CN104409225A - Preparation method of manganese dioxide/ carbon microspheres composite material and application of composite material serving as supercapacitor electrode material - Google Patents
Preparation method of manganese dioxide/ carbon microspheres composite material and application of composite material serving as supercapacitor electrode material Download PDFInfo
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Abstract
本发明提供了一种用于超级电容器电极材料的二氧化锰/碳微球(MnO2/CMSs)复合材料，属于复合材料技术领域。本发明以葡萄糖为起始原料，先通过水热法制得纳米碳微球，再通过原位自组装法使碳微球与二氧化锰复合而得。电化学性能测试表明，本发明制备的MnO2/CMSs复合材料，不仅能够实现两者性能的协同效应，而且具有单一电极不具备的优良性能，显示出较高的电化学电容行为、优良的倍容率，以及较好的循环稳定性，因此可以作为超级电容器电极材料。另外，本发明复合材料的制备过程简单、工艺稳定、易于操作、质量可靠、成本低廉，作为超级电容器电极材料符合商业化的基本要求。The invention provides a manganese dioxide/carbon microsphere (MnO 2 /CMSs) composite material used as an electrode material for a supercapacitor, belonging to the technical field of composite materials. The invention uses glucose as a starting material, firstly prepares nanometer carbon microspheres through a hydrothermal method, and then composes the carbon microspheres and manganese dioxide through an in-situ self-assembly method. The electrochemical performance test shows that the MnO 2 /CMSs composite material prepared by the present invention can not only realize the synergistic effect of the two performances, but also has excellent performance that a single electrode does not possess, showing high electrochemical capacitance behavior, excellent multiplier Capacitance, and better cycle stability, so it can be used as a supercapacitor electrode material. In addition, the preparation process of the composite material of the present invention is simple, the process is stable, easy to operate, reliable in quality, and low in cost, and meets the basic requirements of commercialization as an electrode material of a supercapacitor.
Description
技术领域 technical field
本发明涉及一种二氧化锰/碳微球复合材料的制备，尤其涉及一种二氧化锰/碳微球(MnO2/CMSs)复合材料的制备；本发明同时还涉及该二氧化锰/碳微球(MnO2/CMSs)复合材料作为超级电容器电极材料应用，属于复合材料领域及电化学材料领域。 The present invention relates to the preparation of a kind of manganese dioxide/carbon microsphere composite material, relate in particular to the preparation of a kind of manganese dioxide/carbon microsphere (MnO 2 /CMSs) composite material; The present invention also relates to this manganese dioxide/carbon The microsphere (MnO 2 /CMSs) composite material is used as a supercapacitor electrode material, and belongs to the field of composite materials and the field of electrochemical materials.
背景技术 Background technique
超级电容器是一种新型的能量储存/转化装置，其能量密度高（10kw/kg）、充放时间短、循环寿命长和无污染等优点广泛应用于便携式电子产品，混合动力电动汽车和大型工业设备等。而电极材料的选择是影响超级电容器的主要原因，主要包括金属氧化物，导电聚合物和碳基材料。 Supercapacitor is a new type of energy storage/conversion device, which is widely used in portable electronic products, hybrid electric vehicles and large industrial equipment etc. The selection of electrode materials is the main reason affecting supercapacitors, mainly including metal oxides, conductive polymers and carbon-based materials.
MnO2由于其丰富、价廉、环境友好、活泼的氧化还原活性以及高的理论比电容（1232 F·g-1）而受到了众多的关注。MnO2不但无需在强酸或强碱性电解液中而在中性电解液中就能很好地运行，而且还能够展现出快速的充放电能力和类似于非法拉第能量存储行为，这与水合RuO2的电荷存储机理相似。因此，在超级电容器的应用中MnO2被认为最有前景的一种RuO2的替代物。然而MnO2低的比电容和差的循环稳定性使得其在实际应用中受到了很大的限制，这主要归因于其差的导电性以及在反复循环过程中晶体的膨胀/收缩而造成的剥落，为了弥补这些不足之处，导电碳材料碳微球可以用作支撑材料与MnO2形成复合物。而单纯的MnO2导电性差，电化学利用率低，从而限制其在超期电容器中应用。 MnO 2 has attracted much attention due to its abundance, cheapness, environmental friendliness, lively redox activity, and high theoretical specific capacitance (1232 F·g -1 ). MnO2 not only works well in neutral electrolytes without the need for strong acid or alkaline electrolytes, but also exhibits fast charge-discharge capability and non-faradic energy storage behavior, which is similar to that of hydrated RuO The charge storage mechanism of 2 is similar. Therefore, MnO 2 is considered to be the most promising substitute for RuO 2 in the application of supercapacitors. However, the low specific capacitance and poor cycle stability of MnO2 greatly restrict its practical application, which is mainly attributed to its poor electrical conductivity and crystal expansion/contraction during repeated cycles. Exfoliation, in order to make up for these deficiencies, conductive carbon material carbon microspheres can be used as support materials to form composites with MnO2 . However, pure MnO 2 has poor conductivity and low electrochemical utilization, which limits its application in long-term capacitors.
