CN108054359B - Preparation method of molybdenum disulfide intercalation material - Google Patents
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 78
- 238000009830 intercalation Methods 0.000 title claims abstract description 52
- 230000002687 intercalation Effects 0.000 title claims abstract description 52
- 239000000463 material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 21
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 21
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000004729 solvothermal method Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000004108 freeze drying Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 14
- 229920002873 Polyethylenimine Polymers 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000012546 transfer Methods 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 18
- 239000010410 layer Substances 0.000 abstract description 18
- 229910052799 carbon Inorganic materials 0.000 abstract description 12
- 239000011229 interlayer Substances 0.000 abstract description 9
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- 150000002500 ions Chemical class 0.000 abstract description 2
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- 238000006243 chemical reaction Methods 0.000 description 14
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- 238000005054 agglomeration Methods 0.000 description 5
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- 239000013078 crystal Substances 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 230000037427 ion transport Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004964 aerogel Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 229920000936 Agarose Polymers 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000002065 inelastic X-ray scattering Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000329 molecular dynamics simulation Methods 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
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- 230000001681 protective effect Effects 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Abstract
Description
技术领域technical field
本发明涉及储能器件领域，尤其是涉及一种二硫化钼插层材料的制备方法。The invention relates to the field of energy storage devices, in particular to a preparation method of a molybdenum disulfide intercalation material.
背景技术Background technique
化学电源是能实现电能和化学能互相转换的装置，是一种能更合理利用能源的重要媒介。以锂离子电池和超级电容器为代表的化学电源具有极为广泛的应用。锂离子电池具有工作电压高、能量密度高、自放电率低以及循环寿命长和无记忆效应等优良性能，也存在功率密度低，循环稳定性差等缺陷；超级电容器具有充电速度快，循环使用寿命长，能量转换效率高，安全系数高等诸多优良性能，但依旧难以解决功率密度低等问题。随着新一代储能设备的进一步发展，发展性能更为优异的电极材料成为急需解决的问题。二硫化钼作为一种典型的过渡金属二元化合物,具有类石墨烯结构。层内Mo与S原子之间构成共价键,结构非常稳定。二硫化钼独特的物理化学性质，已经广泛的应用于电化学储能，并展现了极好的性能。当前二硫化钼材料的研究核心，是对其进行002晶面的有效插层。具体而言，在超级电容器领域，通过层间002晶面内引入高电导率的碳材料来提高电子和离子的传导速率，进而充分利用层内活性位点，实现高功率，高能量存储。Chemical power supply is a device that can realize the mutual conversion of electrical energy and chemical energy, and is an important medium for more rational use of energy. Chemical power sources represented by lithium-ion batteries and supercapacitors have an extremely wide range of applications. Lithium-ion batteries have excellent performances such as high operating voltage, high energy density, low self-discharge rate, long cycle life and no memory effect, but also have defects such as low power density and poor cycle stability; supercapacitors have fast charging speed and cycle life. It has many excellent properties, such as high energy conversion efficiency, high safety factor, etc., but it is still difficult to solve the problems of low power density. With the further development of a new generation of energy storage devices, the development of electrode materials with better performance has become an urgent problem to be solved. As a typical transition metal binary compound, molybdenum disulfide has a graphene-like structure. Covalent bonds are formed between Mo and S atoms in the layer, and the structure is very stable. The unique physical and chemical properties of molybdenum disulfide have been widely used in electrochemical energy storage, and showed excellent performance. The core of the current research on molybdenum disulfide materials is the effective intercalation of the 002 crystal plane. Specifically, in the field of supercapacitors, the conduction rate of electrons and ions is improved by introducing high-conductivity carbon materials in the 002 crystal plane between the layers, and then the active sites in the layers are fully utilized to achieve high power and high energy storage.
中国专利CN106848228A公开了制备二硫化钼/碳复合多级孔材料的方法，将钼酸钠、硫代乙酰胺和琼脂糖加水溶解后水浴加热，反应结束后趁热倒出冷却，将冷却后的样品转移至冰箱冷冻，后转移至冻干机中干燥，最后置于管式炉中煅烧，制备得到二硫化钼/碳复合多级孔材料。虽然宏观上同为气凝胶材料，但是该专利只能称为碳材料和二硫化钼的简单复合结构，在纳米尺度不能称为异质结结构，且他的气凝胶材料是以琼脂糖形成的碳骨架为主体。Chinese patent CN106848228A discloses a method for preparing molybdenum disulfide/carbon composite hierarchical porous material. The sodium molybdate, thioacetamide and agarose are dissolved in water and heated in a water bath. The samples were transferred to a refrigerator for freezing, then transferred to a freeze dryer for drying, and finally calcined in a tube furnace to prepare a molybdenum disulfide/carbon composite hierarchical porous material. Although both are aerogel materials macroscopically, this patent can only be called a simple composite structure of carbon materials and molybdenum disulfide, and cannot be called a heterojunction structure at the nanoscale, and his aerogel material is based on agarose The formed carbon skeleton is the main body.
