CN111799464A - A kind of MXene/graphene composite nanosheet and its preparation method and application, electrode pole piece and its application - Google Patents
A kind of MXene/graphene composite nanosheet and its preparation method and application, electrode pole piece and its application Download PDFInfo
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- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims abstract description 46
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
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- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
技术领域technical field
本发明涉及二维材料技术领域，具体涉及一种MXene/石墨烯复合纳米片及其制备方法和应用、电极极片及其应用。The invention relates to the technical field of two-dimensional materials, in particular to an MXene/graphene composite nanosheet, a preparation method and application thereof, an electrode pole piece and application thereof.
背景技术Background technique
二维(2D)过渡金属碳化物(Ti3C2、Ti2C、Ta4C3等)和氮化物(Ti3CN或Ti4N3)Mn+1Xn被标记为MXene，结构与石墨烯相似。MXene是从通式为Mn+1AXn的三维MAX相中选择性腐蚀“A”金属而生产的，其中M代表过渡金属，A代表IIIA或IVA族元素，X为碳(C)或氮(N)，n＝1、2或3。以Ti3AlC2为例，为了从Ti3AlC2相中提取Al原子层而不破坏Ti3AlC2的层状形态，通常将Ti3AlC2粉末在室温下浸泡在氢氟酸中，通过刻蚀得到层状二维材料Ti3C2。MXene具有金属导电特性，具有较高的锂离子存储能力和良好的倍率性能，被认为是一种很有潜力的锂离子电池或锂离子电容器的电极材料，通过对多层MXene进行剥离可以得到锂离子存储量更多的单层或少层的MXene。但是，剥离后的MXene纳米片结构不稳定，易发生重新堆叠，而大幅度降低MXene暴露在电解液中的比表面积并阻碍锂离子的嵌入，从而削弱MXene作为电极材料的性能。目前，防止MXene纳米薄片重新堆叠的有效方法为制备MXene与其他“支柱”材料混合的复合材料，其中，二维片状石墨烯被认为是理想的“支柱”材料。 Two -dimensional (2D) transition metal carbides ( Ti3C2 , Ti2C , Ta4C3 , etc.) and nitrides ( Ti3CN or Ti4N3 ) Mn+ 1Xn are labeled as MXene , structure Similar to graphene. MXenes are produced from the selective corrosion of "A" metals from a three-dimensional MAX phase of the general formula Mn + 1AXn, where M represents a transition metal, A represents a group IIIA or IVA element, and X is carbon (C) or nitrogen (N), n=1, 2 or 3. Taking Ti 3 AlC 2 as an example, in order to extract the Al atomic layer from the Ti 3 AlC 2 phase without destroying the layered morphology of Ti 3 AlC 2 , the Ti 3 AlC 2 powder is usually immersed in hydrofluoric acid at room temperature and passed through The layered two-dimensional material Ti 3 C 2 is obtained by etching. MXene has metal conductive properties, high lithium-ion storage capacity and good rate capability, and is considered to be a potential electrode material for lithium-ion batteries or lithium-ion capacitors. Lithium can be obtained by exfoliating multilayer MXenes. Monolayer or few-layer MXene with more ion storage. However, the exfoliated MXene nanosheets are unstable in structure and prone to re-stacking, which greatly reduces the specific surface area of MXene exposed to the electrolyte and hinders the intercalation of lithium ions, thereby weakening the performance of MXene as an electrode material. At present, an effective method to prevent the rearrangement of MXene nanosheets is to prepare composites of MXene mixed with other "pillar" materials, among which 2D sheet graphene is considered as an ideal "pillar" material.
然而，氧化石墨烯(GO)和MXene的表面具有丰富的官能团，由于官能团的电离作用，GO和MXene表面通常带负电，这使得GO很难与Ti3AlC2偶合，并且不稳定的微观异质结构不利于材料储锂性能的发挥。中国专利CN107633954B公开了一种石墨烯/MXene复合材料及其应用，其中MXene仅作为导电颗粒添加到石墨烯层间，未对MXene进行剥离，储锂性能较差。中国专利CN110942921A公开了一种新型三维复合气凝胶电极材料的制备方法，其中在多层层状MXene表面上生长NiCo-LDH后混合氧化石墨烯，经过冷冻干燥获得三维复合气凝胶，然而该材料中MXene的重新堆叠情况未能解决，储锂性能受到阻碍。However, the surfaces of graphene oxide (GO) and MXene are rich in functional groups, and the surfaces of GO and MXene are usually negatively charged due to the ionization of functional groups, which makes it difficult for GO to couple with Ti3AlC2 , and unstable microscopic heterogeneity The structure is not conducive to the performance of the lithium storage performance of the material. Chinese patent CN107633954B discloses a graphene/MXene composite material and its application, in which MXene is only added as conductive particles between graphene layers, and the MXene is not exfoliated, resulting in poor lithium storage performance. Chinese patent CN110942921A discloses a preparation method of a novel three-dimensional composite aerogel electrode material, wherein NiCo-LDH is grown on the surface of multi-layer layered MXene and then mixed with graphene oxide, and three-dimensional composite aerogel is obtained by freeze-drying. The re-stacking situation of MXene in the material is not resolved, and the lithium storage performance is hindered.
发明内容SUMMARY OF THE INVENTION
鉴于此，本发明的目的在于提供一种MXene/石墨烯复合纳米片及其制备方法和应用、电极极片及其应用。本发明提供的制备方法制备的材料中石墨烯不易发生重新堆叠，储锂性能优异。In view of this, the purpose of the present invention is to provide a kind of MXene/graphene composite nanosheet and its preparation method and application, electrode pole piece and its application. In the material prepared by the preparation method provided by the invention, the graphene is not easy to be re-stacked, and the lithium storage performance is excellent.
为了实现上述发明目的，本发明提供以下技术方案：In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:
本发明提供了一种MXene/石墨烯复合纳米片的制备方法，包括以下步骤：The invention provides a preparation method of MXene/graphene composite nanosheet, comprising the following steps:
将MAX和氢氟酸溶液混合，进行刻蚀，得到MXene；Mix MAX and hydrofluoric acid solution and perform etching to obtain MXene;
将所述MXene和四丁基氢氧化铵溶液混合，进行静电吸附后超声处理静电吸附，得到剥离MXene纳米片分散液；Mixing the MXene and tetrabutylammonium hydroxide solution, performing electrostatic adsorption and ultrasonic treatment for electrostatic adsorption, to obtain a peeled MXene nanosheet dispersion;
将所述剥离MXene纳米片分散液和氧化石墨烯悬浮液混合，进行自组装反应，得到MXene纳米片/氧化石墨烯纳米片；Mixing the exfoliated MXene nanosheet dispersion and the graphene oxide suspension to carry out a self-assembly reaction to obtain MXene nanosheets/graphene oxide nanosheets;
在保护气氛下，将所述MXene纳米片/氧化石墨烯纳米片进行还原反应，得到MXene/石墨烯复合纳米片。Under a protective atmosphere, the MXene nanosheets/graphene oxide nanosheets are subjected to a reduction reaction to obtain MXene/graphene composite nanosheets.
