技术领域technical field
本发明涉及超级电容器电极材料技术领域，具体为一种碳纳米管纱线柔韧超级电容器复合电极材料制备方法。The invention relates to the technical field of supercapacitor electrode materials, in particular to a method for preparing a carbon nanotube yarn flexible supercapacitor composite electrode material.
背景技术Background technique
超级电容器具有功率密度高，充放电速率快，循环寿命达万次以上，工作温度范围宽等优点。在汽车、国防科技、航空航天及家用电器等消费型电子产品行业已得到了广泛应用，已成为世界各国研究的热点。在超级电容器的研究和开发中，如何提高超级电容器的电容含量、能量密度及功率密度是重要的研究课题，而高性能电极材料的开发是解决这一问题的关键技术。Supercapacitors have the advantages of high power density, fast charge and discharge rate, cycle life of more than 10,000 times, and wide operating temperature range. It has been widely used in consumer electronics industries such as automobiles, national defense technology, aerospace and household appliances, and has become a research hotspot in countries all over the world. In the research and development of supercapacitors, how to improve the capacitance content, energy density and power density of supercapacitors is an important research topic, and the development of high-performance electrode materials is the key technology to solve this problem.
目前，碳材料由于具有良好的电学性能、机械性能、抗腐蚀性、化学及高温稳定性等诸多优势，是超级电容器理想的电极材料之一。碳纳米管的管径一般为几纳米到几十纳米，长度在几微米至几十微米，其比表面积大、导电性好，是超级电容器的理想电极材料。但单纯使用碳纳米管作为超级电容器电极材料，其电容容量和能量密度有限，常需将碳纳米管与其他鹰电材料如过渡态金属氧化物复合制备成复合电极材料，来提高组装的超级电容器器件电容容量、能量密度和稳定性等。At present, carbon materials are one of the ideal electrode materials for supercapacitors due to their good electrical properties, mechanical properties, corrosion resistance, chemical and high temperature stability and many other advantages. The diameter of carbon nanotubes is generally several nanometers to tens of nanometers, and the length is several micrometers to tens of micrometers. It has a large specific surface area and good conductivity, and is an ideal electrode material for supercapacitors. However, the simple use of carbon nanotubes as supercapacitor electrode materials has limited capacitance and energy density. It is often necessary to prepare composite electrode materials by combining carbon nanotubes with other eagle electrical materials such as transition metal oxides to improve the assembled supercapacitor. Device capacitance, energy density and stability, etc.
柔性超级电容器可在日用电子产品、国防等领域具有重要的应用价值，制备性能优异的柔性超级电容器仍然是当前的研究中一项重要的挑战，柔性电极材料是制约柔性超级电容器的最为重要因素。一般采用自制撑的碳纸或者碳布作为柔性电极材料来制备柔性超级电容器，但这些柔性超级电容器常为二维或三维，并不能有效纺织在普通可穿戴生活用品中。碳纳米管纱线在形态上是一维线性，且机械性能、导电性能和化学稳定性能很好，是制备线性柔韧超级电容器理想的电极材料。遗憾的是，单纯使用碳纳米管纱线材料，由于其储存机理的限制，其储存的含量仍然不高。Flexible supercapacitors can have important application value in daily electronic products, national defense and other fields. The preparation of flexible supercapacitors with excellent performance is still an important challenge in current research. Flexible electrode materials are the most important factor restricting flexible supercapacitors. . Generally, self-supported carbon paper or carbon cloth is used as flexible electrode materials to prepare flexible supercapacitors, but these flexible supercapacitors are usually two-dimensional or three-dimensional, and cannot be effectively woven into ordinary wearable daily necessities. Carbon nanotube yarns are one-dimensional linear in shape, and have good mechanical properties, electrical conductivity, and chemical stability. They are ideal electrode materials for preparing linear and flexible supercapacitors. Unfortunately, purely using carbon nanotube yarn material, due to the limitation of its storage mechanism, its storage content is still not high.