发明内容SUMMARY OF THE INVENTION
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种二硫化钼插层材料的制备方法。The purpose of the present invention is to provide a preparation method of a molybdenum disulfide intercalation material in order to overcome the defects existing in the above-mentioned prior art.
本发明的目的可以通过以下技术方案来实现：The object of the present invention can be realized through the following technical solutions:
一种二硫化钼插层材料的制备方法，采用以下步骤：A preparation method of molybdenum disulfide intercalation material, adopts the following steps:
(1)将钼酸钠、硫代乙酰胺混合并加入溶剂溶解；(1) sodium molybdate, thioacetamide are mixed and add solvent to dissolve;
(2)对步骤(1)的混合溶液加热进行溶剂热反应；(2) heating the mixed solution of step (1) to carry out solvothermal reaction;
(3)将步骤(2)得到的产物冷却后离心洗涤；(3) centrifugal washing after cooling the product obtained in step (2);
(4)取线性高分子对步骤(3)中获得的产品进行超声混匀插层后，然后转移至冻干机冷冻干燥；(4) after taking the linear polymer to carry out ultrasonic mixing and intercalation to the product obtained in the step (3), then transfer to a freeze-drying machine for freeze-drying;
(5)将步骤(4)中的样品置于管式炉中煅烧，制备得到二硫化钼插层材料。(5) The sample in step (4) is calcined in a tube furnace to prepare a molybdenum disulfide intercalation material.
步骤(1)中所述的钼酸钠、硫代乙酰胺的质量比为0.3～0.6:0.6～1.2，所述的溶剂为水与乙二醇按体积比为2:1混合得到的混合溶剂。所述的钼酸钠在溶剂中的浓度控制为0.01-0.02g/ml。The mass ratio of sodium molybdate and thioacetamide described in the step (1) is 0.3～0.6:0.6～1.2, and the solvent is a mixed solvent obtained by mixing water and ethylene glycol in a volume ratio of 2:1 . The concentration of the sodium molybdate in the solvent is controlled to be 0.01-0.02g/ml.
步骤(2)中所述的溶剂热反应的温度为200-240℃，反应时间为20-24h。The temperature of the solvothermal reaction described in step (2) is 200-240° C., and the reaction time is 20-24 h.
步骤(3)中离心洗涤为采用水和乙醇交替洗涤三次。In step (3), the centrifugal washing is alternately washed with water and ethanol three times.
步骤(4)中所述的线性高分子包括聚乙烯亚胺或聚乙二醇，其质量为二硫化钼分子的20％-100％。所述的超声混匀插层，其超声频率为360-440HZ，时间为1-3h。所述的冷冻干燥控制温度为零下56-40摄氏度，时间为12-24小时。The linear polymer described in step (4) includes polyethyleneimine or polyethylene glycol, and its mass is 20%-100% of the molybdenum disulfide molecule. For the ultrasonic mixing and intercalation, the ultrasonic frequency is 360-440HZ, and the time is 1-3h. The freeze-drying control temperature is minus 56-40 degrees Celsius, and the time is 12-24 hours.
步骤(5)中所述的煅烧控制温度为度为600-800摄氏度持续2-6小时，升温速率为2-5摄氏度每分钟。The calcination control temperature described in the step (5) is 600-800 degrees Celsius for 2-6 hours, and the heating rate is 2-5 degrees Celsius per minute.
本申请利用高分子对二硫化钼实现了有效插层，在纳米尺度上使得原来二硫化钼固有的0.62nm的层间距扩大到0.95nm，碳链在层间和片间的支撑，不仅提供了层间活性位点，而且为片间离子传输提供了快捷通道，同时还大大提高了二硫化钼的导电性，使得每个片层都能有效储能，用于超级电容器中具有比容量高、循环性能好、结构稳定等特点，是一种优良的储能材料，以二硫化钼为主体结构。In this application, the effective intercalation of molybdenum disulfide is realized by polymer, and the interlayer spacing of the original molybdenum disulfide from 0.62 nm is expanded to 0.95 nm on the nanometer scale. The support of carbon chains between layers and sheets not only provides It also provides a fast channel for inter-sheet ion transport, and also greatly improves the conductivity of molybdenum disulfide, so that each sheet can effectively store energy, which is used in supercapacitors with high specific capacity, It has the characteristics of good cycle performance and stable structure. It is an excellent energy storage material with molybdenum disulfide as the main structure.