优选的，所述四丁基氢氧化铵溶液的浓度为20～25wt％；Preferably, the concentration of the tetrabutylammonium hydroxide solution is 20-25wt%;
所述MXene质量和四丁基氢氧化铵溶液体积的比为1g：(25～50)mL。The ratio of the mass of the MXene to the volume of the tetrabutylammonium hydroxide solution is 1 g: (25-50) mL.
优选的，所述静电吸附的温度为室温，时间为10～20h。Preferably, the temperature of the electrostatic adsorption is room temperature, and the time is 10-20 h.
优选的，所述剥离MXene纳米片分散液中的剥离MXene纳米片和氧化石墨烯悬浮液中氧化石墨烯的质量比为1:10～10:1。Preferably, the mass ratio of the exfoliated MXene nanosheets in the exfoliated MXene nanosheet dispersion to the graphene oxide in the graphene oxide suspension is 1:10-10:1.
优选的，所述自组装反应的温度为室温，时间为1～3h。Preferably, the temperature of the self-assembly reaction is room temperature, and the time is 1-3 hours.
优选的，所述还原反应的温度为300～500℃，时间为2～4h。Preferably, the temperature of the reduction reaction is 300-500° C., and the time is 2-4 h.
本发明提供了上述技术方案所述制备方法制备的MXene/石墨烯复合纳米片，具有异质层状结构，包括相互层叠的剥离MXene纳米片层和石墨烯层。The present invention provides the MXene/graphene composite nanosheet prepared by the preparation method described in the above technical solution, which has a heterogeneous layered structure, including exfoliated MXene nanosheet layers and graphene layers stacked on each other.
优选的，所述MXene/石墨烯复合纳米片中相邻两层的间距为1～2nm。Preferably, the distance between two adjacent layers in the MXene/graphene composite nanosheet is 1-2 nm.
本发明还提供了一种电极极片，包括导电基体和涂覆于导电基体表面的导电层，所述导电层包括上述技术方案所述MXene/石墨烯复合纳米片、导电炭黑和聚偏氟乙烯。The present invention also provides an electrode pole piece, comprising a conductive substrate and a conductive layer coated on the surface of the conductive substrate, wherein the conductive layer includes the MXene/graphene composite nanosheets, conductive carbon black and polyvinylidene fluoride described in the above technical solution vinyl.
本发明还提供了上述技术方案所述MXene/石墨烯复合纳米片，上述技术方案所述电极极片在超级电容器、锂离子电池或电催化材料中的应用。The present invention also provides the MXene/graphene composite nanosheet according to the above technical solution, and the application of the electrode pole piece according to the above technical solution in supercapacitors, lithium ion batteries or electrocatalytic materials.
本发明提供了一种MXene/石墨烯复合纳米片的制备方法，包括以下步骤：将MAX和氢氟酸溶液混合，进行刻蚀，得到MXene；将所述MXene和四丁基氢氧化铵溶液混合，进行静电吸附后在保护气氛下进行超声处理，得到剥离MXene纳米片分散液；将所述剥离MXene纳米片分散液和氧化石墨烯悬浮液混合，进行自组装反应后干燥，得到MXene纳米片/氧化石墨烯纳米片；在保护气氛下，将所述MXene纳米片/氧化石墨烯纳米片进行还原反应，得到MXene/石墨烯复合纳米片。本发明采用四丁基铵离子对MXene进行插层剥离后，MXene的表面电荷被四丁基铵离子修饰，携带正电荷，由于静电作用，带正电的剥离MXene纳米片与带负电的氧化石墨烯发生自组装，MXene层间空间进一步增加，能够暴露出更多的储锂活性位点，四丁基铵离子作为阳离子中间体辅助两种纳米片形成独特的面对面排列结构，保持了MXene与石墨烯的独特二维结构，且二维结构稳定，剥离后的MXene和石墨烯不会发生重新堆叠，开放的层间空间能够为锂离子的快速传输提供通道；还原反应过程中不但能够有效还原氧化石墨烯，还能够去除作为耦合剂的四丁基铵离子，在保持微观结构的同时有效提高石墨烯与MXene之间的电子转移能力，导电性能得到进一步优化。而且，本发明提供的制备方法，操作简单，成本低，适宜工业化生产。The invention provides a method for preparing MXene/graphene composite nanosheets, comprising the following steps: mixing MAX and a hydrofluoric acid solution, and performing etching to obtain MXene; mixing the MXene and a tetrabutylammonium hydroxide solution, and performing etching After electrostatic adsorption, ultrasonic treatment is performed under a protective atmosphere to obtain exfoliated MXene nanosheet dispersion; the exfoliated MXene nanosheet dispersion and graphene oxide suspension are mixed, subjected to self-assembly reaction, and then dried to obtain MXene nanosheets/graphite oxide Under a protective atmosphere, the MXene nanosheet/graphene oxide nanosheet is subjected to a reduction reaction to obtain an MXene/graphene composite nanosheet. In the present invention, after MXene is intercalated and exfoliated by tetrabutylammonium ions, the surface charge of MXene is modified by tetrabutylammonium ions and carries positive charges. Due to the electrostatic effect, the positively charged exfoliated MXene nanosheets and the negatively charged graphite oxide are separated. The self-assembly of ene occurs, the interlayer space of MXene is further increased, and more active sites for lithium storage can be exposed. The tetrabutylammonium ion acts as a cation intermediate to assist the two nanosheets to form a unique face-to-face arrangement, which maintains MXene and graphite. The unique two-dimensional structure of ene, and the two-dimensional structure is stable, the exfoliated MXene and graphene will not be re-stacked, and the open interlayer space can provide a channel for the rapid transport of lithium ions; not only can the reduction reaction process effectively reduce oxidation Graphene can also remove tetrabutylammonium ions as a coupling agent, effectively improving the electron transfer ability between graphene and MXene while maintaining the microstructure, and the electrical conductivity is further optimized. Moreover, the preparation method provided by the present invention has simple operation, low cost, and is suitable for industrial production.
本发明制备的MXene/石墨烯复合纳米片中石墨烯不会发生重新堆叠，具有优异的储锂性能，且能够保持MXene与石墨烯的独特二维结构，能够应用于超级电容器、锂离子电池或电催化材料。The graphene in the MXene/graphene composite nanosheets prepared by the invention will not be re-stacked, has excellent lithium storage performance, can maintain the unique two-dimensional structure of MXene and graphene, and can be applied to super capacitors, lithium ion batteries or Electrocatalytic materials.