碳微球是典型的2D碳材料，它具有良好的导电性、大的比表面积、化学性质稳定、机械强度大、振实密度高以及可加工性，可以作为生长活性纳米材料的载体而广泛应用于制备高性能的复合材料。将MnO2与碳微球进行复合期望得到性能更优的复合材料。 Carbon microspheres are typical 2D carbon materials, which have good electrical conductivity, large specific surface area, stable chemical properties, high mechanical strength, high tap density and processability, and can be widely used as carriers for growing active nanomaterials for the preparation of high-performance composite materials. Combining MnO 2 with carbon microspheres is expected to obtain composite materials with better performance.
制备二氧化锰/碳微球(MnO2/CMSs)复合材料作为超级电容器电极材料，得到了具有单一电极不具备的优良性能，应用前景广泛。 Manganese dioxide/carbon microspheres (MnO 2 /CMSs) composites were prepared as electrode materials for supercapacitors, which have excellent properties that single electrodes do not possess, and have broad application prospects.
发明内容 Contents of the invention
本发明的目的是结合MnO2与碳微球CMSs的特性，提供一种二氧化锰/碳微球(MnO2/CMSs)复合材料。 The object of the present invention is to provide a manganese dioxide/carbon microsphere (MnO 2 /CMSs) composite material by combining the characteristics of MnO 2 and carbon microsphere CMSs.
本发明的目的还在于提供一种二氧化锰/碳微球(MnO2/CMSs)复合材料的制备方法。 The object of the present invention is also to provide a preparation method of manganese dioxide/carbon microspheres (MnO 2 /CMSs) composite material.
本发明的更重要目的在于提供一种二氧化锰/碳微球(MnO2/CMSs)复合材料作为超级电容器电极材料的应用。 A more important purpose of the present invention is to provide a composite material of manganese dioxide/carbon microspheres (MnO 2 /CMSs) as an electrode material for a supercapacitor.
一、二氧化锰/碳微球(MnO2/CMSs)复合材料的制备 1. Preparation of manganese dioxide/carbon microspheres (MnO 2 /CMSs) composites
本发明二氧化锰/碳微球复合材料的制备，是以葡萄糖为起始原料，先通过水热法制得纳米碳微球，再通过原位自组装使碳微球与二氧化锰复合而得。具体制备工艺如下： The preparation of the manganese dioxide/carbon microsphere composite material of the present invention is obtained by using glucose as a starting material, firstly preparing nano-carbon microspheres through a hydrothermal method, and then compounding carbon microspheres and manganese dioxide through in-situ self-assembly . Concrete preparation process is as follows:
（1）纳米碳微球的制备：将葡萄糖粉充分溶于去离子水中，于160~200℃下水热反应12~24h；冷却到室温后，抽滤，产物用无水乙醇和去离子水洗涤，烘干，即得纳米碳微球(CMSs)； (1) Preparation of nano-carbon microspheres: Fully dissolve glucose powder in deionized water, hydrothermally react at 160-200°C for 12-24 hours; after cooling to room temperature, filter with suction, and wash the product with absolute ethanol and deionized water , dried to obtain carbon nanospheres (CMSs);
（2）二氧化锰/碳微球复合材料的制备：将纳米碳微球和KMnO4于去离子水中混合均匀，加入浓硫酸使反应体系的pH=1~2；然后在油浴下加热至75~90℃，回流0.5~1.5h；待反应体系冷却到室温后，抽滤，产物用无水乙醇和去离子水洗涤，烘干，即得二氧化锰/碳微球复合材料（MnO2/CMSs）。 其中碳微球和KMnO4的质量比控制在1:8~1:9。 (2) Preparation of manganese dioxide/carbon microsphere composite material: Mix nano-carbon microspheres and KMnO 4 in deionized water evenly, add concentrated sulfuric acid to make the pH of the reaction system = 1~2; then heat in an oil bath to 75~90℃, reflux for 0.5~1.5h; after the reaction system is cooled to room temperature, suction filter, the product is washed with absolute ethanol and deionized water, and dried to obtain the manganese dioxide/carbon microsphere composite material (MnO 2 /CMSs). The mass ratio of carbon microspheres and KMnO 4 is controlled at 1:8~1:9.
二、二氧化锰/碳微球复合材料的制备的结构表征2. Structural characterization of the preparation of manganese dioxide/carbon microsphere composites
下面通过场发射扫描电镜(FE-SEM)、热分析仪(TG)、红外谱图(FTIR)及X射线衍射(XRD)对本发明制备的二氧化锰(MnO2) 纳米棒材料的结构进行详细说明。 The structure of the manganese dioxide (MnO 2 ) nanorod material prepared by the present invention is detailed below by field emission scanning electron microscope (FE-SEM), thermal analyzer (TG), infrared spectrum (FTIR) and X-ray diffraction (XRD) illustrate.
