WO2020147295A1 - Se-doped mxene battery cathode material and preparation method and use thereof - Google Patents

Se-doped mxene battery cathode material and preparation method and use thereof Download PDF

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WO2020147295A1
WO2020147295A1 PCT/CN2019/098259 CN2019098259W WO2020147295A1 WO 2020147295 A1 WO2020147295 A1 WO 2020147295A1 CN 2019098259 W CN2019098259 W CN 2019098259W WO 2020147295 A1 WO2020147295 A1 WO 2020147295A1
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negative electrode
mxene
battery negative
electrode material
doped
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Chinese (zh)
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张业龙
徐晓丹
孙宏阳
陈俞程
汪达
宋伟东
张弛
温锦秀
郭月
刘争
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

Definitions

  • the invention belongs to the technical field of nano materials, and relates to a Se-doped MXene battery negative electrode material and a preparation method and application thereof, in particular to the application as an electrode material in a potassium ion battery.
  • lithium-ion batteries have achieved great success in the fields of electric vehicles and portable electronic devices.
  • the main factor limiting the continuous development of lithium-ion battery technology is that the reserves of lithium resources in the earth's crust are small and unevenly distributed.
  • the price of lithium resources is also rising, which is bound to Limit its application in large-scale electrical energy storage systems. Therefore, from a practical point of view and long-term consideration, relatively inexpensive potassium ion batteries have gradually attracted the attention of researchers.
  • one of the objectives of the present invention is to provide a Se-doped MXene battery negative electrode material.
  • Another object of the present invention is to provide a method for preparing the above-mentioned Se-doped MXene battery negative electrode material.
  • the present invention provides an application of a Se-doped MXene battery negative electrode material, and the Se-doped MXene battery negative electrode material is used as a potassium ion battery negative electrode.
  • a preparation method of Se-doped MXene battery negative electrode material is a heat treatment method and includes the following steps:
  • step (3) Wash the sample prepared in step (2) with a cleaning agent, centrifuge, and vacuum dry for 10-24 hours to obtain the Se-doped MXene battery negative electrode material.
  • the organic Se source is at least one of dibenzyl diselenide, selenophenol, and dimethyl selenium, preferably dibenzyl diselenide, and more preferably the mass ratio is (3 to 5):1 Dibenzyl diselenide and dimethyl selenium.
  • 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
  • Mo 3 N 2 T x , optional V 3 C 2 T x , optional Ti 3 N 2 T x preferably Ti 3 C 2 T x and Ti 3 C 2 T x with a mass ratio of 7-9:1 Mo 3 C 2 T x , Ti 3 C 2 T x , Mo 3 C 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 cleaning agent is at least one of water and ethanol.
  • the sample prepared in step (2) is washed with deionized water and absolute ethanol 2-6 times each, or alternatively with deionized water and absolute ethanol, preferably 3-4 times.
  • the amount of Se doping in the Se-doped MXene battery anode material is 1-10 wt% (for example, 2, 3, 4, 5, 6, 7, 8, 9, 10 wt%).
  • the protective gas is N 2 or Ar
  • the gas flow rate is 150-300 ml/min, such as 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290 , 300ml/min.
  • step (2) the heating temperature is 300-500°C, the reaction time is 2-5h, and the heat preservation is 2-4h.
  • the rotating speed used for centrifugation in step (3) is 4000-6000 revolutions per minute, preferably 5000 revolutions per minute.
  • the vacuum drying temperature in step (3) is 50-70°C, preferably 60°C, and the vacuum degree does not exceed 133 Pa, for example, does not exceed 125, 115, 105, 95, 85 Pa.
  • a Se-doped MXene battery negative electrode material prepared by a method for preparing a Se-doped MXene battery negative electrode material.
  • MXene As a new type of two-dimensional layered material, MXene has the advantages of good conductivity and high specific surface area. At present, MXene has received extensive attention and research as an electrode material for supercapacitors or lithium-ion batteries. The distance is small, the surface adsorbs -F/-OH and other groups, which is not conducive to the rapid migration of electrons or ions in the MXene material. After Se doping, part of the C and N atoms in MXene are replaced by Se atoms, and the surface has a large number of structural defects, resulting in more electrochemically active sites, and further improving the rate, cycle stability, and specific capacity. , The composite material is applied to the anode material of the potassium ion battery, which can construct a potassium ion battery with high performance, high safety and low cost.
  • the potassium ion battery negative electrode prepared by the present invention not only has good electrical conductivity, but also has a higher specific capacity and stable charge-discharge cycle characteristics;
  • the preparation method of the present invention is simple, high in production efficiency, and low in raw material cost, and is suitable for large-scale development and application of potassium ion batteries.
  • Figure 1 is a scanning electron microscope image of the undoped MXene material in Comparative Example 1;
  • Example 2 is a scanning electron microscope image of Se-doped MXene material in Example 1;
  • Figure 3 is a graph showing the cycle performance of the negative electrode of an undoped MXene potassium ion battery in Comparative Example 1;
  • Example 4 is a graph showing the cycle performance of the negative electrode of the Se-doped MXene potassium ion battery in Example 1.
  • a preparation method of Se-doped MXene battery negative electrode material is used.