附图说明Description of drawings
图1为实施例1制备的MXene/石墨烯复合纳米片的X射线衍射谱图；Fig. 1 is the X-ray diffraction spectrum of the MXene/graphene composite nanosheet prepared in Example 1;
图2为实施例1制备的MXene/石墨烯复合纳米片的扫描电子显微镜图；Fig. 2 is the scanning electron microscope picture of the MXene/graphene composite nanosheet prepared by
图3为实施例1制备的MXene/石墨烯复合纳米片的透射电子显微镜图；3 is a transmission electron microscope image of the MXene/graphene composite nanosheet prepared in Example 1;
图4为实施例1制备的MXene/石墨烯复合纳米片的X射线光电子能谱图；Fig. 4 is the X-ray photoelectron spectrogram of the MXene/graphene composite nanosheet prepared in Example 1;
图5为实施例1～3制备的MXene/石墨烯复合纳米片制备的电极极片的的倍率性能图。5 is a graph of the rate performance of the electrode pole pieces prepared from the MXene/graphene composite nanosheets prepared in Examples 1-3.
具体实施方式Detailed ways
本发明提供了一种MXene/石墨烯复合纳米片的制备方法，包括以下步骤：The invention provides a preparation method of MXene/graphene composite nanosheet, comprising the following steps:
将MAX和氢氟酸溶液混合，进行刻蚀，得到MXene；Mix MAX and hydrofluoric acid solution and perform etching to obtain MXene;
将所述MXene和四丁基氢氧化铵溶液混合，进行静电吸附后超声处理，得到剥离MXene纳米片分散液；Mixing the MXene and tetrabutylammonium hydroxide solution, performing electrostatic adsorption and then ultrasonic treatment to obtain the exfoliated MXene nanosheet dispersion;
将所述剥离MXene纳米片分散液和氧化石墨烯悬浮液混合，进行自组装反应，得到MXene纳米片/氧化石墨烯纳米片；Mixing the exfoliated MXene nanosheet dispersion and the graphene oxide suspension to carry out a self-assembly reaction to obtain MXene nanosheets/graphene oxide nanosheets;
在保护气氛下，将所述MXene纳米片/氧化石墨烯纳米片进行还原反应，得到MXene/石墨烯复合纳米片。Under a protective atmosphere, the MXene nanosheets/graphene oxide nanosheets are subjected to a reduction reaction to obtain MXene/graphene composite nanosheets.
在本发明中，若无特殊说明，所有的原料组分均为本领域技术人员熟知的市售商品。In the present invention, unless otherwise specified, all raw material components are commercially available commodities well known to those skilled in the art.
本发明将MAX和氢氟酸溶液混合，进行刻蚀，得到MXene。In the present invention, MAX and a hydrofluoric acid solution are mixed to perform etching to obtain MXene.
在本发明中，所述MAX的粒径优选为20～50μm，更优选为35～45μm；所述MAX的化学组成优选为Ti3AlC2；所述MAX优选购买于福斯曼科技(北京)有限公司。在本发明中，所述氢氟酸溶液的浓度优选为30～50wt％，更优选为35～45wt％，最优选为40wt％。在本发明中，所述MAX和氢氟酸溶液中氢氟酸的质量比优选为1:(15～25)，更优选为1:(16.5～22)，最优选为1:(18～20)。In the present invention, the particle size of the MAX is preferably 20-50 μm, more preferably 35-45 μm; the chemical composition of the MAX is preferably Ti 3 AlC 2 ; the MAX is preferably purchased from Forsman Technology (Beijing) Ltd. In the present invention, the concentration of the hydrofluoric acid solution is preferably 30-50 wt %, more preferably 35-45 wt %, and most preferably 40 wt %. In the present invention, the mass ratio of the MAX to the hydrofluoric acid in the hydrofluoric acid solution is preferably 1:(15-25), more preferably 1:(16.5-22), and most preferably 1:(18-20 ).
在本发明中，所述混合优选为搅拌混合，本发明对于所述搅拌混合的速度和时间没有特殊限定，能够将MAX混合分散于氢氟酸溶液中即可。In the present invention, the mixing is preferably stirring and mixing, and the speed and time of the stirring and mixing are not particularly limited in the present invention, and the MAX can be mixed and dispersed in the hydrofluoric acid solution.
在本发明中，所述刻蚀优选在搅拌条件下进行；所述刻蚀的温度优选为室温；时间优选为12～24h，更优选为15～21h，最优选为18～20h。在本发明中，所述刻蚀过程中MAX中金属被氢氟酸去除。In the present invention, the etching is preferably performed under stirring conditions; the etching temperature is preferably room temperature; the time is preferably 12-24 hours, more preferably 15-21 hours, and most preferably 18-20 hours. In the present invention, the metal in the MAX is removed by hydrofluoric acid during the etching process.
所述刻蚀后，本发明优选还包括将所述刻蚀后的体系进行固液分离，将所得固体组分进行水洗后干燥，得到MXene。本发明对于所述固液分离的方式没有特殊限定，采用本领域技术人员熟知的固液分离方式即可，具体如过滤或离心分离；本发明对于所述离心分离的条件没有特殊限定，采用本领域技术人员熟知的离心分离条件即可。在本发明中，所述水洗优选为去离子水洗，本发明对于所述水洗的次数没有特殊限定，能够将固体组分表面的氢氟酸去除干净即可。在本发明中，所述干燥优选为冷冻干燥，所述冷冻干燥的温度优选为-30～-55℃，更优选为-35～-45℃；时间优选为24～48h，更优选为30～45h，最优选为35～40h。After the etching, the present invention preferably further includes performing solid-liquid separation on the etched system, washing the obtained solid component with water, and drying to obtain MXene. The method of the solid-liquid separation is not particularly limited in the present invention, and a solid-liquid separation method well-known to those skilled in the art can be used, such as filtration or centrifugal separation; Centrifugal separation conditions well known to those skilled in the art are sufficient. In the present invention, the water washing is preferably deionized water washing, and the present invention does not limit the number of times of the water washing, as long as the hydrofluoric acid on the surface of the solid component can be completely removed. In the present invention, the drying is preferably freeze-drying, and the temperature of the freeze-drying is preferably -30～-55°C, more preferably -35～-45°C; the time is preferably 24～48h, more preferably 30～ 45h, most preferably 35-40h.
得到MXene后，本发明将所述MXene和四丁基氢氧化铵溶液混合，进行静电吸附后超声处理，得到剥离MXene纳米片分散液。After the MXene is obtained, the present invention mixes the MXene with the tetrabutylammonium hydroxide solution, performs electrostatic adsorption and then ultrasonic treatment to obtain the exfoliated MXene nanosheet dispersion.
在本发明中，所述四丁基氢氧化铵(TBAOH)溶液的浓度优选为20～25wt％，更优选为21～24wt％，最优选为22～23wt％。在本发明中，所述MXene质量和四丁基氢氧化铵溶液体积的比优选为1g：(25～50)mL，更优选为1g：(27.5～45)mL，最优选为1g：(30～40)mL。In the present invention, the concentration of the tetrabutylammonium hydroxide (TBAOH) solution is preferably 20-25 wt %, more preferably 21-24 wt %, and most preferably 22-23 wt %. In the present invention, the ratio of the mass of the MXene to the volume of the tetrabutylammonium hydroxide solution is preferably 1g:(25-50)mL, more preferably 1g:(27.5-45)mL, most preferably 1g:(30-40) )mL.