1、扫描电镜（SEM）分析 1. Scanning electron microscope (SEM) analysis
图1(a)为本发明制备的碳微球CMSs材料的场发射扫描电镜(SEM)图片。由图a可以见，大规模均一单分散的炭微球(CMSs)的尺寸约为700nm左右，该材料具有大比表面积的和良好的导电性和强的机械性能。图1(b)、(c)和(d)分别为本发明制备的MnO2/CMSs复合材料不同放大倍数下的场发射扫描电镜图(SEM)。由图1可以见，MnO2均匀的包覆在炭微球上，形成纳米花形貌。MnO2均匀的负载于CMSs上，CMSs提供了很好的导电基底，更有利于MnO2赝电容的彰显。复合材料这一独特的结构不仅能够在MnO2表面提供充足的电化学活性位点，而且还能大大增加有效的液固接触面积，给电解液离子的嵌入/脱出提供了快速路径，进而促使法拉第反应的进行，而且更有利于MnO2产生更高赝电容。 Fig. 1 (a) is the field emission scanning electron microscope (SEM) picture of the carbon microsphere CMSs material prepared by the present invention. It can be seen from Figure a that the size of large-scale uniform monodisperse carbon microspheres (CMSs) is about 700nm, and the material has a large specific surface area and good electrical conductivity and strong mechanical properties. Fig. 1 (b), (c) and (d) are the field emission scanning electron microscope images (SEM) under different magnifications of the MnO 2 /CMSs composite material prepared by the present invention respectively. It can be seen from Figure 1 that MnO 2 is uniformly coated on the carbon microspheres, forming a nanoflower shape. MnO 2 is uniformly loaded on CMSs, and CMSs provide a good conductive substrate, which is more conducive to the display of MnO 2 pseudocapacitance. The unique structure of the composite material can not only provide sufficient electrochemically active sites on the surface of MnO2 , but also greatly increase the effective liquid-solid contact area, providing a fast path for the intercalation/extraction of electrolyte ions, thereby promoting Faraday The progress of the reaction is more conducive to the higher pseudocapacitance of MnO 2 .
2、X衍射谱图（XRD）分析 2. X-ray diffraction (XRD) analysis
图2为纯CMSs、MnO2和MnO2/CMSs复合材料的X衍射谱图（XRD）。纯CMSs在22°处有一个宽化衍射峰，是炭微球的特征峰。MnO2/CMSs复合物衍射峰出峰位置，分别对应于MnO2的出峰位置，只是强度减弱。CMSs的特征峰在MnO2/CMSs的XRD谱图中的强度很弱，但是还是能够与其它衍射峰区分开来。从图2中可以看出，CMSs和MnO2进行了很好的复合。 Fig. 2 is the X-ray diffraction spectrum (XRD) of pure CMSs, MnO 2 and MnO 2 /CMSs composite materials. Pure CMSs have a broadened diffraction peak at 22°, which is a characteristic peak of carbon microspheres. The positions of the diffraction peaks of the MnO 2 /CMSs composite correspond to the peak positions of MnO 2 , but the intensity is weakened. The intensity of the characteristic peaks of CMSs in the XRD pattern of MnO 2 /CMSs is very weak, but they can still be distinguished from other diffraction peaks. It can be seen from Fig. 2 that the CMSs and MnO2 were well composited.
3、红外光谱图（FT-IR）分析 3. Infrared spectrum (FT-IR) analysis
图3为本发明制备的MnO2/CMSs复合材料的红外光谱图（FT-IR）。从图3可以看出，CMSs有较强的特征吸收峰，对于MnO2/CMSs复合材料的红外光谱图，吸收峰的出峰位置和纯的MnO2、CMSs出峰位置一致，从而证明MnO2和CMSs进行了很好的复合。 Fig. 3 is the infrared spectrogram (FT-IR) of the MnO 2 /CMSs composite material prepared in the present invention. It can be seen from Figure 3 that CMSs has a strong characteristic absorption peak. For the infrared spectrum of the MnO 2 /CMSs composite material, the peak position of the absorption peak is consistent with that of pure MnO 2 and CMSs, thus proving that MnO 2 Composite well with CMSs.
4、热重分析 4. Thermogravimetric analysis
图4 为本发明制备的MnO2/CMSs复合材料的热重分析仪图（TG）。从图4可知，在100℃附近，TG曲线上出现了轻微的质量损失，这是由样品失去表面物理吸附水造成的。复合物样品在350℃后有明显的失重现象，这是由复合物中CMSs的分解所致。在500℃之后，TG曲线基本趋于稳定，说明CMSs已完全分解。经估算得出，复合物中MnO2和CMSs的质量比约为3:1~2:1。 Fig. 4 is the thermal gravimetric analysis diagram (TG) of the MnO 2 /CMSs composite material prepared in the present invention. It can be seen from Figure 4 that there is a slight mass loss on the TG curve near 100 °C, which is caused by the loss of physical adsorption water on the surface of the sample. The composite samples had obvious weight loss phenomenon after 350 °C, which was caused by the decomposition of CMSs in the composites. After 500 °C, the TG curve basically tends to be stable, indicating that the CMSs have been completely decomposed. It is estimated that the mass ratio of MnO 2 and CMSs in the composite is about 3:1~2:1.
5、吸-脱附等温线分析 5. Adsorption-desorption isotherm analysis
图5为本发明制备的MnO2/CMSs复合材料的吸-脱附等温线。复合物MnO2/CMSs的曲线中都有较为明显的滞后环，表明复合材料是介孔材料。BET测试结果显示复合物MnO2/CMSs的比表面积是71.2m2/g。 Fig. 5 is the adsorption-desorption isotherm of the MnO 2 /CMSs composite material prepared in the present invention. The curves of the composite MnO 2 /CMSs have obvious hysteresis loops, indicating that the composite material is a mesoporous material. The BET test results show that the specific surface area of the composite MnO 2 /CMSs is 71.2m 2 /g.