本申请首先得益于选材。二硫化钼是一种层状类石墨烯结构的二维材料，其层间靠较弱的范德华力相支撑；水热法合成的二硫化钼材料表面带有负电荷，而高分子聚乙烯亚胺带有正电荷，所以在插层驱动力上来讲，正负电荷的这种相互吸引的静电作用力起到了非常大的作用；此外，在分子动力学上，频率为400HZ的超声助力有利于加快两种分子的运动和均匀混合。This application first benefits from material selection. Molybdenum disulfide is a two-dimensional material with a layered graphene-like structure, and its interlayers are supported by weak van der Waals forces. Amines have positive charges, so in terms of intercalation driving force, the electrostatic force of mutual attraction between positive and negative charges plays a very large role; in addition, in terms of molecular dynamics, ultrasonic assistance at a frequency of 400HZ is beneficial to Accelerates the movement and uniform mixing of the two molecules.
与现有技术相比，本发明通过上述方法制备得到二硫化钼/碳异质结材料，碳链***二硫化钼层间，提高了层间的活性位点，同时在片间也起到很好的支撑作用，有效阻止了二硫化钼片的团聚，为离子传输提供了快捷通道。同时还大大提高了二硫化钼的导电性，使得每个片层都能有效储能，用于超级电容器中具有比容量高、循环性能好、结构稳定等优势，是一种优良的储能材料。Compared with the prior art, in the present invention, the molybdenum disulfide/carbon heterojunction material is prepared by the above-mentioned method, and the carbon chain is inserted between the molybdenum disulfide layers, which improves the active sites between the layers, and also plays an important role in the interlayer. Good support can effectively prevent the agglomeration of molybdenum disulfide sheets and provide a fast channel for ion transport. At the same time, the conductivity of molybdenum disulfide is greatly improved, so that each layer can effectively store energy. It has the advantages of high specific capacity, good cycle performance and stable structure when used in supercapacitors. It is an excellent energy storage material. .
附图说明Description of drawings
图1为实施例1、2、3、4制备的二硫化钼插层材料的扫描电子显微镜照片。1 is a scanning electron microscope photograph of the molybdenum disulfide intercalation materials prepared in Examples 1, 2, 3, and 4.
图2为实施例1制备的二硫化钼插层材料的透射电子显微镜照片。2 is a transmission electron microscope photograph of the molybdenum disulfide intercalation material prepared in Example 1.
图3为实施例1制备的二硫化钼插层材料XRD及Raman图。3 is the XRD and Raman diagrams of the molybdenum disulfide intercalated material prepared in Example 1.
图4为实施例1制备的二硫化钼插层材料组装的超级电容器的充放电性能曲线。4 is the charge-discharge performance curve of the supercapacitor assembled with the molybdenum disulfide intercalation material prepared in Example 1.
具体实施方式Detailed ways
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。The present invention will be described in detail below with reference to specific embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that, for those skilled in the art, several modifications and improvements can be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.
实施例1Example 1
将0.3克钼酸钠和0.6克硫代乙酰胺加入至反应釜中，并加入20毫升水和10毫升乙二醇溶解。将反应釜放入烘箱中加热进行溶剂热反应，设定烘箱的温度为220摄氏度。反应24小时后，关闭装置，待冷却后离心洗涤得二硫化钼。然后取分子量600的线性高分子聚乙烯亚胺对二硫化钼样品进行超声混匀插层，后转移至零下56摄氏度冻干机中干燥24小时。将上述样品置于管式炉中煅烧，实验条件为800摄氏度持续6小时，升温速率为2摄氏度每分钟。所制备的样品如图1A所示，该图能够看出该水热方法合成的二硫化钼呈花片状均匀分布，没有明显的堆积和团聚，且呈现出一定的透明度，表明该二硫化钼片层非常薄，层间和片间的含有少量的均匀分布的部分石墨化的碳。Add 0.3 g of sodium molybdate and 0.6 g of thioacetamide into the reaction kettle, and add 20 ml of water and 10 ml of ethylene glycol to dissolve. The reaction kettle was heated in an oven for solvothermal reaction, and the temperature of the oven was set to 220 degrees Celsius. After 24 hours of reaction, the device was turned off, and after cooling, it was centrifuged and washed to obtain molybdenum disulfide. Then, the molybdenum disulfide sample was ultrasonically mixed and intercalated with linear macromolecular polyethyleneimine with a molecular weight of 600, and then transferred to a freeze dryer at minus 56 degrees Celsius to dry for 24 hours. The above samples were calcined in a tube furnace, and the experimental conditions were 800 degrees Celsius for 6 hours, and the heating rate was 2 degrees Celsius per minute. The prepared sample is shown in Figure 1A, which shows that the molybdenum disulfide synthesized by the hydrothermal method is evenly distributed in a flower-like shape, without obvious accumulation and agglomeration, and shows a certain transparency, indicating that the molybdenum disulfide is The lamellae are very thin, with small amounts of evenly distributed partially graphitized carbon between the lamellae and between the lamellae.