  • a heat treatment method is used to prepare Se-doped MXene material by using MXene and dibenzyl diselenide in a mass ratio of 1:1 as raw materials, including the following steps :
  • step (3) The sample prepared in step (2) was washed 3 times with deionized water and absolute ethanol each, centrifuged, and dried under vacuum at 60° C. for 10 hours to finally prepare Se-doped MXene material.
  • the specific surface area of MXene doped with Se in this example is 208.5m 2 /g, the interlayer spacing is 0.73nm, and the selenium atom content is 1%, which is much larger than the specific surface area (61.9m 2 /g) and interlayer spacing of undoped MXene (0.57nm);
  • the negative electrode of the doped MXene potassium ion battery shown in Figure 4 has a reversible capacity of 234mAh/g after 100 cycles at a current density of 100mA/g, which is the undoped MXene potassium ion shown in Figure 3.
  • the negative electrode (121.7mAh/g) of the battery is 1.9 times, and the Se-doped MXene battery negative electrode material of this embodiment has very stable charge-discharge cycle characteristics.
  • a method for preparing Se-doped MXene battery negative electrode material includes the following steps:
  • step (3) The sample prepared in step (2) was washed with deionized water and absolute ethanol 3 times each, centrifuged, and dried under vacuum at 60° C. for 18 hours to finally prepare Se-doped MXene material.
  • the specific surface area of Se-doped MXene in this example is 341.7m 2 /g, the interlayer spacing is 0.79nm, and the selenium atom content is 7%, which is much larger than the specific surface area (61.9m 2 /g) and interlayer spacing of undoped MXene. (0.57nm);
  • the negative electrode of the doped MXene potassium ion battery in this embodiment has a reversible capacity of 328mAh/g after 100 cycles at a current density of 100mA/g, which is an undoped MXene potassium ion battery negative electrode (121.7mAh /g), and the Se-doped MXene battery negative electrode material of this embodiment has very stable charge-discharge cycle characteristics.
  • a preparation method of Se-doped MXene battery negative electrode material is adopted to use MXene and dibenzyl diselenide as raw materials in a mass ratio of 1:5, and the method includes the following steps:
  • step (3) The sample prepared in step (2) was washed with deionized water and absolute ethanol 3 times each, centrifuged, and dried under vacuum at 60° C. for 24 hours to finally prepare Se-doped MXene material.
  • the specific surface area of MXene doped with Se in this example is 291.3m 2 /g, the interlayer spacing is 0.80nm, and the selenium atom content is 9%, which is much larger than the specific surface area (61.9m 2 /g) and interlayer spacing of undoped MXene. (0.57nm);
  • the reversible capacity of the negative electrode of the doped MXene potassium ion battery in this embodiment at a current density of 100mA/g after 100 cycles is 279mAh/g, which is an undoped MXene potassium ion battery negative electrode (121.7mAh /g), and the Se-doped MXene battery negative electrode material of this embodiment has very stable charge-discharge cycle characteristics.
  • a method for preparing Se-doped MXene battery negative electrode material includes the following steps:
  • step (3) The sample prepared in step (2) was washed 3 times with deionized water and absolute ethanol each, centrifuged, and dried at 60° C. under vacuum for 12 hours to finally prepare Se-doped MXene material.
  • the reversible capacity of the Se-doped MXene potassium ion battery negative electrode in this example at a current density of 100mA/g after 100 cycles is 363mAh/g, which is the negative electrode of the undoped MXene potassium ion battery (121.7mAh/g) 3.0 times, and the Se-doped MXene battery negative electrode material of this embodiment has very stable charge-discharge cycle characteristics.
  • a preparation method of Se-doped MXene battery negative electrode material is adopted.
  • a heat treatment method is adopted to use MXene and an organic Se source as raw materials in a mass ratio of 1:4, including the following steps:
  • step (3) The sample prepared in step (2) was washed 3 times with deionized water and absolute ethanol each, centrifuged, and dried under vacuum at 60° C. for 10 hours to finally prepare Se-doped MXene material.
  • the reversible capacity of the negative electrode of the doped MXene potassium ion battery in this example at a current density of 100mA/g after 100 cycles is 406mAh/g, which is 3.34 of that of the non-doped MXene potassium ion battery negative electrode (121.7mAh/g)
  • the Se-doped MXene battery negative electrode material of this embodiment has very stable charge-discharge cycle characteristics.
  • Comparative Example 1 Undoped MXene potassium ion battery negative electrode.
  • Comparative Example 2 Using an inorganic selenium source (such as selenium powder), the negative electrode of a potassium ion battery doped with MXene, the doping process is the same as in Example 2.
  • an inorganic selenium source such as selenium powder
  • the negative electrode of a potassium ion battery doped with MXene the doping process is the same as in Example 2.

Abstract

A Se-doped MXene battery cathode material and a preparation method thereof, comprising the following steps: (1) placing MXene and an organic Se source into two ends of a quartz boat, respectively, at a mass ratio of 1:1-5; (2) placing the quartz boat into a tube furnace, placing the organic Se source upstream in the tube furnace, introducing a protective gas, heating to 300-1100°C at a heating rate of 4-6°C/min, a reaction time being 2-10 h, holding temperature for 2-6 h, then naturally cooling to room temperature; (3) cleaning with a cleaning agent then centrifuging the sample obtained in step (2), and vacuum drying for 10-24 h, obtaining a Se-doped MXene battery cathode material. A potassium ion battery cathode thus prepared not only has good electrical conductivity, but also has relatively high specific capacity and stable charge-discharge cycle characteristics.