图6为本发明制备的MnO2/CMSs复合材料的孔径分布曲线。从图6中可以看到，复合物MnO2/CMSs有两个孔径分布，一个是在2.5 nm左右的孔径分布；另一个是在10~30 nm范围内的宽分布，这主要是交叉联接的MnO2纳米片形成的大孔结构。这一特殊的双孔结构扩大了电极材料与电解液的接触面积并且提供了更多的电化学活性位点，从而提高了电极材料的电化学性能。 Fig. 6 is the pore size distribution curve of the MnO 2 /CMSs composite material prepared in the present invention. It can be seen from Fig. 6 that the composite MnO 2 /CMSs has two pore size distributions, one is a pore size distribution around 2.5 nm; the other is a broad distribution in the range of 10–30 nm, which is mainly cross-linked Macroporous structure formed by MnO2 nanosheets. This special double-pore structure expands the contact area between the electrode material and the electrolyte and provides more electrochemically active sites, thereby improving the electrochemical performance of the electrode material.
三、电化学性能 3. Electrochemical properties
下面通过电化学工作站CHI660B对本发明制备的MnO2/CMSs复合材料的电化学性能表征进行详细说明。 The electrochemical performance characterization of the MnO 2 /CMSs composite material prepared by the present invention will be described in detail below through the electrochemical workstation CHI660B.
1、超级电容器电极的制备：将MnO2/CMSs复合材料和乙炔黑的混合固体粉末共5.88 mg（MnO2/CMSs复合材料与乙炔黑的质量百分数分别85%、15%））均匀分散于1ml Nafion溶液中，超声30min后，用移液枪量取5ul混合溶液滴在直径为5mm的玻碳电极上，自然晾干，即得测试电极。 1. Preparation of supercapacitor electrodes: 5.88 mg of mixed solid powder of MnO 2 /CMSs composite material and acetylene black (the mass percentages of MnO 2 /CMSs composite material and acetylene black are 85% and 15% respectively)) were uniformly dispersed in 1ml In the Nafion solution, after ultrasonication for 30 minutes, use a pipette gun to measure 5ul of the mixed solution and drop it on a glassy carbon electrode with a diameter of 5mm, and let it dry naturally to obtain the test electrode.
2、电化学性能测试 2. Electrochemical performance test
图7为本发明制备的MnO2/CMSs复合材料作为超级电容器电极材料在1mol/L的Na2SO4电解液溶液中，在电势窗口范围为-1.3-1.4V，不同扫速下的循环伏安曲线（CV）。结果表明，在所有样品的CV曲线上均都可以看见两对氧化还原峰，是产生法拉第电容的象征。而且，随着扫描速率的增大，CV曲线的形状基本保持不变，说明复合材料的倍容率较好，复合材料具有做超级电容器电极材料的潜能。 Fig. 7 is the MnO 2 /CMSs composite material prepared by the present invention as a supercapacitor electrode material in 1mol/L Na 2 SO 4 electrolyte solution, in the potential window range of -1.3-1.4V, cyclic volts at different scan rates Safety Curve (CV). The results show that two pairs of redox peaks can be seen on the CV curves of all samples, which is a symbol of the generation of Faraday capacitance. Moreover, as the scan rate increases, the shape of the CV curve remains basically unchanged, indicating that the composite material has a better capacity ratio, and the composite material has the potential to be used as a supercapacitor electrode material.
图8为本发明制备的MnO2/CMSs复合材料作为超级电容器电极材料在1mol/L的Na2SO4电解液中，电势窗口范围为-1.3-1.4V，不同电流密度下的恒电流充放电曲线图。由图6可知，当电流密度为0.5 A/g时，电极材料的比电容可以达到151F/g，说明材料在宽的电位窗口下具有较高的比电容，具有做超级电容器电极材料的潜能，这与循环伏安曲线测试结果相一致。 Figure 8 shows the constant current charge and discharge of the MnO 2 /CMSs composite material prepared by the present invention as a supercapacitor electrode material in a 1mol/L Na 2 SO 4 electrolyte with a potential window range of -1.3-1.4V and different current densities Graph. It can be seen from Figure 6 that when the current density is 0.5 A/g, the specific capacitance of the electrode material can reach 151F/g, indicating that the material has a high specific capacitance under a wide potential window and has the potential to be used as a supercapacitor electrode material. This is consistent with the cyclic voltammetry test results.
图9为本发明制备的MnO2/CMSs复合材料在频率范围为0.1~100kHz，偏置电压为0.8V时的交流阻抗图。由图7可知，复合材料的电荷迁移电阻较小，这主要是由于复合材料特殊的结构可以使得电解液快速的渗透到电极材料中并且能够大大提高固液反应界面，从而有效地降低了复合材料的电荷迁移电阻。 Fig. 9 is an AC impedance diagram of the MnO 2 /CMSs composite material prepared in the present invention at a frequency range of 0.1-100 kHz and a bias voltage of 0.8 V. It can be seen from Figure 7 that the charge transfer resistance of the composite material is small, which is mainly due to the special structure of the composite material that allows the electrolyte to penetrate into the electrode material quickly and can greatly improve the solid-liquid reaction interface, thereby effectively reducing the charge transfer resistance of the composite material. charge transfer resistance.
实验表明，在制备超级电容器电极时，MnO2/CMSs复合材料与乙炔黑的质量比为6.0:1~6.5:1，分散于Nafion溶液中的MnO2/CMSs复合材料和乙炔黑的质量浓度为5.5~6.0mg/mL，涂覆于玻碳电极上混合液的量为23.5~26.5uL/cm2时，作为超级电容器电极材料，均具有优良的电化学性能。 Experiments show that when preparing supercapacitor electrodes, the mass ratio of MnO 2 /CMSs composite material to acetylene black is 6.0:1~6.5:1, and the mass concentration of MnO 2 /CMSs composite material and acetylene black dispersed in Nafion solution is 5.5~6.0mg/mL, when the amount of the mixed solution coated on the glassy carbon electrode is 23.5~26.5uL/cm 2 , as a supercapacitor electrode material, it has excellent electrochemical performance.