在本发明中，所述混合优选为搅拌混合，本发明对于所述搅拌混合的速度和时间没有特殊限定，能够将MXene混合分散于四丁基氢氧化铵溶液中即可。In the present invention, the mixing is preferably stirring and mixing, and the speed and time of the stirring and mixing are not particularly limited in the present invention, as long as the MXene can be mixed and dispersed in the tetrabutylammonium hydroxide solution.
在本发明中，所述静电吸附优选在搅拌条件下进行；所述静电吸附的温度优选为室温；时间优选为10～20h，更优选为12～18h，最优选为14～16h。在本发明中，所述静电吸附过程中四丁基铵离子(TBA+)插层到MXene层间，打开MXene层间空间，形成TBA+剥离MXene纳米片。In the present invention, the electrostatic adsorption is preferably performed under stirring conditions; the temperature of the electrostatic adsorption is preferably room temperature; the time is preferably 10-20 hours, more preferably 12-18 hours, and most preferably 14-16 hours. In the present invention, during the electrostatic adsorption process, tetrabutylammonium ions (TBA + ) are intercalated into the interlayers of MXene to open the interlayer space of MXene to form TBA + exfoliated MXene nanosheets.
所述静电吸附后，本发明优选还包括将所述静电吸附反应的体系进行固液分离，将所得固体组分进行水洗后干燥，然后将干燥物置于水中进行超声分散，得到剥离MXene纳米片分散液。After the electrostatic adsorption, the present invention preferably further includes performing solid-liquid separation on the electrostatic adsorption reaction system, washing the obtained solid component with water and then drying, and then placing the dried product in water for ultrasonic dispersion to obtain exfoliated MXene nanosheet dispersion. liquid.
本发明对于所述固液分离的方式没有特殊限定，采用本领域技术人员熟知的固液分离方式即可，具体如过滤或离心分离；本发明对于所述离心分离的条件没有特殊限定，采用本领域技术人员熟知的离心分离条件即可。在本发明中，所述水洗优选为去离子水洗，本发明对于所述水洗的次数没有特殊限定，能将氢氟酸去除干净即可。在本发明中，所述干燥优选为冷冻干燥，所述冷冻干燥的温度优选为-30～-55℃，更优选为-35～-45℃；时间优选为20～30h，更优选为24h。The method of the solid-liquid separation is not particularly limited in the present invention, and a solid-liquid separation method well-known to those skilled in the art can be used, such as filtration or centrifugal separation; Centrifugal separation conditions well known to those skilled in the art are sufficient. In the present invention, the water washing is preferably deionized water washing, and the present invention does not specifically limit the number of times of the water washing, as long as the hydrofluoric acid can be completely removed. In the present invention, the drying is preferably freeze-drying, and the temperature of the freeze-drying is preferably -30～-55°C, more preferably -35～-45°C; the time is preferably 20～30h, more preferably 24h.
在本发明中，所述水优选为去离子水，所述剥离MXene纳米片分散液的浓度优选为0.1～10g/L，更优选为0.5～8g/L，最优选为1～5g/L。在本发明中，所述超声分散优选在保护气氛中进行；本发明对于所述保护气氛的种类没有特殊限定，采用本领域技术人员熟知的保护气氛即可，具体如氮气或氩气；本发明在保护气氛中进行超声分散能够防止MXene被氧化；本发明对于所述超声处理的超声功率没有特殊限定，采用本领域技术人员熟知的超声功率即可；所述超声处理的温度优选为室温；所述超声处理的时间优选为90～120min，更优选为100～110min；所述超声处理的目的是使TBA+插层的MXene分散开成少片或单片；所述少片的片数优选为2～6片，更有选为2～3片。In the present invention, the water is preferably deionized water, and the concentration of the exfoliated MXene nanosheet dispersion liquid is preferably 0.1-10 g/L, more preferably 0.5-8 g/L, and most preferably 1-5 g/L. In the present invention, the ultrasonic dispersion is preferably carried out in a protective atmosphere; the present invention does not specifically limit the type of the protective atmosphere, and a protective atmosphere well-known to those skilled in the art can be used, such as nitrogen or argon; the present invention Carrying out ultrasonic dispersion in a protective atmosphere can prevent MXene from being oxidized; the present invention does not specifically limit the ultrasonic power of the ultrasonic treatment, and the ultrasonic power well-known to those skilled in the art can be used; the temperature of the ultrasonic treatment is preferably room temperature; The time of the ultrasonic treatment is preferably 90-120min, more preferably 100-110min; the purpose of the ultrasonic treatment is to disperse the TBA + intercalated MXene into a few pieces or a single piece; the number of the few pieces is preferably 2 to 6 tablets, more preferably 2 to 3 tablets.
得到剥离MXene纳米片分散液后，本发明将所述剥离MXene纳米片分散液和氧化石墨烯悬浮液混合，进行自组装反应，得到MXene纳米片/氧化石墨烯纳米片。After the exfoliated MXene nanosheet dispersion is obtained, the present invention mixes the exfoliated MXene nanosheet dispersion with the graphene oxide suspension to perform a self-assembly reaction to obtain MXene nanosheets/graphene oxide nanosheets.
在本发明中，所述氧化石墨烯悬浮液的浓度优选为0.1～10g/L，更优选为0.5～8g/L，最优选为1～5g/L。在本发明中，所述剥离MXene纳米片分散液中剥离MXene纳米片的和氧化石墨烯悬浮液中氧化石墨烯的质量比优选为1:10～10:1，更优选为1:5～5:1，最优选为1:3～3:1。In the present invention, the concentration of the graphene oxide suspension is preferably 0.1-10 g/L, more preferably 0.5-8 g/L, and most preferably 1-5 g/L. In the present invention, the mass ratio of exfoliated MXene nanosheets in the exfoliated MXene nanosheet dispersion to graphene oxide in the graphene oxide suspension is preferably 1:10-10:1, more preferably 1:5-5 : 1, most preferably 1:3 to 3:1.
在本发明中，所述剥离MXene纳米片分散液和氧化石墨烯悬浮液混合优选为搅拌混合，本发明对于所述搅拌混合的速度和时间没有特殊限定，能够将剥离MXene纳米片混合分散于氧化石墨烯悬浮液中即可。In the present invention, the mixture of the exfoliated MXene nanosheet dispersion and the graphene oxide suspension is preferably stirred and mixed. The present invention has no special limitations on the speed and time of the stirring and mixing. The exfoliated MXene nanosheets can be mixed and dispersed in the oxidized in graphene suspension.