Description

一种Se掺杂MXene电池负极材料及其制备方法和应用Se-doped MXene battery negative electrode material and preparation method and application thereof 技术领域Technical field
本发明属于纳米材料技术领域，涉及一种Se掺杂MXene电池负极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。The invention belongs to the technical field of nano materials, and relates to a Se-doped MXene battery negative electrode material and a preparation method and application thereof, in particular to the application as an electrode material in a potassium ion battery.
背景技术Background technique
近年来，人类过度使用化石能源引起的能源与环境危机严重影响了人类社会的可持续发展，为此，研究开发新型可再生清洁能源已经成为目前的研究重点。In recent years, the energy and environmental crises caused by human overuse of fossil energy have seriously affected the sustainable development of human society. For this reason, research and development of new renewable clean energy has become the current research focus.
目前，锂离子电池作为一种二次电池储能***已经在电动汽车和便携电子设备等领域取得了巨大的成功。目前来讲，限制锂离子电池技术持续发展的主要因素是锂资源在地壳中的储量较少且分布不均，随着锂离子电池用量不断增加，锂资源的价格也节节攀升，这势必会限制其在大型电能储存***中的应用。因此，从现实角度及长远考虑，相对廉价的钾离子电池逐渐引起了研究人员的关注。At present, as a secondary battery energy storage system, lithium-ion batteries have achieved great success in the fields of electric vehicles and portable electronic devices. At present, the main factor limiting the continuous development of lithium-ion battery technology is that the reserves of lithium resources in the earth's crust are small and unevenly distributed. With the continuous increase in the use of lithium-ion batteries, the price of lithium resources is also rising, which is bound to Limit its application in large-scale electrical energy storage systems. Therefore, from a practical point of view and long-term consideration, relatively inexpensive potassium ion batteries have gradually attracted the attention of researchers.
因为钾在自然界中储量丰富(钾元素在地壳中丰度为2.47％)，成本低廉，氧化还原电位较负(K+/K，-2.936V相对于标准氢电极电位)，能量密度高，较长的循环使用寿命及良好的倍率性能等方面的优势，基于以上优点，对钾离子电池研究越来越受到人们的关注。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。Because potassium is abundant in nature (the abundance of potassium in the crust is 2.47%), the cost is low, the redox potential is relatively negative (K+/K, -2.936V relative to the standard hydrogen electrode potential), and the energy density is high and longer Based on the advantages of long cycle life and good rate performance, the research of potassium ion batteries has attracted more and more attention. Therefore, the development of low-cost potassium ion batteries with good cycle performance has great commercial value.
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Se掺杂MXene电池负极材料及其钾离子电池具有重要的现实意义。 However, in the existing battery industry, there are many methods or process steps for preparing potassium 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 a low-cost, safer and environmentally friendly Se-doped MXene battery negative electrode material and its potassium ion battery through a simple method.
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Se掺杂MXene电池负极材料。本发明的另一目的在于提供上述Se掺杂MXene电池负极材料的制备方法。进一步的，本发明提供一种Se掺杂MXene电池负极材料的应用，将所述Se掺杂MXene电池负极材料用作钾离子电池负极。In view of the problems in the prior art, one of the objectives of the present invention is to provide a Se-doped MXene battery negative electrode material. Another object of the present invention is to provide a method for preparing the above-mentioned Se-doped MXene battery negative electrode material. Further, the present invention provides an application of a Se-doped MXene battery negative electrode material, and the Se-doped MXene battery negative electrode material is used as a potassium ion battery negative electrode.
本发明采用以下技术方案：The present invention adopts the following technical solutions:
一种Se掺杂MXene电池负极材料的制备方法，所述制备方法为热处理法，包括以下步骤：A preparation method of Se-doped MXene battery negative electrode material. The preparation method is a heat treatment method and includes the following steps:
(1)将MXene和有机Se源按照质量比为1∶(1～5)，可选1∶(2～4)，例如1∶3， 分别放置于石英舟的两端；(1) Place the MXene and the organic Se source at the two ends of the quartz boat according to the mass ratio of 1:(1～5), optional 1:(2～4), for example 1:3;
(2)将石英舟放于管式炉中，其中，将盛放有机Se源的一端放置于管式炉的上游，通入保护气体，以4～6℃/min的升温速度加热至300-1100℃(例如400℃、500℃、600℃、700℃、800℃、900℃、1000℃)，反应时间为2-10h(例如2、3、4、5、6、7、8、9、10h)，保温2-6h(例如2、3、4、5、6h)，然后自然冷却到室温；(2) Put the quartz boat in a tube furnace, in which, place the end containing the organic Se source upstream of the tube furnace, pass in protective gas, and heat it to 300- at a heating rate of 4-6°C/min. 1100℃ (for example, 400℃, 500℃, 600℃, 700℃, 800℃, 900℃, 1000℃), the reaction time is 2-10h (for example 2, 3, 4, 5, 6, 7, 8, 9, 10h), keep for 2-6h (for example, 2, 3, 4, 5, 6h), then cool to room temperature naturally;
(3)将步骤(2)所制样品用清洗剂进行洗涤后离心，真空干燥10-24h，得到所述Se掺杂MXene电池负极材料。(3) Wash the sample prepared in step (2) with a cleaning agent, centrifuge, and vacuum dry for 10-24 hours to obtain the Se-doped MXene battery negative electrode material.