发明内容Contents of the invention
本发明为克服常规线性柔韧超级电容器电容容量低，能量密度及功率密度不理想以及机械稳定性差等的问题，提供一种碳纳米管纱线基柔韧线性超级电容器复合电极材料的制备方法，具有应用前景广阔、机械性能优异和工艺绿色环保的特点。In order to overcome the problems of low capacitance capacity, unsatisfactory energy density and power density, and poor mechanical stability of conventional linear flexible supercapacitors, the present invention provides a method for preparing a carbon nanotube yarn-based flexible linear supercapacitor composite electrode material, which has application It has the characteristics of broad prospects, excellent mechanical properties and green and environmental protection technology.
本发明可以通过以下技术方案来实现：The present invention can be realized through the following technical solutions:
本发明公开了一种碳纳米管纱线柔韧超级电容器复合电极材料制备方法，包括以下步骤：The invention discloses a method for preparing a carbon nanotube yarn flexible supercapacitor composite electrode material, which comprises the following steps:
第一步、碳纳米管纱线的纺织法制备：过化学气相沉积制备的碳纳米管阵列，采用纺织设备控制转速为1000～5000rpm条件下，通过电机从阵列碳纳米管中抽拉出碳纳米管并旋转加捻后纺织得到直径为20～50μm碳纳米管纱线；The first step, the preparation of carbon nanotube yarn by textile method: the carbon nanotube array prepared by chemical vapor deposition is controlled by the textile equipment at a speed of 1000-5000rpm, and the carbon nanotube is pulled out from the carbon nanotube array by a motor. Tubes are rotated and twisted to obtain carbon nanotube yarns with a diameter of 20-50 μm;
第二步、电极材料粗产品的电镀法复合制备：采用三电极电镀法，以第一步所得的碳纳米管纱线作为阴极，Ag/AgCl为参比电极，金属铂为对比电极，在含有过渡态金属盐的电镀液中进行电镀得到电极材料的粗产品；The second step, the composite preparation of the electroplating method of the crude product of the electrode material: adopt the three-electrode electroplating method, use the carbon nanotube yarn obtained in the first step as the cathode, Ag/AgCl as the reference electrode, and metal platinum as the contrast electrode. Perform electroplating in the electroplating solution of the transition metal salt to obtain the crude product of the electrode material;
第三步、电极材料的加热提纯处理：在第二步电极材料粗产品的电镀法复合制备完后，将第二步所得的第二步电极材料粗产品在150～250℃条件下加热10～60min，即可得到最终的碳纳米管负载过渡态金属氧化物复合电极材料。The third step, the heating and purification treatment of the electrode material: After the electroplating method of the second step electrode material crude product is compounded and prepared, the second step electrode material crude product obtained in the second step is heated at 150-250°C for 10~ After 60 minutes, the final carbon nanotube-loaded transition-state metal oxide composite electrode material can be obtained.
优选地，第一步所述碳纳米管阵列为化学气相沉积制的多壁碳纳米管，所述碳纳米管阵列中单个碳纳米管长度为250～400μm，直径为10～30nm。Preferably, the carbon nanotube array in the first step is multi-walled carbon nanotubes produced by chemical vapor deposition, and the length of a single carbon nanotube in the carbon nanotube array is 250-400 μm, and the diameter is 10-30 nm.
优选地，第二步所述三电极电镀法为恒电位电镀，电镀的电压为～0.5～2.0V；电镀时间为5～500s；电镀液为含金属钠盐及过渡态金属盐的水溶液。Preferably, the three-electrode electroplating method in the second step is constant potential electroplating, the electroplating voltage is ~0.5-2.0V; the electroplating time is 5-500s; the electroplating solution is an aqueous solution containing metal sodium salt and transition metal salt.
优选地，所述电镀液所含的金属钠盐为NaNO3、Na2SO4、NaCl等中的一种或多种。Preferably, the metal sodium salt contained in the electroplating solution is one or more of NaNO3 , Na2 SO4 , NaCl and the like.
优选地，所述电镀液中所含过渡态金属盐为Co(NO3)2、CoSO4、Co(CH3COO)2及他们水合物中的一种或多种，此时附着在碳纳米管负载过渡态金属氧化物复合电极材料的负载过渡态金属氧化物为Co3O4纳米颗粒。Preferably, the transition state metal salt contained in the electroplating solution is one or more of Co(NO3 )2 , CoSO4 , Co(CH3 COO)2 and their hydrates. The transition-state metal oxide loaded by the tube-loaded transition-state metal oxide composite electrode material is Co3 O4 nanoparticles.