在本发明中，所述自组装反应优选在搅拌条件下进行；所述自组装反应的温度优选为室温；时间优选为1～3h，更优选为1.5～2.5h，最优选为2h。在本发明中，所述自组装反应过程中，带正电荷(TBA+)的剥离MXene纳米片与带负电的氧化石墨烯通过静电吸附作用发生自组装，四丁基铵离子作为阳离子中间体辅助两种纳米片形成独特的面对面排列结构，保持了MXene与石墨烯的独特二维结构，石墨烯不会发生重新堆叠，为锂离子的嵌入提供更多的活性位点，扩大的MXene层间距能够为锂离子的快速传输提供途径。In the present invention, the self-assembly reaction is preferably carried out under stirring conditions; the temperature of the self-assembly reaction is preferably room temperature; the time is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours, and most preferably 2 hours. In the present invention, during the self-assembly reaction, the exfoliated MXene nanosheets with positive charges (TBA + ) and the negatively charged graphene oxide self-assemble through electrostatic adsorption, and tetrabutylammonium ions are used as cation intermediates to assist The two nanosheets form a unique face-to-face arrangement, which maintains the unique two-dimensional structure of MXene and graphene. The graphene does not re-stack, providing more active sites for the insertion of lithium ions. The enlarged MXene interlayer spacing can Provide a pathway for the rapid transport of lithium ions.
所述自组装反应后，本发明优选还包括将所述自组装反应的体系进行干燥，得到MXene纳米片/氧化石墨烯纳米片。在本发明中，所述干燥优选为冷冻干燥，所述冷冻干燥的温度优选为-30～-55℃，更优选为-35～-45℃；时间优选为15～20h，更优选为16～19h，最优选为17～18h。After the self-assembly reaction, the present invention preferably further includes drying the self-assembly reaction system to obtain MXene nanosheets/graphene oxide nanosheets. In the present invention, the drying is preferably freeze-drying, and the temperature of the freeze-drying is preferably -30～-55°C, more preferably -35～-45°C; the time is preferably 15～20h, more preferably 16～ 19h, most preferably 17-18h.
得到MXene纳米片/氧化石墨烯纳米片后，本发明在保护气氛下，将所述MXene纳米片/氧化石墨烯纳米片进行还原反应，得到MXene/石墨烯复合纳米片。After obtaining the MXene nanosheets/graphene oxide nanosheets, the present invention performs a reduction reaction on the MXene nanosheets/graphene oxide nanosheets under a protective atmosphere to obtain MXene/graphene composite nanosheets.
所述还原反应前，本发明优选还包括将所述MXene纳米片/氧化石墨烯纳米片进行研磨；所述研磨优选在研钵中进行，本发明对于所述研磨的时间没有特殊限定，能够将MXene纳米片/氧化石墨烯纳米片研磨至均匀无大块团聚即可。Before the reduction reaction, the present invention preferably further comprises grinding the MXene nanosheets/graphene oxide nanosheets; the grinding is preferably performed in a mortar, and the present invention does not specifically limit the grinding time, and can The MXene nanosheets/graphene oxide nanosheets can be ground until they are homogeneous without large agglomeration.
本发明对于所述保护气氛的种类没有特殊限定，采用本领域技术人员熟知的保护气氛即可，具体如氮气或氩气。In the present invention, the type of the protective atmosphere is not particularly limited, and a protective atmosphere well known to those skilled in the art can be used, such as nitrogen or argon.
在本发明中，所述还原反应的温度优选为300～500℃，更优选为350～450℃，最优选为400℃；温度由室温升温至所述还原反应的温度的升温速率优选为3～7℃/min，更优选为5℃/min；保温的时间优选为2～4h，更优选为2.5～3.5h，最优选为3h。本发明优选将所述MXene纳米片/氧化石墨烯纳米片优选置于刚玉坩埚在管式炉中进行还原反应。在本发明中，所述还原反应过程中氧化石墨烯有效还原为石墨烯，作为耦合剂的四丁基铵离子高温分解而被去除，在保持微观结构的同时有效提高石墨烯与MXene之间的电子转移能力。In the present invention, the temperature of the reduction reaction is preferably 300-500°C, more preferably 350-450°C, and most preferably 400°C; the temperature rising rate from room temperature to the temperature of the reduction reaction is preferably 3～400°C 7°C/min, more preferably 5°C/min; the holding time is preferably 2-4h, more preferably 2.5-3.5h, most preferably 3h. In the present invention, the MXene nanosheets/graphene oxide nanosheets are preferably placed in a corundum crucible for reduction reaction in a tube furnace. In the present invention, during the reduction reaction, graphene oxide is effectively reduced to graphene, and the tetrabutylammonium ion as a coupling agent is decomposed and removed at high temperature, and the microstructure is maintained while effectively improving the bond between graphene and MXene. Electron transfer capability.
本发明提供了上述技术方案所述制备方法制备的MXene/石墨烯复合纳米片，具有异质层状结构，包括相互层叠的剥离MXene纳米片层和石墨烯层。The present invention provides the MXene/graphene composite nanosheet prepared by the preparation method described in the above technical solution, which has a heterogeneous layered structure, including exfoliated MXene nanosheet layers and graphene layers stacked on each other.
在本发明中，所述MXene/石墨烯复合纳米片中相邻两层的间距优选为1～2nm，更优选为1.1～1.5nm。In the present invention, the distance between two adjacent layers in the MXene/graphene composite nanosheet is preferably 1-2 nm, more preferably 1.1-1.5 nm.
本发明提供的MXene/石墨烯复合纳米片中石墨烯不会发生重新堆叠，具有优异的储锂性能，且能够保持MXene与石墨烯的独特二维结构。The graphene in the MXene/graphene composite nanosheet provided by the present invention will not be re-stacked, has excellent lithium storage performance, and can maintain the unique two-dimensional structure of MXene and graphene.
本发明还提供了一种电极极片，包括导电基体和涂覆于导电基体表面的导电层，所述导电层包括上述技术方案所述MXene/石墨烯复合纳米片、导电炭黑和聚偏氟乙烯。The present invention also provides an electrode pole piece, comprising a conductive substrate and a conductive layer coated on the surface of the conductive substrate, wherein the conductive layer includes the MXene/graphene composite nanosheets, conductive carbon black and polyvinylidene fluoride described in the above technical solution vinyl.
在本发明中，所述电极极片的制备方法优选包括以下步骤：将MXene/石墨烯复合纳米片、导电炭黑、聚偏氟乙烯和溶剂混合，将所得浆料涂覆于导电基体表面，得到电极极片。In the present invention, the preparation method of the electrode sheet preferably includes the following steps: mixing MXene/graphene composite nanosheets, conductive carbon black, polyvinylidene fluoride and a solvent, and coating the obtained slurry on the surface of the conductive substrate, Get electrode pads.