图2为实施例1制备的二硫化钼插层材料的透射电子显微镜照片。图A和B为该MoS2/C异质结气凝胶材料的低倍透射图片，随着高分子的插层，二硫化钼层呈一定的弯曲折叠状，而且在二硫化钼的层间和片间能够明显的看出有部分晶化的石墨碳的存在；图C更是测量的插层后的异质结材料由原来的0.62nm扩大到0.95nm。而且碳的插层，对面内二硫化钼原子的排布有一定的扰动作用，使得面内晶格的排布有一定的扭曲，见图D。图3为实施例1制备的二硫化钼插层材料XRD及Raman图。采用X射线衍射和拉曼光谱对样品的晶型结构进行分析，发现插层前原材料h-MoS2的衍射峰位置主要在13.8°，33.1°，40.3°和60.0°的位置，如图3A，分别对应于(002)，(100)，(103)，和(100)晶面(JCPDS card 37-1492)。而无论是高分子PEI，还是PEG，在插层后002峰位置均出现了明显的前移，在8.9°和17.6°各有一个明显的尖峰，分别标记为峰1和峰2.对应的层间距为0.98nm，比纯二硫化钼的002面间距0.65nm，扩大了近0.33nm，刚好对应一层碳的距离。这要归因于高分子有效的***了二硫化钼分子的层间，在惰性保护气氛下高温热处理之后，高分子变为部分石墨化的碳留在层间，该实验结果与TEM观察到的数据吻合。图3B拉曼光谱测试结果显示，h-MoS2的A1g和E2g振动模式的峰分别位于375.6和405.9cm-1，分别代表了Mo-S键的面外振动和面内振动。而对于插层后的材料而言，无论是PEG还是PEI插层后的异质结材料，在1350.1和1590.9cm-1均有两个较强的峰，分别对应于插层后碳材料的D和G峰。且高分子的插层，对二硫化钼本身的振动频率有一定的干扰，使得A1g和E2g分别有一定的红移和蓝移现象，偏移后的峰位置分别位于378.1和403.2cm-1。图4为实施例1制备的二硫化钼插层材料组装的超级电容器的充放电性能曲线。在1Ag-1时，容量高达4143.8F g-1。这得益于高分子材料的有效插层，经煅烧得到层间距扩大的异质结电极材料。碳链在二硫化钼层间的插层和片间的支撑，不仅提高了层间的活性位点，而且为片间离子传输提供了快捷通道，同时还大大提高了二硫化钼的导电性，使得每个片层都能有效储能，因此获得了超高的储能效果，且在高倍率10Ag-1时，容量也能达到2483.02F g-1。2 is a transmission electron microscope photograph of the molybdenum disulfide intercalation material prepared in Example 1. Figures A and B are low magnification transmission pictures of the MoS 2 /C heterojunction aerogel material. With the intercalation of the polymer, the molybdenum disulfide layer is in a certain bending and folded shape, and the molybdenum disulfide layer is between the layers of the molybdenum disulfide. The existence of partially crystallized graphitic carbon can be clearly seen between the intercalation and the intercalation; in Figure C, the measured heterojunction material after intercalation has expanded from the original 0.62 nm to 0.95 nm. Moreover, the intercalation of carbon has a certain perturbation effect on the arrangement of molybdenum disulfide atoms in the plane, which makes the arrangement of the lattice in the plane have a certain distortion, as shown in Figure D. 3 is the XRD and Raman diagrams of the molybdenum disulfide intercalated material prepared in Example 1. The crystal structure of the sample was analyzed by X-ray diffraction and Raman spectroscopy, and it was found that the diffraction peak positions of the raw material h-MoS 2 before intercalation were mainly at 13.8°, 33.1°, 40.3° and 60.0°, as shown in Figure 3A, Corresponding to (002), (100), (103), and (100) crystal planes, respectively (JCPDS card 37-1492). Regardless of whether it is polymer PEI or PEG, the position of the 002 peak has a significant forward shift after intercalation, and there is an obvious sharp peak at 8.9° and 17.6°, respectively marked as
实施例2Example 2
将0.3克钼酸钠和0.6克硫代乙酰胺加入至反应釜中，并加入20毫升水和10毫升乙二醇溶解。将反应釜放入烘箱中加热进行溶剂热反应，设定烘箱的温度为220摄氏度。反应24小时后，关闭装置，待冷却后离心洗涤得二硫化钼。然后取分子量70000的线性高分子聚乙烯亚胺对二硫化钼样品进行超声混匀插层，后转移至零下56摄氏度冻干机中干燥24小时。将上述样品置于管式炉中煅烧，实验条件为800摄氏度持续6小时，升温速率为2摄氏度每分钟。所制备的样品如图1B所示，该图能够看出该水热方法合成的二硫化钼呈花片状均匀分布，没有明显的堆积和团聚，且呈现出一定的透明度，表明该二硫化钼片层非常薄，层间和片间的含有少量的均匀分布的部分石墨化的碳。该图同时说明对于同一种类型的高分子而言，不同的分子量插层对其样品形貌影响不大，且高分子PEI的插层能力较强。