进一步地，所述有机Se源为二苄基二硒醚、苯硒酚、二甲基硒中的至少一种，优选二苄基二硒醚，更优选质量比为(3～5)∶1的二苄基二硒醚和二甲基硒。Further, the organic Se source is at least one of dibenzyl diselenide, selenophenol, and dimethyl selenium, preferably dibenzyl diselenide, and more preferably the mass ratio is (3 to 5):1 Dibenzyl diselenide and dimethyl selenium.
进一步地，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中的一种或多种，可选Mo 3N 2T x，可选V 3C 2T x，可选Ti 3N 2T x，优选质量比为7～9∶1的Ti 3C 2T x和Mo 3C 2T x，可选Ti 3C 2T x、Mo 3C 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。 Further, 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 One or more, optional Mo 3 N 2 T x , optional V 3 C 2 T x , optional Ti 3 N 2 T x , preferably Ti 3 C 2 T x and Ti 3 C 2 T x with a mass ratio of 7-9:1 Mo 3 C 2 T x , Ti 3 C 2 T x , Mo 3 C 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，所述清洗剂为水、乙醇中的至少一种。优选地，步骤(2)所制样品用去离子水和无水乙醇各清洗2-6次，也可以用去离子水和无水乙醇交替清洗，优选3-4次。Further, the cleaning agent is at least one of water and ethanol. Preferably, the sample prepared in step (2) is washed with deionized water and absolute ethanol 2-6 times each, or alternatively with deionized water and absolute ethanol, preferably 3-4 times.
进一步地，所述Se掺杂MXene电池负极材料中Se掺杂量为1-10wt％(例如2、3、4、5、6、7、8、9、10wt％)。Further, the amount of Se doping in the Se-doped MXene battery anode material is 1-10 wt% (for example, 2, 3, 4, 5, 6, 7, 8, 9, 10 wt%).
进一步地，所述保护气体为N 2或Ar，气体流速为150-300ml/min，例如160、170、180、190、200、210、220、230、240、250、260、270、280、290、300ml/min。 Further, the protective gas is N 2 or Ar, and the gas flow rate is 150-300 ml/min, such as 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290 , 300ml/min.
进一步地，步骤(2)中加热温度为300-500℃，反应时间为2-5h，保温2-4h。Further, in step (2), the heating temperature is 300-500°C, the reaction time is 2-5h, and the heat preservation is 2-4h.
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。Further, the rotating speed used for centrifugation in step (3) is 4000-6000 revolutions per minute, preferably 5000 revolutions per minute.
进一步地，步骤(3)中真空干燥的温度为50-70℃，优选60℃，真空度不超过133Pa，例如不超过125、115、105、95、85Pa。Further, the vacuum drying temperature in step (3) is 50-70°C, preferably 60°C, and the vacuum degree does not exceed 133 Pa, for example, does not exceed 125, 115, 105, 95, 85 Pa.
一种Se掺杂MXene电池负极材料的制备方法制备得到的Se掺杂MXene电池负极材料。A Se-doped MXene battery negative electrode material prepared by a method for preparing a Se-doped MXene battery negative electrode material.
一种Se掺杂MXene电池负极材料的应用，将所述Se掺杂MXene电池负极材料用于钾离子电池负极。An application of Se-doped MXene battery negative electrode material, using the Se-doped MXene battery negative electrode material for potassium ion battery negative electrode.
MXene材料作为一种新型二维层状材料，MXene具有导电性好、比表面积高等优点，目前，MXene作为超级电容器或锂离子电池的电极材料，受到广泛的关注与研究，然而，MXene材料由于层间距小，表面吸附-F/-OH等基团，不利于电子或离子在MXene材料中快速迁移。通过Se掺杂后，MXene中部分C、N原子被Se原子取代，表面具有大量的结构缺陷，从而造成更多地电化学活性位点，使其倍率性、循环稳定性、比容量等进一步提高，将该复合材 料应用于钾离子电池负极材料，可以构建高性能、高安全、低成本的钾离子电池。As a new type of two-dimensional layered material, MXene has the advantages of good conductivity and high specific surface area. At present, MXene has received extensive attention and research as an electrode material for supercapacitors or lithium-ion batteries. The distance is small, the surface adsorbs -F/-OH and other groups, which is not conducive to the rapid migration of electrons or ions in the MXene material. After Se doping, part of the C and N atoms in MXene are replaced by Se atoms, and the surface has a large number of structural defects, resulting in more electrochemically active sites, and further improving the rate, cycle stability, and specific capacity. , The composite material is applied to the anode material of the potassium ion battery, which can construct a potassium ion battery with high performance, high safety and low cost.