在本发明中，所述MXene/石墨烯复合纳米片、导电炭黑和聚偏氟乙烯(PVDF)的质量比优选为(7～9)：(0.5～1.5)：(0.5～1.5)，更优选为(7.5～8.5)：(0.8～1.2)：(0.8～1.2)，最优选为8:1:1。In the present invention, the mass ratio of the MXene/graphene composite nanosheets, conductive carbon black and polyvinylidene fluoride (PVDF) is preferably (7-9):(0.5-1.5):(0.5-1.5), more It is preferably (7.5-8.5):(0.8-1.2):(0.8-1.2), and most preferably 8:1:1.
在本发明中，所述溶剂优选包括吡咯烷酮类溶剂，所述吡咯烷酮类溶剂优选包括N-甲基吡咯烷酮、2-吡咯烷酮或N-乙基吡咯烷酮。本发明对于所述吡咯烷酮类溶剂的用量没有特殊限定，在本发明的实施例中，所述MXene/石墨烯复合纳米片质量和吡咯烷酮类溶剂体积的比优选为1g:20mL。In the present invention, the solvent preferably includes a pyrrolidone-based solvent, and the pyrrolidone-based solvent preferably includes N-methylpyrrolidone, 2-pyrrolidone or N-ethylpyrrolidone. The present invention does not specifically limit the amount of the pyrrolidone-based solvent. In the embodiment of the present invention, the ratio of the mass of the MXene/graphene composite nanosheet to the volume of the pyrrolidone-based solvent is preferably 1 g:20 mL.
在本发明中，所述混合优选为搅拌混合，本发明对于所述搅拌混合的速度和时间没有特殊限定，能够将原料混合均匀即可。In the present invention, the mixing is preferably stirring and mixing, and the speed and time of the stirring and mixing are not particularly limited in the present invention, as long as the raw materials can be uniformly mixed.
在本发明中，所述导电基体优选包括铜箔或涂炭铜箔。In the present invention, the conductive substrate preferably includes copper foil or carbon-coated copper foil.
本发明对于所述涂覆的方式没有特殊限定，采用本领域技术人员熟知的涂覆方式即可。在本发明中，以MXene/石墨烯复合纳米片的量计，所述浆料的涂覆量优选为0.004～0.01g/cm2，更优选为0.005～0.007g/cm2。The present invention does not specifically limit the coating method, and a coating method well known to those skilled in the art can be used. In the present invention, in terms of the amount of MXene/graphene composite nanosheets, the coating amount of the slurry is preferably 0.004-0.01 g/cm 2 , more preferably 0.005-0.007 g/cm 2 .
所述涂覆后，本发明优选还包括将所述涂覆后的湿膜进行干燥。在本发明中，所述干燥的方式优选为真空干燥；所述干燥的温度优选为100～150℃，更优选为110～120℃；时间优选为5～15h，更优选为6～10h。After the coating, the present invention preferably further comprises drying the coated wet film. In the present invention, the drying method is preferably vacuum drying; the drying temperature is preferably 100-150°C, more preferably 110-120°C; the time is preferably 5-15h, more preferably 6-10h.
本发明还提供了上述技术方案所述MXene/石墨烯复合纳米片和上述技术方案所述电极极片在超级电容器、锂离子电池或电催化材料中的应用。The present invention also provides the application of the MXene/graphene composite nanosheets described in the above technical solution and the electrode pole pieces described in the above technical solution in supercapacitors, lithium ion batteries or electrocatalytic materials.
下面将结合本发明中的实施例，对本发明中的技术方案进行清楚、完整地描述。显然，所描述的实施例仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some, but not all, embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
实施例1Example 1
(1)将3g MAX粉体置于60mL 40wt％氢氟酸溶液在搅拌条件下刻蚀24h，离心分离，将所得固体组分进行去离子水洗涤后在-45℃条件下冷冻干燥24h，得到MXene；(1) 3g of MAX powder was placed in 60mL of 40wt% hydrofluoric acid solution for 24h etching under stirring conditions, centrifuged, and the obtained solid component was washed with deionized water and then freeze-dried at -45°C for 24h to obtain MXene;
(2)将2g所述MXene置于70mL 25wt％TBAOH溶液中，在室温、搅拌条件下静电吸附18h，离心分离，将所得固体组分去离子水洗涤后在-45℃条件下冷冻干燥24h，得到剥离MXene纳米片；将0.1g剥离MXene纳米片置于100mL去离子水中，在保护气氛下超声120min，得到浓度为1g/L的剥离MXene纳米片分散液；(2) 2 g of the MXene was placed in 70 mL of a 25 wt% TBAOH solution, electrostatically adsorbed for 18 h under stirring conditions at room temperature, centrifuged, washed with deionized water, and freeze-dried at -45°C for 24 h. The exfoliated MXene nanosheets were obtained; 0.1 g of exfoliated MXene nanosheets were placed in 100 mL of deionized water, and sonicated for 120 min under a protective atmosphere to obtain a dispersion of exfoliated MXene nanosheets with a concentration of 1 g/L;
(3)在室温、搅拌条件下，将所述1g/L的剥离MXene纳米片分散液和20g/L氧化石墨烯悬浮液(剥离MXene纳米片和氧化石墨烯的质量比为1:1)混合，自组装反应2h，然后冷冻干燥20h，得到MXene纳米片/氧化石墨烯纳米片；(3) Mix the 1 g/L exfoliated MXene nanosheet dispersion with 20 g/L graphene oxide suspension (the mass ratio of exfoliated MXene nanosheets and graphene oxide is 1:1) at room temperature and under stirring conditions , self-assembly reaction for 2h, and then freeze-drying for 20h to obtain MXene nanosheets/graphene oxide nanosheets;
(4)将所述MXene纳米片/氧化石墨烯纳米片在研钵中磨均匀，然后均匀铺在刚玉坩埚中，将坩埚置于管式炉内，在氩气保护下，以5℃/min的速率升温至400℃后还原2h，冷却至室温，得到MXene/石墨烯复合纳米片。(4) grind the MXene nanosheets/graphene oxide nanosheets evenly in a mortar, then spread them evenly in a corundum crucible, place the crucible in a tube furnace, under the protection of argon, at a temperature of 5°C/min The rate of heating to 400 °C, reduction for 2 h, and cooling to room temperature to obtain MXene/graphene composite nanosheets.
本实施例制备的MXene/石墨烯复合纳米片的X射线衍射谱图如图1所示，由图1可知，本发明制备的MXene/石墨烯复合纳米片的结晶度好、纯度高。与步骤(1)得到的MXene相比，MXene/石墨烯复合纳米片位于9.1°附近的(0002)峰向左移动到6.2°左右，说明MXene与石墨烯复合后，二维片层之间的距离由0.99nm增加到1.28nm，增大的层间距有利于离子的快速传输以及进一步增加锂离子储存位点。The X-ray diffraction spectrum of the MXene/graphene composite nanosheet prepared in this example is shown in FIG. 1 . It can be seen from FIG. 1 that the MXene/graphene composite nanosheet prepared by the present invention has good crystallinity and high purity. Compared with the MXene obtained in step (1), the (0002) peak of the MXene/graphene composite nanosheets located around 9.1° is shifted to the left to about 6.2°, indicating that after the MXene and graphene are composited, the two-dimensional sheet has a The distance is increased from 0.99 nm to 1.28 nm, and the increased interlayer spacing facilitates the rapid transport of ions and further increases the lithium ion storage sites.