综上所述，本发明制备的MnO2/CMSs复合材料，不仅能够实现两者性能的协同效应，而且具有单一电极不具备的优良性能，显示出较高的电化学电容行为，优良的倍容率，以及较好的循环稳定性，因此可以作为超级电容器电极材料。另外，本发明复合材料的制备过程简单、工艺稳定、易于操作、质量可靠、成本低廉，作为超级电容器电极材料符合商业化的基本要求。 In summary, the MnO 2 /CMSs composite material prepared by the present invention can not only realize the synergistic effect of the properties of the two, but also has excellent properties that a single electrode does not possess, showing high electrochemical capacitance behavior, excellent capacity doubling rate, and good cycle stability, so it can be used as a supercapacitor electrode material. In addition, the preparation process of the composite material of the present invention is simple, the process is stable, easy to operate, reliable in quality, and low in cost, and meets the basic requirements of commercialization as an electrode material of a supercapacitor.
附图说明 Description of drawings
图1为本发明制备的碳微球CMSs及MnO2/CMSs复合材料的场发射扫描电镜图(SEM)。 Fig. 1 is a field emission scanning electron microscope image (SEM) of carbon microsphere CMSs and MnO 2 /CMSs composite materials prepared in the present invention.
图2为纯CMSs、MnO2和MnO2/CMSs复合材料的X衍射谱图（XRD）。 Fig. 2 is the X-ray diffraction spectrum (XRD) of pure CMSs, MnO 2 and MnO 2 /CMSs composite materials.
图3为本发明制备的MnO2/CMSs复合材料的红外光谱图（FT-IR）。 Fig. 3 is the infrared spectrogram (FT-IR) of the MnO 2 /CMSs composite material prepared in the present invention.
图4 为本发明制备的MnO2/CMSs复合材料的热重分析仪图（TG）。 Fig. 4 is the thermal gravimetric analysis diagram (TG) of the MnO 2 /CMSs composite material prepared in the present invention.
图5为本发明制备的MnO2/CMSs复合材料的吸-脱附等温线。 Fig. 5 is the adsorption-desorption isotherm of the MnO 2 /CMSs composite material prepared in the present invention.
图6为本发明制备的MnO2/CMSs复合材料的孔径分布曲线。 Fig. 6 is the pore size distribution curve of the MnO 2 /CMSs composite material prepared in the present invention.
图7为本发明制备的MnO2/CMSs复合材料作为超级电容器电极材料在1mol/L的Na2SO4电解液溶液中不同扫速下的循环伏安曲线（CV）。 Fig. 7 is the cyclic voltammetry curve (CV) of the MnO 2 /CMSs composite prepared in the present invention as a supercapacitor electrode material in a 1 mol/L Na 2 SO 4 electrolyte solution at different scan rates.
图8为本发明制备的MnO2/CMSs复合材料作为超级电容器电极材料在1mol/L的Na2SO4电解液中不同电流密度下的恒电流充放电曲线图。 Fig. 8 is a galvanostatic charge-discharge curve at different current densities of the MnO 2 /CMSs composite prepared in the present invention as a supercapacitor electrode material in 1 mol/L Na 2 SO 4 electrolyte.
图9为本发明制备的MnO2/CMSs复合材料在频率范围为0.1~ 100kHz，偏置电压为0.8V时的交流阻抗图。 Fig. 9 is an AC impedance diagram of the MnO 2 /CMSs composite material prepared in the present invention at a frequency range of 0.1-100 kHz and a bias voltage of 0.8 V.
具体实施方式 Detailed ways
下面通过具体实施例对本发明MnO2/CMSs复合材料的制备及其电极材料的制备和电化学性能作进一步详细的说明。 The preparation of the MnO 2 /CMSs composite material and the preparation and electrochemical performance of the electrode material of the present invention will be further described in detail through specific examples below.
使用的仪器和试剂：CHI660B电化学工作站 (上海辰华仪器公司) 用于电化学性能测试；电子天平 (北京赛多利斯仪器有限公司)用于称量药品；JSM－6701F 冷场发射型扫描电镜 (日本电子株式会社) 用于材料的形貌表征；Perkin-Elmer TG/DTA-6300型热分析仪用于热分析；FTS3000型傅里叶红外光谱仪（美国DIGILAB公司）用来分析组成;比表面积和孔径分布测试是由物理自动吸附仪（ASAP 2020）完成的。硫酸（白银西区银环化学试剂厂），葡萄糖(烟台市双双化工有限公司, 分析纯)，乙炔黑（湖南省桂阳谭沙石墨厂），高锰酸钾（天津市科密欧化学试剂开发中心），无水乙醇（安徽安特生物化学有限公司），硫酸钠（国药集团化学试剂有限公司），玻碳电极（上海众维新材料有限公司）。实验过程中使用的水均为一次蒸馏水，实验所用的试剂均为分析纯。 Instruments and reagents used: CHI660B electrochemical workstation (Shanghai Chenhua Instrument Co., Ltd.) for electrochemical performance testing; electronic balance (Beijing Sartorius Instrument Co., Ltd.) for weighing drugs; JSM-6701F cold field emission scanning electron microscope ( Japan Electronics Co., Ltd.) for the morphology characterization of materials; Perkin-Elmer TG/DTA-6300 thermal analyzer for thermal analysis; FTS3000 Fourier transform infrared spectrometer (DIGILAB, USA) for composition analysis; specific surface area and The pore size distribution test was done by a physical automatic adsorption instrument (ASAP 2020). Sulfuric acid (Yinhuan Chemical Reagent Factory, Baiyin West District), glucose (Yantai Shuangshuang Chemical Co., Ltd., analytically pure), acetylene black (Hunan Guiyang Tansha Graphite Factory), potassium permanganate (developed by Tianjin Kemiou Chemical Reagents) Center), absolute ethanol (Anhui Ante Biochemical Co., Ltd.), sodium sulfate (Sinopharm Chemical Reagent Co., Ltd.), glassy carbon electrode (Shanghai Zhongwei New Material Co., Ltd.). The water used in the experiment was primary distilled water, and the reagents used in the experiment were of analytical grade.