本发明的有益效果：The beneficial effects of the present invention:
(1)本发明制备的钾离子电池负极，不但具有良好的导电性能，还具有较高的比容量及稳定的充放电循环特性；(1) The potassium ion battery negative electrode prepared by the present invention not only has good electrical conductivity, but also has a higher specific capacity and stable charge-discharge cycle characteristics;
(2)本发明的制备方法简单、生产效率高、原料成本低，适用于钾离子电池的大规模开发和应用。(2) The preparation method of the present invention is simple, high in production efficiency, and low in raw material cost, and is suitable for large-scale development and application of potassium ion batteries.
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1中Se掺杂MXene材料的扫描电镜图；2 is a scanning electron microscope image of Se-doped MXene material in Example 1;
图3是对比例1中未掺杂MXene钾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 potassium ion battery in Comparative Example 1;
图4是实施例1中Se掺杂MXene钾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 Se-doped MXene potassium ion battery in Example 1.
具体实施方式detailed description
为了更好的解释本发明，现结合以下具体实施例做进一步说明，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Se掺杂MXene电池负极材料的制备方法，本实施例中采用热处理的方法将MXene和二苄基二硒醚按照质量比为1∶1为原料，制备Se掺杂MXene材料，包括以下步骤：A preparation method of Se-doped MXene battery negative electrode material. In this embodiment, a heat treatment method is used to prepare Se-doped MXene material by using MXene and dibenzyl diselenide in a mass ratio of 1:1 as raw materials, including the following steps :
(1)将50mg MXene材料(Ti 3C 2T x)和50mg二苄基二硒醚分别放置于石英舟的两端； (1) Place 50 mg of MXene material (Ti 3 C 2 T x ) and 50 mg of dibenzyl diselenide on both ends of the quartz boat;
(2)将石英舟放于管式炉中，其中，二苄基二硒醚放置于管式炉的上游，通入高纯度Ar气，流速为150ml/min，加热温度为300℃，加热速率为5℃/min，反应时间为2h，并在此温度下保温2h，之后自然冷却到室温；(2) Put the quartz boat in a tube furnace, where the dibenzyl diselenide is placed upstream of the tube furnace, and high-purity Ar gas is introduced, the flow rate is 150ml/min, the heating temperature is 300℃, and the heating rate It is 5℃/min, the reaction time is 2h, and it is kept at this temperature for 2h, and then it is naturally cooled to room temperature;
(3)将步骤(2)所制样品用去离子水和无水乙醇各清洗3次，离心后，在60℃真空下干燥10h，最终制得Se掺杂MXene材料。(3) The sample prepared in step (2) was washed 3 times with deionized water and absolute ethanol each, centrifuged, and dried under vacuum at 60° C. for 10 hours to finally prepare Se-doped MXene material.
(4)钾离子电池负极制备：将(3)所得的Se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，制成钾离子电池负极片。(4) Preparation of negative electrode for potassium ion battery: Mix the Se-doped MXene obtained in (3) with polyvinylidene fluoride binder and carbon black in a mass ratio of 8:1:1, and add an appropriate amount of N-formaldehyde The base pyrrolidone solution is stirred and dispersed, stirred evenly to form a slurry and coated on the current collector, dried and sliced in vacuum to form the negative electrode sheet of the potassium ion battery.
本实施例Se掺杂后的MXene比表面积为208.5m 2/g，层间距为0.73nm，硒原子含量为1％，远大于未掺杂MXene的比表面积(61.9m 2/g)、层间距(0.57nm)；图4所示掺杂的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234mAh/g，是图3所示未掺杂MXene钾离子电池负极(121.7mAh/g)的1.9倍，且本实施例Se掺杂MXene电池负极材料具有非常稳定的充放电循环特性。 The specific surface area of MXene doped with Se in this example is 208.5m 2 /g, the interlayer spacing is 0.73nm, and the selenium atom content is 1%, which is much larger than the specific surface area (61.9m 2 /g) and interlayer spacing of undoped MXene (0.57nm); the negative electrode of the doped MXene potassium ion battery shown in Figure 4 has a reversible capacity of 234mAh/g after 100 cycles at a current density of 100mA/g, which is the undoped MXene potassium ion shown in Figure 3. The negative electrode (121.7mAh/g) of the battery is 1.9 times, and the Se-doped MXene battery negative electrode material of this embodiment has very stable charge-discharge cycle characteristics.
实施例2Example 2
一种Se掺杂MXene电池负极材料的制备方法，本实施例中采用热处理的方法将MXene和二苄基二硒醚按照质量比为1∶3为原料，包括以下步骤：A method for preparing Se-doped MXene battery negative electrode material. In this embodiment, a heat treatment method is adopted to use MXene and dibenzyl diselenide as raw materials in a mass ratio of 1:3, and the method includes the following steps:
(1)将100mg MXene材料(Ti 3C 2T x)和300mg二苄基二硒醚分别放置于石英舟的两端； (1) Place 100 mg of MXene material (Ti 3 C 2 T x ) and 300 mg of dibenzyl diselenide on both ends of the quartz boat;
(2)将石英舟放于管式炉中，其中，二苄基二硒醚放置于管式炉的上游，通入高纯度Ar气，气体流速为200ml/min，加热温度为700℃，加热速率为5℃/min，反应时间为6h，并在此温度下保温4h，之后自然冷却到室温；(2) Put the quartz boat in a tube furnace, where the dibenzyl diselenide is placed upstream of the tube furnace, and high-purity Ar gas is introduced. The gas flow rate is 200ml/min, and the heating temperature is 700℃. The rate is 5℃/min, the reaction time is 6h, and it is kept at this temperature for 4h, and then it is naturally cooled to room temperature;
(3)将步骤(2)所制样品用去离子水和无水乙醇各清洗3次，离心后，在60℃真空下干燥18h，最终制得Se掺杂MXene材料。(3) The sample prepared in step (2) was washed with deionized water and absolute ethanol 3 times each, centrifuged, and dried under vacuum at 60° C. for 18 hours to finally prepare Se-doped MXene material.