本实施例制备的MXene/石墨烯复合纳米片的扫描电子显微镜图如图2所示，由图2可知，MXene/石墨烯复合纳米片具有异质层状相互面对面排列的片状形貌。The scanning electron microscope image of the MXene/graphene composite nanosheets prepared in this example is shown in Figure 2. It can be seen from Figure 2 that the MXene/graphene composite nanosheets have a sheet-like morphology with heterogeneous layers arranged face to face with each other.
本实施例制备的MXene/石墨烯复合纳米片的透射电子显微镜图如图3所示，由图3可知，MXene/石墨烯复合纳米片中石墨烯薄片与剥离MXene薄片呈现出面对面排列的方式，并且，片层表面光滑，结构稳定，具有一定的透光型，说明复合后的MXene/石墨烯复合纳米片的异质结构能够保持良好的二维特性。The transmission electron microscope image of the MXene/graphene composite nanosheets prepared in this example is shown in Figure 3. It can be seen from Figure 3 that the graphene sheets and the exfoliated MXene sheets in the MXene/graphene composite nanosheets are arranged in a face-to-face manner. In addition, the surface of the sheet is smooth, the structure is stable, and it has a certain light transmission type, indicating that the heterostructure of the composite MXene/graphene composite nanosheets can maintain good two-dimensional properties.
本实施例制备的MXene纳米片/氧化石墨烯纳米片和MXene/石墨烯复合纳米片的X射线光电子能谱图如图4所示，其中，C1s即碳原子中1s轨道电子被激发所测光电子能量。由图4可知，MXene/石墨烯复合纳米片经过高温还原后，C-O结合键大幅减少，证明石墨烯表面含氧官能团高温下得到还原，因此材料的导电性能得到提升。The X-ray photoelectron spectra of the MXene nanosheets/graphene oxide nanosheets and the MXene/graphene composite nanosheets prepared in this example are shown in Figure 4, where C1s, the 1s orbital electron in the carbon atom, is excited to measure the photoelectron energy. It can be seen from Figure 4 that after the MXene/graphene composite nanosheet is reduced at high temperature, the C-O bond is greatly reduced, which proves that the oxygen-containing functional groups on the surface of graphene are reduced at high temperature, so the electrical conductivity of the material is improved.
实施例2Example 2
按照实施例1的方法制备MXene/石墨烯复合纳米片，与实施例1的区别在于，步骤(2)中剥离MXene纳米片分散液的浓度为2g/L；步骤(3)中剥离MXene纳米片和氧化石墨烯的质量比为1:2。The MXene/graphene composite nanosheets were prepared according to the method of Example 1. The difference from Example 1 is that the concentration of the dispersion liquid for exfoliating MXene nanosheets in step (2) is 2 g/L; in step (3), the concentration of exfoliating MXene nanosheets is 2 g/L The mass ratio of graphene oxide and graphene oxide is 1:2.
实施例3Example 3
按照实施例1的方法制备MXene/石墨烯复合纳米片，与实施例1的区别在于，步骤(2)中剥离MXene纳米片分散液的浓度为0.1g/L；步骤(3)中剥离MXene纳米片和氧化石墨烯的质量比为2:1。The MXene/graphene composite nanosheets were prepared according to the method of Example 1. The difference from Example 1 is that the concentration of the dispersion liquid for exfoliating MXene nanosheets in step (2) is 0.1 g/L; The mass ratio of flakes and graphene oxide is 2:1.
实施例4Example 4
按照实施例1的方法制备MXene/石墨烯复合纳米片，与实施例1的区别在于，步骤(2)中TBAOH溶液的体积为55mL，剥离MXene纳米片分散液的浓度为0.8g/L，步骤(3)中剥离MXene纳米片和氧化石墨烯的质量比为1:4。The MXene/graphene composite nanosheets were prepared according to the method of Example 1. The difference from Example 1 was that the volume of the TBAOH solution in step (2) was 55 mL, and the concentration of the exfoliated MXene nanosheet dispersion was 0.8 g/L. (3) The mass ratio of exfoliated MXene nanosheets and graphene oxide is 1:4.
实施例5Example 5
按照实施例1的方法制备MXene/石墨烯复合纳米片，与实施例1的区别在于，步骤(2)中TBAOH溶液的体积为55mL，剥离MXene纳米片分散液的浓度为0.8g/L；步骤(3)中剥离MXene纳米片和氧化石墨烯的质量比为4:1。The MXene/graphene composite nanosheets were prepared according to the method of Example 1. The difference from Example 1 was that the volume of the TBAOH solution in step (2) was 55 mL, and the concentration of the exfoliated MXene nanosheet dispersion was 0.8 g/L; step (3) The mass ratio of exfoliated MXene nanosheets and graphene oxide is 4:1.
实施例6Example 6
按照实施例1的方法制备MXene/石墨烯复合纳米片，与实施例1的区别在于，步骤(2)中TBAOH溶液的体积为55mL，剥离MXene纳米片分散液的浓度为0.8g/L；步骤(3)中剥离MXene纳米片和氧化石墨烯的质量比为1:6。The MXene/graphene composite nanosheets were prepared according to the method of Example 1. The difference from Example 1 was that the volume of the TBAOH solution in step (2) was 55 mL, and the concentration of the exfoliated MXene nanosheet dispersion was 0.8 g/L; step (3) The mass ratio of exfoliated MXene nanosheets and graphene oxide is 1:6.
实施例7Example 7
按照实施例1的方法制备MXene/石墨烯复合纳米片，与实施例1的区别在于，步骤(2)中TBAOH溶液的体积为85mL，剥离MXene纳米片分散液的浓度为1.2g/L，步骤(3)中剥离MXene纳米片和氧化石墨烯的质量比为6:1。The MXene/graphene composite nanosheets were prepared according to the method of Example 1. The difference from Example 1 was that the volume of the TBAOH solution in step (2) was 85 mL, and the concentration of the exfoliated MXene nanosheet dispersion was 1.2 g/L. (3) The mass ratio of exfoliated MXene nanosheets and graphene oxide is 6:1.
实施例8Example 8
按照实施例1的方法制备MXene/石墨烯复合纳米片，与实施例1的区别在于，步骤(2)中TBAOH溶液的体积为85mL，剥离MXene纳米片分散液的浓度为1.2g/L；步骤(3)中剥离MXene纳米片和氧化石墨烯的质量比为1:8。The MXene/graphene composite nanosheets were prepared according to the method of Example 1. The difference from Example 1 is that the volume of the TBAOH solution in step (2) is 85 mL, and the concentration of the exfoliated MXene nanosheet dispersion liquid is 1.2 g/L; step (3) The mass ratio of exfoliated MXene nanosheets and graphene oxide is 1:8.