实施例1 Example 1
（1）二氧化锰/碳微球(MnO2/CMSs)复合材料的制备 (1) Preparation of manganese dioxide/carbon microspheres (MnO 2 /CMSs) composites
在装有100mL去离子水的烧杯中加入6 g葡萄糖粉末，搅拌1h，然后将混合溶液置于高压反应釜中，于180℃下水热反应24h，待高压反应釜冷却到室温后，将产物抽滤、用无水乙醇和去离子水洗涤数次，60℃下真空干燥12h，即得碳微球(CMSs)。然后将0.86g KMnO4和0.15g CMSs加入到100mL去离子水中不断搅拌，混合物搅拌5min后加入1mL的浓硫酸使反应体系的pH为1~2，室温下搅拌30 min，随即采用油浴加热的方法将混合物加热到80℃，回流1h；待反应体系冷却到室温后，抽滤，产物用无水乙醇和去离子水洗涤数次，60℃下烘12h，即得产物MnO2/CMSs复合材料。 Add 6 g of glucose powder into a beaker containing 100 mL of deionized water, stir for 1 h, then place the mixed solution in an autoclave, and conduct a hydrothermal reaction at 180 °C for 24 h, and after the autoclave is cooled to room temperature, pump the product Filter, wash several times with absolute ethanol and deionized water, and vacuum dry at 60°C for 12 hours to obtain carbon microspheres (CMSs). Then 0.86g KMnO 4 and 0.15g CMSs were added to 100mL deionized water and stirred continuously. After the mixture was stirred for 5min, 1mL of concentrated sulfuric acid was added to make the pH of the reaction system 1~2, stirred at room temperature for 30min, and then heated in an oil bath. Method Heat the mixture to 80°C and reflux for 1 hour; after the reaction system is cooled to room temperature, filter it with suction, wash the product several times with absolute ethanol and deionized water, and dry it at 60°C for 12 hours to obtain the product MnO 2 /CMSs composite material .
（2）超级电容器电极材料的制备 (2) Preparation of supercapacitor electrode materials
将二氧化锰/碳微球(MnO2/CMSs)复合材料5 mg、乙炔黑的混合固体粉末共0.88 mg（二者的质量百分比分别85%、15%）均匀分散于1ml Nafion溶液中，超声30min后，用移液枪量取5uL混合溶液滴在直径为5mm的玻碳电极上，自然晾干，即得测试电极。 5 mg of manganese dioxide/carbon microspheres (MnO 2 /CMSs) composite material and 0.88 mg of mixed solid powder of acetylene black (85% and 15% by mass, respectively) were uniformly dispersed in 1ml of Nafion solution, ultrasonically After 30 minutes, use a pipette gun to measure 5uL of the mixed solution and drop it on a glassy carbon electrode with a diameter of 5mm, and let it dry naturally to obtain the test electrode.
（3）电化学性能测试：以上述制备的电极材料为工作电极，以铂网为对电极、以Ag/AgCl电极为参比电极组成三电极体系进行电化学性能测试，电解液为1mol/L的Na2SO4溶液，电位窗口范围为-1.3-1.4V。采用origin 8.0软件作图。测试结果显示当电流密度为0.5A/g时，电极材料的比电容可以达到151 F/g，说明材料在宽的电位窗口下具有较高的比电容，具有做超级电容器电极材料的潜能。 (3) Electrochemical performance test: The electrode material prepared above was used as the working electrode, the platinum mesh was used as the counter electrode, and the Ag/AgCl electrode was used as the reference electrode to form a three-electrode system for electrochemical performance testing. The electrolyte was 1mol/L Na 2 SO 4 solution, the potential window range is -1.3-1.4V. Figures were drawn using Origin 8.0 software. The test results show that when the current density is 0.5A/g, the specific capacitance of the electrode material can reach 151 F/g, indicating that the material has a high specific capacitance under a wide potential window and has the potential to be used as a supercapacitor electrode material.