(4)钾离子电池负极制备：将(3)所得的Se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。(4) Preparation of negative electrode for potassium ion battery: Mix the Se-doped MXene obtained in (3) with polyvinylidene fluoride binder and carbon black in a mass ratio of 8:1:1, and add an appropriate amount of N-formaldehyde The base pyrrolidone solution is stirred and dispersed, stirred evenly to form a slurry and coated on the current collector, vacuum dried and sliced, to prepare a potassium ion battery negative electrode sheet.
本实施例Se掺杂后的MXene比表面积为341.7m 2/g，层间距为0.79nm，硒原子含量为7％，远大于未掺杂MXene的比表面积(61.9m 2/g)、层间距(0.57nm)；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328mAh/g，是未掺杂MXene钾离子电池负极(121.7mAh/g)的2.7倍，且本实施例Se掺杂MXene电池负极材料具有非常稳定的充放电循环特性。 The specific surface area of Se-doped MXene in this example is 341.7m 2 /g, the interlayer spacing is 0.79nm, and the selenium atom content is 7%, which is much larger than the specific surface area (61.9m 2 /g) and interlayer spacing of undoped MXene. (0.57nm); the negative electrode of the doped MXene potassium ion battery in this embodiment has a reversible capacity of 328mAh/g after 100 cycles at a current density of 100mA/g, which is an undoped MXene potassium ion battery negative electrode (121.7mAh /g), and the Se-doped MXene battery negative electrode material of this embodiment has very stable charge-discharge cycle characteristics.
实施例3Example 3
一种Se掺杂MXene电池负极材料的制备方法，本实施例中采用热处理的方法将MXene和二苄基二硒醚按照质量比为1∶5为原料，包括以下步骤：A preparation method of Se-doped MXene battery negative electrode material. In this embodiment, a heat treatment method is adopted to use MXene and dibenzyl diselenide as raw materials in a mass ratio of 1:5, and the method includes the following steps:
(1)将200mg MXene材料(Ti 3C 2T x)和1000mg二苄基二硒醚分别放置于石英舟的两端； (1) Place 200 mg of MXene material (Ti 3 C 2 T x ) and 1000 mg of dibenzyl diselenide on both ends of the quartz boat;
(2)将石英舟放于管式炉中，其中，二苄基二硒醚放置于管式炉的上游，通入高纯度Ar气，气体流速为300ml/min，加热温度为1100℃，加热速率为5℃/min，反应时间为10h，并在此温度下保温6h，之后自然冷却到室温；(2) Place the quartz boat in a tube furnace, where the dibenzyl diselenide is placed upstream of the tube furnace, and high-purity Ar gas is introduced. The gas flow rate is 300ml/min, and the heating temperature is 1100°C. The rate is 5℃/min, the reaction time is 10h, and it is kept at this temperature for 6h, and then it is naturally cooled to room temperature;
(3)将步骤(2)所制样品用去离子水和无水乙醇各清洗3次，离心后，在60℃真空下干燥24h，最终制得Se掺杂MXene材料。(3) The sample prepared in step (2) was washed with deionized water and absolute ethanol 3 times each, centrifuged, and dried under vacuum at 60° C. for 24 hours to finally prepare Se-doped MXene material.
(4)钾离子电池负极制备：将(3)所得的Se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。(4) Preparation of negative electrode for potassium ion battery: Mix the Se-doped MXene obtained in (3) with polyvinylidene fluoride binder and carbon black in a mass ratio of 8:1:1, and add an appropriate amount of N-formaldehyde The base pyrrolidone solution is stirred and dispersed, stirred evenly to form a slurry and coated on the current collector, vacuum dried and sliced, to prepare a potassium ion battery negative electrode sheet.
本实施例Se掺杂后的MXene比表面积为291.3m 2/g，层间距为0.80nm，硒原子含量为9％，远大于未掺杂MXene的比表面积(61.9m 2/g)、层间距(0.57nm)；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279mAh/g，是未掺杂MXene钾离子电池负极(121.7mAh/g)的2.3倍，且本实施例Se掺杂MXene电池负极材料具有非常稳定的充放电循环特性。 The specific surface area of MXene doped with Se in this example is 291.3m 2 /g, the interlayer spacing is 0.80nm, and the selenium atom content is 9%, which is much larger than the specific surface area (61.9m 2 /g) and interlayer spacing of undoped MXene. (0.57nm); The reversible capacity of the negative electrode of the doped MXene potassium ion battery in this embodiment at a current density of 100mA/g after 100 cycles is 279mAh/g, which is an undoped MXene potassium ion battery negative electrode (121.7mAh /g), and the Se-doped MXene battery negative electrode material of this embodiment has very stable charge-discharge cycle characteristics.