Add 0.3 g of sodium molybdate and 0.6 g of thioacetamide into the reaction kettle, and add 20 ml of water and 10 ml of ethylene glycol to dissolve. The reaction kettle was heated in an oven for solvothermal reaction, and the temperature of the oven was set to 220 degrees Celsius. After 24 hours of reaction, the device was turned off, and after cooling, it was centrifuged and washed to obtain molybdenum disulfide. Then, the molybdenum disulfide sample was ultrasonically mixed and intercalated with linear macromolecular polyethyleneimine with a molecular weight of 70,000, and then transferred to a freeze dryer at minus 56 degrees Celsius to dry for 24 hours. The above samples were calcined in a tube furnace, and the experimental conditions were 800 degrees Celsius for 6 hours, and the heating rate was 2 degrees Celsius per minute. The prepared sample is shown in Figure 1B, which shows that the molybdenum disulfide synthesized by the hydrothermal method is evenly distributed in a flower-like shape, without obvious accumulation and agglomeration, and shows a certain degree of transparency, indicating that the molybdenum disulfide is The lamellae are very thin, with small amounts of evenly distributed partially graphitized carbon between the lamellae and between the lamellae. The figure also shows that for the same type of polymer, the intercalation of different molecular weights has little effect on the morphology of the sample, and the intercalation ability of the polymer PEI is stronger.
实施例3Example 3
将0.3克钼酸钠和0.6克硫代乙酰胺加入至反应釜中，并加入20毫升水和10毫升乙二醇溶解。将反应釜放入烘箱中加热进行溶剂热反应，设定烘箱的温度为220摄氏度。反应24小时后，关闭装置，待冷却后离心洗涤得二硫化钼。然后取分子量400的线性高分子聚乙二醇对二硫化钼样品进行超声混匀插层，后转移至零下56摄氏度冻干机中干燥24小时。将上述样品置于管式炉中煅烧，实验条件为800摄氏度持续6小时，升温速率为2摄氏度每分钟。所制备的样品如图1C所示，该图能够看出该水热方法合成的二硫化钼呈花片状均匀分布，没有明显的堆积和团聚，且呈现出一定的透明度，表明该二硫化钼片层非常薄，层间和片间的含有少量的均匀分布的部分石墨化的碳。该图同时说明对于分子量相近的不同高分子而言，有着同样的插层效果，形貌相似。Add 0.3 g of sodium molybdate and 0.6 g of thioacetamide into the reaction kettle, and add 20 ml of water and 10 ml of ethylene glycol to dissolve. The reaction kettle was heated in an oven for solvothermal reaction, and the temperature of the oven was set to 220 degrees Celsius. After 24 hours of reaction, the device was turned off, and after cooling, it was centrifuged and washed to obtain molybdenum disulfide. Then, a linear macromolecular polyethylene glycol with a molecular weight of 400 was taken to perform ultrasonic mixing and intercalation on the molybdenum disulfide sample, and then transferred to a freeze dryer at minus 56 degrees Celsius to dry for 24 hours. The above samples were calcined in a tube furnace, and the experimental conditions were 800 degrees Celsius for 6 hours, and the heating rate was 2 degrees Celsius per minute. The prepared sample is shown in Figure 1C, which shows that the molybdenum disulfide synthesized by the hydrothermal method is evenly distributed in a flower-like shape, without obvious accumulation and agglomeration, and shows a certain degree of transparency, indicating that the molybdenum disulfide is The lamellae are very thin, with small amounts of evenly distributed partially graphitized carbon between the lamellae and between the lamellae. The figure also shows that different polymers with similar molecular weights have the same intercalation effect and similar morphology.