实施例2 Example 2
1）二氧化锰/碳微球(MnO2/CMSs)复合材料的制备 1) Preparation of manganese dioxide/carbon microspheres (MnO 2 /CMSs) composites
在装有100mL去离子水的烧杯中加入5.5 葡萄糖粉末，搅拌1h，然后将混合溶液置于高压反应釜中，于185℃下水热反应12h，待高压反应釜冷却到室温后，将产物抽滤、用无水乙醇和去离子水洗涤数次，60℃下真空干燥12h，即得碳微球(CMSs)。然后将0.9g KMnO4和0.15g CMSs加入到100mL去离子水中不断搅拌，混合物搅拌5min后加入1mL的浓硫酸使反应体系的pH为1~2，室温下搅拌50 min，随即采用油浴加热的方法将混合物加热到80℃，回流1h；待反应体系冷却到室温后，抽滤，产物用无水乙醇和去离子水洗涤数次，60℃下烘12h，即得产物MnO2/CMSs复合材料。 Add 5.5% glucose powder into a beaker filled with 100mL deionized water, stir for 1h, then place the mixed solution in an autoclave, and conduct a hydrothermal reaction at 185°C for 12h. After the autoclave is cooled to room temperature, filter the product with suction 1. Washing several times with absolute ethanol and deionized water, and drying in vacuum at 60° C. for 12 hours to obtain carbon microspheres (CMSs). Then 0.9g KMnO 4 and 0.15g CMSs were added to 100mL deionized water and stirred continuously. After the mixture was stirred for 5min, 1mL of concentrated sulfuric acid was added to make the pH of the reaction system 1~2, stirred at room temperature for 50min, and then heated in an oil bath. Method Heat the mixture to 80°C and reflux for 1 hour; after the reaction system is cooled to room temperature, filter it with suction, wash the product several times with absolute ethanol and deionized water, and dry it at 60°C for 12 hours to obtain the product MnO 2 /CMSs composite material .
（2）超级电容器电极材料的制备 (2) Preparation of supercapacitor electrode materials
将二氧化锰/碳微球(MnO2/CMSs)复合材料5.1 mg、乙炔黑的混合固体粉末共0.88 mg（二者的质量百分比分别85%、15%）均匀分散于1ml Nafion溶液中，超声30min后，用移液枪量取5uL混合溶液滴在直径为5mm的玻碳电极上，自然晾干，即得测试电极。 5.1 mg of manganese dioxide/carbon microspheres (MnO 2 /CMSs) composite material and 0.88 mg of mixed solid powder of acetylene black (85% and 15% by mass, respectively) were uniformly dispersed in 1ml Nafion solution, ultrasonically After 30 minutes, use a pipette gun to measure 5uL of the mixed solution and drop it on a glassy carbon electrode with a diameter of 5mm, and let it dry naturally to obtain the test electrode.
（3）电化学性能测试：以上述制备的电极材料为工作电极，以铂网为对电极、以Ag/AgCl电极为参比电极组成三电极体系进行电化学性能测试，电解液为1mol/L的Na2SO4溶液，电位窗口范围为-1.3-1.4V。测试结果显示：在循环伏安测试中，随着扫描速率的增大，CV曲线的形状基本保持不变，说明复合材料的倍容率较好，复合材料具有做超级电容器电极材料的潜能。 (3) Electrochemical performance test: The electrode material prepared above was used as the working electrode, the platinum mesh was used as the counter electrode, and the Ag/AgCl electrode was used as the reference electrode to form a three-electrode system for electrochemical performance testing. The electrolyte was 1mol/L Na 2 SO 4 solution, the potential window range is -1.3-1.4V. The test results show that in the cyclic voltammetry test, as the scan rate increases, the shape of the CV curve remains basically unchanged, indicating that the composite material has a good capacity ratio, and the composite material has the potential to be used as a supercapacitor electrode material.
实施例3 Example 3
1）二氧化锰/碳微球(MnO2/CMSs)复合材料的制备 1) Preparation of manganese dioxide/carbon microspheres (MnO 2 /CMSs) composites
在装有100mL去离子水的烧杯中加入6 g葡萄糖粉末，搅拌2h，然后将混合溶液置于高压反应釜中，于180℃下水热反应24h，待高压反应釜冷却到室温后，将产物抽滤、用无水乙醇和去离子水洗涤数次，60℃下真空干燥12h，即得碳微球(CMSs)。然后将0.8g KMnO4和0.16g CMSs加入到100mL去离子水中不断搅拌，混合物搅拌5min后加入1mL的浓硫酸使反应体系的pH为1~2，室温下搅拌30 min，随即采用油浴加热的方法将混合物加热到80℃，回流1h；待反应体系冷却到室温后，抽滤，产物用无水乙醇和去离子水洗涤数次，60℃下烘12h，即得产物MnO2/CMSs复合材料。 Add 6 g of glucose powder into a beaker with 100 mL of deionized water, stir for 2 h, then place the mixed solution in an autoclave, and conduct a hydrothermal reaction at 180 ° C for 24 h. After the autoclave is cooled to room temperature, the product is extracted Filter, wash several times with absolute ethanol and deionized water, and vacuum dry at 60°C for 12 hours to obtain carbon microspheres (CMSs). Then 0.8g KMnO 4 and 0.16g CMSs were added to 100mL deionized water and stirred continuously. After the mixture was stirred for 5min, 1mL of concentrated sulfuric acid was added to make the pH of the reaction system 1~2, stirred at room temperature for 30min, and then heated in an oil bath. Method Heat the mixture to 80°C and reflux for 1 hour; after the reaction system is cooled to room temperature, filter it with suction, wash the product several times with absolute ethanol and deionized water, and dry it at 60°C for 12 hours to obtain the product MnO 2 /CMSs composite material .