优选地，所述电镀液中所含的过渡态金属盐为Ni(NO3)2、NiSO4、Ni(CH3COO)2及他们的水合物中的一种或多种，此时附着在碳纳米管负载过渡态金属氧化物复合电极材料的负载过渡态金属氧化物为NiO纳米颗粒。Preferably, the transition state metal salt contained in the electroplating solution is one or more of Ni(NO3 )2 , NiSO4 , Ni(CH3 COO)2 and their hydrates. The carbon nanotube-loaded transition-state metal oxide composite electrode material supports transition-state metal oxides as NiO nanoparticles.
优选地，所述电镀液中所含过渡态金属盐为Mn(NO3)2、Mn(SO4)2、Mn(CH3COO)2及他们的水合物中的一种或多种，此时附着在碳纳米管负载过渡态金属氧化物复合电极材料的负载过渡态金属氧化物为MnO2纳米颗粒。Preferably, the transition state metal salt contained in the electroplating solution is one or more of Mn(NO3)2 , Mn(SO4 )2 , Mn(CH3 COO)2 and their hydrates. The transition-state metal oxide attached to the carbon nanotube-supported transition-state metal oxide composite electrode material isMnO2 nanoparticles.
优选地，所述金属钠盐的浓度为0.05～0.5mol/L，过渡态金属盐的浓度为0.01～1.0mol/L。所述水溶液的溶剂为二次蒸馏水。Preferably, the concentration of the metal sodium salt is 0.05-0.5 mol/L, and the concentration of the transition state metal salt is 0.01-1.0 mol/L. The solvent of the aqueous solution is twice distilled water.
本发明一种碳纳米管纱线柔韧超级电容器复合电极材料制备方法，具有如下的有益效果：A method for preparing a carbon nanotube yarn flexible supercapacitor composite electrode material according to the present invention has the following beneficial effects:
第一、应用前景广阔，本发明所制备的碳纳米管纱线基超级电容器复合电极材料，是先通过简单机械纺纱纺织碳纳米管纱线，再通过一步电镀法负载过渡态金属氧化物。不需要复杂的加工设备，制备过程简单，具有很好的应用价值。First, the application prospect is broad. The carbon nanotube yarn-based supercapacitor composite electrode material prepared by the present invention is to weave the carbon nanotube yarn through simple mechanical spinning, and then load the transition state metal oxide through a one-step electroplating method. No complicated processing equipment is needed, the preparation process is simple, and the method has good application value.
第二、力学性能稳定，本发明所制备的碳纳米管纱线基复合材料可作为柔韧线性超级电容器电极材料，具有机械稳定性好、柔韧性优异及可随意弯曲等性能，该类超级电容器可通过纺织方法纺织到日常生活穿戴用品中。Second, the mechanical properties are stable. The carbon nanotube yarn-based composite material prepared by the present invention can be used as a flexible linear supercapacitor electrode material. It has good mechanical stability, excellent flexibility and can be bent at will. This type of supercapacitor can be It is woven into daily wear articles by weaving method.
第三、工艺绿色环保，本发明所采用一步恒电位电镀法在碳纳米管纱线负载过渡态金属氧化物，所用电镀液成分简单，对环境友好。电镀工艺简单可控，不含腐蚀性气体，电镀常温进行，电镀过程无蒸汽排放。Third, the process is green and environmentally friendly. The carbon nanotube yarn is loaded with transition state metal oxides by the one-step constant potential electroplating method adopted in the present invention. The electroplating solution used has simple components and is environmentally friendly. The electroplating process is simple and controllable, does not contain corrosive gases, is carried out at room temperature, and has no steam emission during the electroplating process.
具体实施方式detailed description
为了使本技术领域的人员更好地理解本发明的技术方案，下面结合实施例对本发明产品作进一步详细的说明。In order to enable those skilled in the art to better understand the technical solution of the present invention, the product of the present invention will be further described in detail below in conjunction with examples.