实施例4Example 4
将0.3克钼酸钠和0.6克硫代乙酰胺加入至反应釜中，并加入20毫升水和10毫升乙二醇溶解。将反应釜放入烘箱中加热进行溶剂热反应，设定烘箱的温度为220摄氏度。反应24小时后，关闭装置，待冷却后离心洗涤得二硫化钼。然后取分子量20000的线性高分子聚乙二醇对二硫化钼样品进行超声混匀插层，后转移至零下56摄氏度冻干机中干燥24小时。将上述样品置于管式炉中煅烧，实验条件为800摄氏度持续6小时，升温速率为2摄氏度每分钟。所制备的样品如图1D所示，该图能够看出该水热方法合成的二硫化钼呈花片状均匀分布，没有明显的堆积和团聚，且呈现出一定的透明度，表明该二硫化钼片层非常薄，层间和片间的含有少量的均匀分布的部分石墨化的碳，该图同时说明对于同一种类型的高分子而言，不同的分子量插层对其样品形貌影响不大。Add 0.3 g of sodium molybdate and 0.6 g of thioacetamide into the reaction kettle, and add 20 ml of water and 10 ml of ethylene glycol to dissolve. The reaction kettle was heated in an oven for solvothermal reaction, and the temperature of the oven was set to 220 degrees Celsius. After 24 hours of reaction, the device was turned off, and after cooling, it was centrifuged and washed to obtain molybdenum disulfide. Then, a linear macromolecular polyethylene glycol with a molecular weight of 20,000 was taken to ultrasonically mix and intercalate the molybdenum disulfide sample, and then transferred to a freeze dryer at minus 56 degrees Celsius to dry for 24 hours. The above samples were calcined in a tube furnace, and the experimental conditions were 800 degrees Celsius for 6 hours, and the heating rate was 2 degrees Celsius per minute. The prepared sample is shown in Figure 1D, which shows that the molybdenum disulfide synthesized by the hydrothermal method is evenly distributed in a flower-like shape, without obvious accumulation and agglomeration, and shows a certain degree of transparency, indicating that the molybdenum disulfide is The lamellae are very thin, and there is a small amount of evenly distributed partially graphitized carbon between the layers and between the lamellae. The figure also shows that for the same type of polymer, the intercalation of different molecular weights has little effect on the morphology of the sample. .
与现有技术相比，本发明采用的方法合成的二硫化钼特殊插层结构材料，首次实现以高分子对二硫化钼分子进行有效插层，而且可以选用不同类型，不同分子量的高分子材料，制得层间距扩大的“M-C-M”三明治异质结电极材料，导电性好，制备方法简单，创新性强。碳链在层间和片间的支撑，不仅提供了层间活性位点，而且为片间离子传输提供了快捷通道，同时还大大提高了二硫化钼的导电性，使得每个片层都能有效储能，用于超级电容器中具有比容量高、循环性能好、结构稳定等优势。Compared with the prior art, the molybdenum disulfide special intercalation structure material synthesized by the method adopted in the present invention realizes the effective intercalation of molybdenum disulfide molecules with macromolecules for the first time, and different types and different molecular weight macromolecular materials can be selected. , The "M-C-M" sandwich heterojunction electrode material with expanded interlayer spacing is obtained, which has good conductivity, simple preparation method and strong innovation. The support of carbon chains between layers and sheets not only provides interlayer active sites, but also provides a fast channel for ion transport between sheets, and also greatly improves the conductivity of molybdenum disulfide, so that each sheet can Effective energy storage, used in supercapacitors has the advantages of high specific capacity, good cycle performance, and stable structure.