（2）超级电容器电极材料的制备 (2) Preparation of supercapacitor electrode materials
将二氧化锰/碳微球(MnO2/CMSs)复合材料5.1 mg、乙炔黑的混合固体粉末共0.88 mg（二者的质量百分比分别85%、15%）均匀分散于1ml Nafion溶液中，超声40min后，用移液枪量取5uL混合溶液滴在直径为5mm的玻碳电极上，自然晾干，即得测试电极。 5.1 mg of manganese dioxide/carbon microspheres (MnO 2 /CMSs) composite material and 0.88 mg of mixed solid powder of acetylene black (85% and 15% by mass, respectively) were uniformly dispersed in 1ml Nafion solution, ultrasonically After 40 minutes, use a pipette gun to measure 5uL of the mixed solution and drop it on a glassy carbon electrode with a diameter of 5mm, and let it dry naturally to obtain the test electrode.
（3）电化学性能测试：以上述制备的电极材料为工作电极，以铂网为对电极、以Ag/AgCl电极为参比电极组成三电极体系进行电化学性能测试，电解液为1mol/L的Na2SO4溶液，电位窗口范围为-1.3-1.4V。测试结果显示：当电流密度为0.5A/g时，电极材料的比电容可以达到155F/g。 (3) Electrochemical performance test: The electrode material prepared above was used as the working electrode, the platinum mesh was used as the counter electrode, and the Ag/AgCl electrode was used as the reference electrode to form a three-electrode system for electrochemical performance testing. The electrolyte was 1mol/L Na 2 SO 4 solution, the potential window range is -1.3-1.4V. The test results show that when the current density is 0.5A/g, the specific capacitance of the electrode material can reach 155F/g.
实施例4 Example 4
1）二氧化锰/碳微球(MnO2/CMSs)复合材料的制备 1) Preparation of manganese dioxide/carbon microspheres (MnO 2 /CMSs) composites
在装有150mL去离子水的烧杯中加入6 g葡萄糖粉末，搅拌3h，然后将混合溶液置于高压反应釜中，于180℃下水热反应16h，待高压反应釜冷却到室温后，将产物抽滤、用无水乙醇和去离子水洗涤数次，60℃下真空干燥24h，即得碳微球(CMSs)。然后将1.0g KMnO4和0.12g CMSs加入到100mL去离子水中不断搅拌，混合物搅拌5min后加入1mL的浓硫酸使反应体系的pH为1~2，室温下搅拌30 min，随即采用油浴加热的方法将混合物加热到80℃，回流1h；待反应体系冷却到室温后，抽滤，产物用无水乙醇和去离子水洗涤数次，60℃下烘12h，即得产物MnO2/CMSs复合材料。 Add 6 g of glucose powder into a beaker containing 150 mL of deionized water, stir for 3 h, then place the mixed solution in an autoclave, and conduct a hydrothermal reaction at 180 °C for 16 h, and after the autoclave is cooled to room temperature, pump the product Filter, wash several times with absolute ethanol and deionized water, and dry in vacuum at 60°C for 24 hours to obtain carbon microspheres (CMSs). Then 1.0g KMnO 4 and 0.12g CMSs were added to 100mL deionized water and stirred continuously. After the mixture was stirred for 5min, 1mL of concentrated sulfuric acid was added to make the pH of the reaction system 1~2, stirred at room temperature for 30min, and then heated in an oil bath. Method Heat the mixture to 80°C and reflux for 1 hour; after the reaction system is cooled to room temperature, filter it with suction, wash the product several times with absolute ethanol and deionized water, and dry it at 60°C for 12 hours to obtain the product MnO 2 /CMSs composite material .
（2）超级电容器电极材料的制备 (2) Preparation of supercapacitor electrode materials
将二氧化锰/碳微球(MnO2/CMSs)复合材料4.9mg、乙炔黑的混合固体粉末共0.88 mg（二者的质量百分比分别85%、15%）均匀分散于1ml Nafion溶液中，超声30min后，用移液枪量取5.2uL混合溶液滴在直径为5mm的玻碳电极上，自然晾干，即得测试电极。 4.9 mg of manganese dioxide/carbon microspheres (MnO 2 /CMSs) composite material and 0.88 mg of mixed solid powder of acetylene black (85% and 15% by mass respectively) were uniformly dispersed in 1ml of Nafion solution, ultrasonically After 30 minutes, use a pipette gun to measure 5.2uL of the mixed solution and drop it on a glassy carbon electrode with a diameter of 5mm, and let it dry naturally to obtain the test electrode.
（3）电化学性能测试：以上述制备的电极材料为工作电极，以铂网为对电极、以Ag/AgCl电极为参比电极组成三电极体系进行电化学性能测试，电解液为1mol/L的Na2SO4溶液，电位窗口范围为-1.3-1.2V。测试结果显示：当电流密度为0.5A/g时，电极材料的比电容可以达到165F/g。 (3) Electrochemical performance test: The electrode material prepared above was used as the working electrode, the platinum mesh was used as the counter electrode, and the Ag/AgCl electrode was used as the reference electrode to form a three-electrode system for electrochemical performance testing. The electrolyte was 1mol/L Na 2 SO 4 solution, the potential window range is -1.3-1.2V. The test results show that when the current density is 0.5A/g, the specific capacitance of the electrode material can reach 165F/g.
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