实施例9Example 9
按照实施例1的方法制备MXene/石墨烯复合纳米片，与实施例1的区别在于，步骤(2)中TBAOH溶液的体积为85mL，剥离MXene纳米片分散液的浓度为1.2g/L；步骤(3)中剥离MXene纳米片和氧化石墨烯的质量比为8:1。The MXene/graphene composite nanosheets were prepared according to the method of Example 1. The difference from Example 1 is that the volume of the TBAOH solution in step (2) is 85 mL, and the concentration of the exfoliated MXene nanosheet dispersion liquid is 1.2 g/L; step (3) The mass ratio of exfoliated MXene nanosheets and graphene oxide is 8:1.
实施例10Example 10
按照实施例1的方法制备MXene/石墨烯复合纳米片，与实施例1的区别在于，步骤(2)中TBAOH溶液的体积为100mL，剥离MXene纳米片分散液的浓度为1.4g/L，步骤(3)中剥离MXene纳米片和氧化石墨烯的质量比为1:10。The MXene/graphene composite nanosheets were prepared according to the method of Example 1. The difference from Example 1 was that the volume of the TBAOH solution in step (2) was 100 mL, and the concentration of the exfoliated MXene nanosheet dispersion was 1.4 g/L. (3) The mass ratio of exfoliated MXene nanosheets and graphene oxide is 1:10.
实施例11Example 11
按照实施例1的方法制备MXene/石墨烯复合纳米片，与实施例1的区别在于，步骤(2)中TBAOH溶液的体积为100mL，剥离MXene纳米片分散液的浓度为1.4g/L；步骤(3)中剥离MXene纳米片和氧化石墨烯的质量比为10:1。The MXene/graphene composite nanosheets were prepared according to the method of Example 1. The difference from Example 1 is that the volume of the TBAOH solution in step (2) is 100 mL, and the concentration of the exfoliated MXene nanosheet dispersion liquid is 1.4 g/L; step (3) The mass ratio of exfoliated MXene nanosheets and graphene oxide is 10:1.
实施例12Example 12
按照实施例1的方法制备MXene/石墨烯复合纳米片，与实施例1的区别在于，步骤(4)还原温度为300℃；步骤(3)中剥离MXene纳米片和氧化石墨烯的质量比为1:1。The MXene/graphene composite nanosheets were prepared according to the method of Example 1. The difference from Example 1 is that the reduction temperature in step (4) is 300°C; the mass ratio of exfoliated MXene nanosheets to graphene oxide in step (3) is 1:1.
实施例13Example 13
按照实施例1的方法制备MXene/石墨烯复合纳米片，与实施例1的区别在于，步骤(4)还原温度为500℃；步骤(3)中剥离MXene纳米片和氧化石墨烯的质量比为1:1。The MXene/graphene composite nanosheets were prepared according to the method of Example 1. The difference from Example 1 is that the reduction temperature in step (4) is 500°C; the mass ratio of exfoliated MXene nanosheets to graphene oxide in step (3) is 1:1.
实施例14Example 14
按照实施例1的方法制备MXene/石墨烯复合纳米片，与实施例1的区别在于，步骤(4)升温速率为3℃/min；步骤(3)中剥离MXene纳米片和氧化石墨烯的质量比为1:1。The MXene/graphene composite nanosheets were prepared according to the method of Example 1. The difference from Example 1 is that the heating rate in step (4) is 3°C/min; The ratio is 1:1.
实施例15Example 15
按照实施例1的方法制备MXene/石墨烯复合纳米片，与实施例1的区别在于，步骤(4)升温速率为7℃/min；步骤(3)中剥离MXene纳米片和氧化石墨烯的质量比为1:1。The MXene/graphene composite nanosheets were prepared according to the method of Example 1. The difference from Example 1 is that the heating rate in step (4) is 7°C/min; The ratio is 1:1.
应用例Application example
分别将实施例1～3制备的MXene/石墨烯复合纳米片、导电炭黑和聚偏氟乙烯(PVDF)和N-甲基吡咯烷酮搅拌混合后涂敷在铜箔上，进行真空干燥，得到电极极片，其中MXene/石墨烯复合纳米片、导电炭黑和PVDF的质量比为8:1:1，电极极片的倍率性能图如表1和图5所示，其中，MXene:石墨烯的质量比为1:1代表实施例1，MXene:石墨烯的质量比为1:2代表实施例2，MXene:石墨烯的质量比为2:1代表实施例3。The MXene/graphene composite nanosheets, conductive carbon black, polyvinylidene fluoride (PVDF) and N-methylpyrrolidone prepared in Examples 1 to 3 were stirred and mixed, respectively, and then coated on copper foil, and vacuum-dried to obtain electrodes. The pole piece, in which the mass ratio of MXene/graphene composite nanosheets, conductive carbon black and PVDF is 8:1:1, and the rate performance diagram of the electrode pole piece is shown in Table 1 and Figure 5, where the ratio of MXene:graphene is A mass ratio of 1:1 represents Example 1, a mass ratio of MXene:graphene of 1:2 represents Example 2, and a mass ratio of MXene:graphene of 2:1 represents Example 3.
表1实施例1～3制备的电极极片的倍率性能Table 1 Rate performance of electrode pieces prepared in Examples 1-3
由图5和表1可知，当MXene与石墨烯的质量比为1:1时，电流密度50mA/g时储锂比容量约为1394mAh/g；当MXene与石墨烯的质量比为1:2时，电流密度50mA/g时储锂比容量约为656Ah/g；当MXene与石墨烯的质量比为2:1时，电流密度50mA/g时储锂比容量约为457mAh/g；当MXene与石墨烯的质量比为1:1时，即使电流密度增加到2A/g时也具有651mAh/g的比容量。电池性能会随着电流密度增大而出现衰减，对于MXene/石墨烯复合纳米片结构的破坏是不可逆的，因而电流从小到大再到小电池性能会有一些衰减。说明，本发明制备的MXene/石墨烯复合纳米片具有作为储锂电极材料的优秀潜力。It can be seen from Figure 5 and Table 1 that when the mass ratio of MXene to graphene is 1:1, the specific lithium storage capacity is about 1394mAh/g when the current density is 50mA/g; when the mass ratio of MXene to graphene is 1:2 When the current density is 50mA/g, the specific lithium storage capacity is about 656Ah/g; when the mass ratio of MXene to graphene is 2:1, the specific lithium storage capacity is about 457mAh/g when the current density is 50mA/g; when MXene When the mass ratio to graphene is 1:1, it has a specific capacity of 651mAh/g even when the current density is increased to 2A/g. The battery performance will decay with the increase of the current density, and the damage to the MXene/graphene composite nanosheet structure is irreversible, so the battery performance will have some attenuation from small to large to small. It shows that the MXene/graphene composite nanosheets prepared by the present invention have excellent potential as lithium storage electrode materials.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made. It should be regarded as the protection scope of the present invention.
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