实施例5Example 5
一种二硫化钼插层材料的制备方法，采用以下步骤：A preparation method of molybdenum disulfide intercalation material, adopts the following steps:
(1)将钼酸钠、硫代乙酰胺混合并加入水与乙二醇按体积比为2:1混合得到的混合溶剂溶解，钼酸钠、硫代乙酰胺的质量比为0.3:1.2，并且控制钼酸钠在溶剂中的浓度控制为0.01g/ml；(1) mixing sodium molybdate and thioacetamide and adding water and ethylene glycol in a volume ratio of 2:1 to obtain the mixed solvent to dissolve, the mass ratio of sodium molybdate and thioacetamide is 0.3:1.2, And control the concentration of sodium molybdate in the solvent to be 0.01g/ml;
(2)对步骤(1)的混合溶液加热至200℃进行溶剂热反应24h；(2) heating the mixed solution in step (1) to 200° C. for solvothermal reaction for 24h;
(3)将步骤(2)得到的产物冷却后采用水和乙醇交替离心洗涤三次；(3) water and ethanol are alternately centrifuged and washed three times after the product obtained in step (2) is cooled;
(4)取聚乙烯亚胺对步骤(3)中获得的产品进行超声混匀插层后，聚乙烯亚胺的加入质量为二硫化钼的20％，超声处理时控制超声频率为360HZ，时间为3h，然后转移至冻干机，控制温度为零下56摄氏度，冷冻干燥12小时；(4) after the product obtained in step (3) is ultrasonically mixed and intercalated with polyethyleneimine, the added mass of polyethyleneimine is 20% of that of molybdenum disulfide, and the ultrasonic frequency is controlled to be 360HZ during ultrasonic treatment, and the time for 3h, then transferred to a freeze dryer, controlled at a temperature of minus 56 degrees Celsius, and freeze dried for 12 hours;
(5)将步骤(4)中的样品置于管式炉中，控制升温速率为2摄氏度每分钟，升温至600摄氏度持续6小时，制备得到二硫化钼插层材料。(5) placing the sample in step (4) in a tube furnace, controlling the heating rate to be 2 degrees Celsius per minute, and heating to 600 degrees Celsius for 6 hours to prepare a molybdenum disulfide intercalation material.
实施例6Example 6
一种二硫化钼插层材料的制备方法，采用以下步骤：A preparation method of molybdenum disulfide intercalation material, adopts the following steps:
(1)将钼酸钠、硫代乙酰胺混合并加入水与乙二醇按体积比为2:1混合得到的混合溶剂溶解，钼酸钠、硫代乙酰胺的质量比为0.4:0.9，并且控制钼酸钠在溶剂中的浓度控制为0.01g/ml；(1) mixing sodium molybdate and thioacetamide and adding water and ethylene glycol in a volume ratio of 2:1 to obtain the mixed solvent to dissolve, the mass ratio of sodium molybdate and thioacetamide is 0.4:0.9, And control the concentration of sodium molybdate in the solvent to be 0.01g/ml;
(2)对步骤(1)的混合溶液加热至220℃进行溶剂热反应24h；(2) heating the mixed solution of step (1) to 220°C for solvothermal reaction for 24h;
(3)将步骤(2)得到的产物冷却后采用水和乙醇交替离心洗涤三次；(3) water and ethanol are alternately centrifuged and washed three times after the product obtained in step (2) is cooled;
(4)取聚乙烯亚胺对步骤(3)中获得的产品进行超声混匀插层后，聚乙烯亚胺的加入质量为二硫化钼的50％，超声处理时控制超声频率为400HZ，时间为2h，然后转移至冻干机，控制温度为零下50摄氏度，冷冻干燥18小时；(4) after the product obtained in step (3) is ultrasonically mixed and intercalated with polyethyleneimine, the added mass of polyethyleneimine is 50% of that of molybdenum disulfide, and the ultrasonic frequency is controlled to be 400HZ during ultrasonic treatment, and the time for 2h, then transferred to a freeze dryer, the temperature was controlled at minus 50 degrees Celsius, and freeze-dried for 18 hours;
(5)将步骤(4)中的样品置于管式炉中，控制升温速率为3摄氏度每分钟，升温至700摄氏度持续5小时，制备得到二硫化钼插层材料。(5) placing the sample in step (4) in a tube furnace, controlling the heating rate to be 3 degrees Celsius per minute, and heating to 700 degrees Celsius for 5 hours to prepare a molybdenum disulfide intercalation material.