实施例4Example 4
一种Se掺杂MXene电池负极材料的制备方法，本实施例中采用热处理的方法将MXene和二苄基二硒醚按照质量比为1∶2为原料，包括以下步骤：A method for preparing Se-doped MXene battery negative electrode material. In this embodiment, a heat treatment method is adopted to use MXene and dibenzyl diselenide as raw materials in a mass ratio of 1:2, and the method includes the following steps:
(1)将100mg MXene材料(90mg Ti 3C 2T x和10mg Mo 3C 2T x)和200mg二苄基二硒醚分别放置于石英舟的两端； (1) Place 100 mg of MXene material (90 mg Ti 3 C 2 T x and 10 mg Mo 3 C 2 T x ) and 200 mg of dibenzyl diselenide on both ends of the quartz boat;
(2)将石英舟放于管式炉中，其中，二苄基二硒醚放置于管式炉的上游，通入高纯度Ar气，气体流速为180ml/min，加热温度为500℃，加热速率为5℃/min，反应时间为4h，并在此温度下保温2h，之后自然冷却到室温；(2) Place the quartz boat in a tube furnace, where the dibenzyl diselenide is placed upstream of the tube furnace, and high-purity Ar gas is introduced. The gas flow rate is 180ml/min, and the heating temperature is 500°C. The rate is 5℃/min, the reaction time is 4h, and it is kept at this temperature for 2h, and then it is naturally cooled to room temperature;
(3)将步骤(2)所制样品用去离子水和无水乙醇各清洗3次，离心后，在60℃真空下干燥12h，最终制得Se掺杂MXene材料。(3) The sample prepared in step (2) was washed 3 times with deionized water and absolute ethanol each, centrifuged, and dried at 60° C. under vacuum for 12 hours to finally prepare Se-doped MXene material.
(4)钾离子电池负极制备：将(3)所得的Se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。(4) Preparation of negative electrode for potassium ion battery: Mix the Se-doped MXene obtained in (3) with polyvinylidene fluoride binder and carbon black in a mass ratio of 8:1:1, and add an appropriate amount of N-formaldehyde The base pyrrolidone solution is stirred and dispersed, stirred evenly to form a slurry and coated on the current collector, vacuum dried and sliced, to prepare a potassium ion battery negative electrode sheet.
本实施例Se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363mAh/g，是未掺杂MXene钾离子电池负极(121.7mAh/g)的3.0倍，且本实施例Se掺杂MXene电池负极材料具有非常稳定的充放电循环特性。The reversible capacity of the Se-doped MXene potassium ion battery negative electrode in this example at a current density of 100mA/g after 100 cycles is 363mAh/g, which is the negative electrode of the undoped MXene potassium ion battery (121.7mAh/g) 3.0 times, and the Se-doped MXene battery negative electrode material of this embodiment has very stable charge-discharge cycle characteristics.
实施例5Example 5
一种Se掺杂MXene电池负极材料的制备方法，本实施例中采用热处理的方法将MXene和有机Se源按照质量比为1∶4为原料，包括以下步骤：A preparation method of Se-doped MXene battery negative electrode material. In this embodiment, a heat treatment method is adopted to use MXene and an organic Se source as raw materials in a mass ratio of 1:4, including the following steps:
(1)将100mg MXene材料(V 3C 2T x)和有机Se源(300mg二苄基二硒醚和100mg二甲基硒混合均匀)分别放置于石英舟的两端； (1) Place 100 mg of MXene material (V 3 C 2 T x ) and organic Se source (300 mg of dibenzyl diselenide and 100 mg of dimethyl selenium mixed uniformly) on both ends of the quartz boat;
(2)将石英舟放于管式炉中，其中，有机Se源放置于管式炉的上游，通入高纯度Ar气，气体流速为230ml/min，加热温度为600℃，加热速率为5℃/min，反应时间为3h，并在此温度下保温2h，之后自然冷却到室温；(2) Put the quartz boat in a tube furnace, where the organic Se source is placed upstream of the tube furnace, and high-purity Ar gas is introduced. The gas flow rate is 230ml/min, the heating temperature is 600℃, and the heating rate is 5 ℃/min, the reaction time is 3h, and keep it at this temperature for 2h, then cool to room temperature naturally;
(3)将步骤(2)所制样品用去离子水和无水乙醇各清洗3次，离心后，在60℃真空下干燥10h，最终制得Se掺杂MXene材料。(3) The sample prepared in step (2) was washed 3 times with deionized water and absolute ethanol each, centrifuged, and dried under vacuum at 60° C. for 10 hours to finally prepare Se-doped MXene material.
(4)钾离子电池负极制备：将(3)所得的Se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。(4) Preparation of negative electrode for potassium ion battery: Mix the Se-doped MXene obtained in (3) with polyvinylidene fluoride binder and carbon black in a mass ratio of 8:1:1, and add an appropriate amount of N-formaldehyde The base pyrrolidone solution is stirred and dispersed, stirred evenly to form a slurry and coated on the current collector, vacuum dried and sliced, to prepare a potassium ion battery negative electrode sheet.
