source is at least one of tellurium powder and sodium tellurite.
  3. 根据权利要求1所述的碲掺杂MXene材料的制备方法，其特征在于，所述MXene为Ti 3C 2T x、Mo 3C 2T x、V 3C 2T x、Ti 3N 2T x、Mo 3N 2T x、V 3N 2T x、Ti 2CT x中的一种或多种。 The preparation method of tellurium-doped MXene material according to claim 1, wherein the MXene is Ti 3 C 2 T x , Mo 3 C 2 T x , V 3 C 2 T x , Ti 3 N 2 T One or more of x , Mo 3 N 2 T x , V 3 N 2 T x , and Ti 2 CT x .
  4. 根据权利要求1所述的碲掺杂MXene材料的制备方法，其特征在于，所述碲掺杂MXene材料中碲掺杂量为0.5wt％-15wt％。The method for preparing a tellurium-doped MXene material according to claim 1, wherein the doping amount of tellurium in the tellurium-doped MXene material is 0.5wt%-15wt%.
  5. 根据权利要求1所述的碲掺杂MXene材料的制备方法，其特征在于，所述碲掺杂MXene材料中碲掺杂量为1.5wt％-10wt％。The method for preparing a tellurium-doped MXene material according to claim 1, wherein the doping amount of tellurium in the tellurium-doped MXene material is 1.5wt%-10wt%.
  6. 根据权利要求1所述的碲掺杂MXene材料的制备方法，其特征在于，所述惰性气体为Ar。The method for preparing tellurium-doped MXene material according to claim 1, wherein the inert gas is Ar.
  7. 根据权利要求1所述的碲掺杂MXene材料的制备方法，其特征在于，步骤(3)中在气体流速为220-300ml/min的惰性气体保护下，以4～6℃/min的升温速度加热至350-450℃，保温3-5小时后冷却至室温。The method for preparing the tellurium-doped MXene material according to claim 1, wherein in step (3), under the protection of an inert gas with a gas flow rate of 220-300 ml/min, a heating rate of 4-6°C/min Heat to 350-450°C, keep for 3-5 hours and then cool to room temperature.
  8. 一种碲掺杂MXene材料，其特征在于，所述碲掺杂MXene材料由权利要求1-7中任一项所述的制备方法制备得到。A tellurium-doped MXene material, characterized in that the tellurium-doped MXene material is prepared by the preparation method of any one of claims 1-7.
  9. 一种根据权利要求8所述的碲掺杂MXene材料的应用，其特征在于，将所述碲掺杂MXene材料用于钠离子电池负极。An application of the tellurium-doped MXene material according to claim 8, wherein the tellurium-doped MXene material is used for the negative electrode of a sodium ion battery.
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