实施例7Example 7
一种二硫化钼插层材料的制备方法，采用以下步骤：A preparation method of molybdenum disulfide intercalation material, adopts the following steps:
(1)将钼酸钠、硫代乙酰胺混合并加入水与乙二醇按体积比为2:1混合得到的混合溶剂溶解，钼酸钠、硫代乙酰胺的质量比为0.6:0.6，并且控制钼酸钠在溶剂中的浓度控制为0.02g/ml；(1) mixing sodium molybdate and thioacetamide and adding water and ethylene glycol in a volume ratio of 2:1 to obtain the mixed solvent to dissolve, the mass ratio of sodium molybdate and thioacetamide is 0.6:0.6, And control the concentration of sodium molybdate in the solvent to be 0.02g/ml;
(2)对步骤(1)的混合溶液加热至240℃进行溶剂热反应20h；(2) heating the mixed solution of step (1) to 240°C to carry out a solvothermal reaction for 20h;
(3)将步骤(2)得到的产物冷却后采用水和乙醇交替离心洗涤三次；(3) water and ethanol are alternately centrifuged and washed three times after the product obtained in step (2) is cooled;
(4)取聚乙二醇对步骤(3)中获得的产品进行超声混匀插层后，聚乙二醇的加入质量为二硫化钼的100％，超声处理时控制超声频率为440HZ，时间为1h，然后转移至冻干机，控制温度为零下40摄氏度，冷冻干燥12小时；(4) after taking polyethylene glycol to carry out ultrasonic mixing and intercalation to the product obtained in step (3), the added mass of polyethylene glycol is 100% of that of molybdenum disulfide, and the ultrasonic frequency is controlled to be 440HZ during ultrasonic treatment, and the time for 1h, then transferred to a freeze dryer, controlled at a temperature of minus 40 degrees Celsius, and freeze-dried for 12 hours;
(5)将步骤(4)中的样品置于管式炉中，控制升温速率为5摄氏度每分钟，升温至800摄氏度持续2小时，制备得到二硫化钼插层材料。(5) placing the sample in step (4) in a tube furnace, controlling the heating rate to be 5 degrees Celsius per minute, and heating the temperature to 800 degrees Celsius for 2 hours to prepare a molybdenum disulfide intercalation material.
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变形或修改，这并不影响本发明的实质内容。Specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the above-mentioned specific embodiments, and those skilled in the art can make various variations or modifications within the scope of the claims, which do not affect the essential content of the present invention.
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| CN109470761B (en) * | 2018-10-19 | 2020-12-04 | 重庆医科大学 | An electrochemical DNA aptamer sensor for zearalenone ZEN detection and method for detecting ZEN |
| CN111393641B (en) * | 2020-03-24 | 2021-10-12 | 四川大学 | Surfactant for simultaneous exfoliation and vinylation of two-dimensional sheet materials and their preparation and application |
| CN112599752B (en) * | 2021-01-06 | 2023-07-18 | 天津工业大学 | Preparation method of a carbon-coated hollow kapok fiber bearing flower-shaped molybdenum disulfide composite material as anode material for sodium-ion batteries |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863955A (en) * | 2012-10-12 | 2013-01-09 | 上海交通大学 | Polyethylene glycol/stannic sulfide intercalation quantum dot and hydrothermal synthesis method |
| CN103915630A (en) * | 2014-04-28 | 2014-07-09 | 华东理工大学 | Molybdenum disulfide/mesoporous carbon composite electrode material as well as preparation method and application thereof |
| CN104495937A (en) * | 2014-12-31 | 2015-04-08 | 中国地质大学（武汉） | Preparation method of carbon-doped molybdenum disulfide nanometer material |
| CN105617956A (en) * | 2016-01-28 | 2016-06-01 | 复旦大学 | Molybdenum disulfide nanosheet/polyimide based composite aerogel and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863955A (en) * | 2012-10-12 | 2013-01-09 | 上海交通大学 | Polyethylene glycol/stannic sulfide intercalation quantum dot and hydrothermal synthesis method |
| CN103915630A (en) * | 2014-04-28 | 2014-07-09 | 华东理工大学 | Molybdenum disulfide/mesoporous carbon composite electrode material as well as preparation method and application thereof |
| CN104495937A (en) * | 2014-12-31 | 2015-04-08 | 中国地质大学（武汉） | Preparation method of carbon-doped molybdenum disulfide nanometer material |
| CN105617956A (en) * | 2016-01-28 | 2016-06-01 | 复旦大学 | Molybdenum disulfide nanosheet/polyimide based composite aerogel and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Exfoliated MoS2 Nanocomposite as an Anode Material;Jie Xiao et al.;《Chem. Mater.》;20100730;第22卷;第4522-4524页 * |
| Surfactant‐assisted hydrothermally synthesized MoS2 samples with controllable morphologies and structures for anthracene hydrogenation;Min Li et al.;《Chinese Journal of Catalysis》;20170305;第38卷;第597-606页 * |
| Ultrathin MoS2 nanosheets tightly anchoring onto nitrogen-doped graphene for enhanced lithium storage properties;Saisai Xia et al.;《chemical engineering journal》;20170919;第332卷;第431-439页 * |
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