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406mAh/g，是未掺杂MXene钾离子电池负极(121.7mAh/g)的3.34倍，且本实施例Se掺杂MXene电池负极材料具有非常稳定的充放电循环特性。The reversible capacity of the negative electrode of the doped MXene potassium ion battery in this example at a current density of 100mA/g after 100 cycles is 406mAh/g, which is 3.34 of that of the non-doped MXene potassium ion battery negative electrode (121.7mAh/g) Moreover, the Se-doped MXene battery negative electrode material of this embodiment has very stable charge-discharge cycle characteristics.
对比例1：未掺杂MXene钾离子电池负极。Comparative Example 1: Undoped MXene potassium ion battery negative electrode.
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。Comparative Example 2: Using an inorganic selenium source (such as selenium powder), the negative electrode of a potassium ion battery doped with MXene, the doping process is the same as in Example 2.
表1：性能测试Table 1: Performance test
Figure PCTCN2019098259-appb-000001
Figure PCTCN2019098259-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 (10)

  1. 一种Se掺杂MXene电池负极材料的制备方法，其特征在于，包括以下步骤：A preparation method of Se-doped MXene battery negative electrode material is characterized in that it comprises the following steps:
    (1)将MXene和有机Se源按照质量比为1∶1～5分别放置于石英舟的两端；(1) Place MXene and organic Se sources on the two ends of the quartz boat according to a mass ratio of 1:1～5;
    (2)将石英舟放于管式炉中，其中，将放有有机Se源的一端放置于管式炉的上游，通入保护气体，以4～6℃/min的升温速度加热至300-1100℃，反应时间为2-10h，保温2-6h，然后自然冷却到室温；(2) Put the quartz boat in a tube furnace, and place the end with the organic Se source on the upstream of the tube furnace, pass in protective gas, and heat to 300- at a temperature rise rate of 4-6°C/min. 1100℃, the reaction time is 2-10h, keep for 2-6h, then cool to room temperature naturally;
    (3)将步骤(2)所得样品用清洗剂进行洗涤后离心，真空干燥10-24h，得到所述Se掺杂MXene电池负极材料。(3) The sample obtained in step (2) is washed with a cleaning agent, centrifuged, and vacuum dried for 10-24 hours to obtain the Se-doped MXene battery negative electrode material.
  2. 根据权利要求1所述的Se掺杂MXene电池负极材料的制备方法，其特征在于，所述有机Se源为二苄基二硒醚、苯硒酚、二甲基硒中的至少一种。The preparation method of Se-doped MXene battery negative electrode material according to claim 1, wherein the organic Se source is at least one of dibenzyl diselenide, selenophenol, and dimethyl selenium.
  3. 根据权利要求1所述的Se掺杂MXene电池负极材料的制备方法，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中的一种或多种。 The method for preparing Se-doped MXene battery negative electrode 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 One or more of 2 T x , Mo 3 N 2 T x , and V 3 N 2 T x .
  4. 根据权利要求1所述的Se掺杂MXene电池负极材料的制备方法，其特征在于，所述清洗剂为水、乙醇中的至少一种。The method for preparing Se-doped MXene battery negative electrode material according to claim 1, wherein the cleaning agent is at least one of water and ethanol.
  5. 根据权利要求1所述的Se掺杂MXene电池负极材料的制备方法，其特征在于，所述Se掺杂MXene电池负极材料中Se掺杂量为1-10wt％。The method for preparing Se-doped MXene battery negative electrode material according to claim 1, wherein the Se doping amount in the Se-doped MXene battery negative electrode material is 1-10 wt%.
  6. 根据权利要求1所述的Se掺杂MXene电池负极材料的制备方法，其特征在于，所述保护气体为N 2或Ar，气体流速为150-300ml/min。 The method for preparing Se-doped MXene battery negative electrode material according to claim 1, wherein the protective gas is N 2 or Ar, and the gas flow rate is 150-300 ml/min.
  7. 根据权利要求1所述的Se掺杂MXene电池负极材料的制备方法，其特征在于，步骤(2)中加热温度为300-500℃，反应时间为2-5h，保温2-4h。The method for preparing Se-doped MXene battery negative electrode material according to claim 1, wherein the heating temperature in step (2) is 300-500°C, the reaction time is 2-5h, and the heat preservation is 2-4h.
  8. 根据权利要求1所述的Se掺杂MXene电池负极材料的制备方法，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℃，真空度为不超过133Pa。The method for preparing Se-doped MXene battery negative electrode material according to claim 1, characterized in that, in step (3), the rotation speed used for centrifugation is 4000-6000 rpm; the temperature of vacuum drying is 50-70°C , The vacuum degree is not more than 133Pa.
  9. 一种Se掺杂MXene电池负极材料，其特征在于，所述Se掺杂MXene电池负极材料由权利要求1-8中任一项所述的制备方法制备得到。A Se-doped MXene battery negative electrode material, characterized in that the Se-doped MXene battery negative electrode material is prepared by the preparation method of any one of claims 1-8.
  10. 一种根据权利要求9所述的Se掺杂MXene电池负极材料的应用，其特征在于，将所述Se掺杂MXene电池负极材料用于钾离子电池负极。An application of the Se-doped MXene battery negative electrode material according to claim 9, characterized in that the Se-doped MXene battery negative electrode material is used as a potassium ion battery negative electrode.
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