实施例1Example 1
本发明所述一种碳纳米管纱线柔韧超级电容器复合电极材料制备方法，具体按以下步骤进行：通过自制纺纱设备在转速为2000rpm条件下纺织制备直径约为30μm的碳纳米管纱线；采用一步恒电位电镀法，以该碳纳米管纱线作为阴极，Ag/AgCl为参比电极，金属铂为对比电极，在含有1.0mol/LCo(NO3)2，0.1mol/L的NaNO3的蒸馏水电镀液中电镀，在-1.0V恒电压条件下电镀5min，电镀完成后将该碳纳米管复合纱线在200oC条件下在烘箱中加热10min，即得该碳纳米管纱线负载Co3O4复合电极材料。A preparation method of a carbon nanotube yarn flexible supercapacitor composite electrode material according to the present invention is specifically carried out as follows: a carbon nanotube yarn with a diameter of about 30 μm is spun and prepared by self-made spinning equipment at a speed of 2000 rpm; Using the one- step constant potential electroplating method, the carbon nanotube yarn is used as the cathode,Ag /AgCl is used as the reference electrode, and metal platinum is used as the reference electrode. electroplating in the distilled water electroplating solution, and electroplating at -1.0V constant voltage for 5 minutes, after the electroplating, the carbon nanotube composite yarn was heated in an oven at 200o C for 10 minutes to obtain the carbon nanotube yarn loaded Co3 O4 composite electrode material.
实施例2Example 2
本发明所述一种碳纳米管纱线柔韧超级电容器复合电极材料制备方法，具体按以下步骤进行：通过自制纺纱设备在转速为2000rpm条件下纺织制备直径约为31μm的碳纳米管纱线；采用一步恒电位电镀法以该碳纳米管纱线作为阴极，Ag/AgCl为参比电极，金属铂为对比电极，在含有1.0mol/LNi(NO3)2，0.1mol/L的NaNO3的蒸馏水电镀液中电镀，在-1.0V恒电压条件下电镀6min，电镀完成后将该碳纳米管复合纱线在170oC条件下在烘箱中加热30min，即得该碳纳米管纱线负载NiO复合电极材料。A preparation method of a carbon nanotube yarn flexible supercapacitor composite electrode material according to the present invention is specifically carried out according to the following steps: the carbon nanotube yarn with a diameter of about 31 μm is spun and prepared by self-made spinning equipment at a speed of 2000 rpm; Using the one- step constant potential electroplating method, the carbon nanotube yarn is used as the cathode,Ag /AgCl is used as the reference electrode, and metal platinum is used as the reference electrode. Electroplating in distilled water electroplating solution, electroplating under the condition of -1.0V constant voltage for 6min, after the electroplating is completed, the carbon nanotube composite yarn is heated in an oven at 170o C for 30min to obtain the carbon nanotube yarn loaded with NiO Composite electrode material.
实施例3Example 3
本发明所述一种碳纳米管纱线柔韧超级电容器复合电极材料制备方法，具体按以下步骤进行：通过自制纺纱设备在转速为5000rpm条件下纺织制备直径约为36μm的碳纳米管纱线；采用一步恒电位电镀法，以该碳纳米管纱线作为阴极，Ag/AgCl为参比电极，金属铂为对比电极，在含有0.2mol/LMnSO4，0.1mol/L的Na2SO4的蒸馏水电镀液中电镀，在-1.5V恒电压条件下电镀1min，电镀完成后将该碳纳米管复合纱线在170oC条件下在烘箱中加热30min，即得该碳纳米管纱线负载MnO2复合电极材料。A method for preparing a carbon nanotube yarn flexible supercapacitor composite electrode material according to the present invention is specifically carried out according to the following steps: a carbon nanotube yarn with a diameter of about 36 μm is spun and prepared by self-made spinning equipment at a speed of 5000 rpm; Using a one-step constant potential electroplating method, using the carbon nanotube yarn as the cathode, Ag/AgCl as the reference electrode, and metal platinum as the reference electrode, in distilled water containing 0.2mol/LMnSO4 and 0.1mol/L Na2 SO4 Electroplating in the electroplating solution, electroplating at a constant voltage of -1.5V for 1 min, and heating the carbon nanotube composite yarn in an oven at 170o C for 30 min after electroplating, to obtain the carbon nanotube yarn loaded with MnO2 Composite electrode material.
实施例4Example 4
本发明所述一种碳纳米管纱线柔韧超级电容器复合电极材料制备方法，具体按以下步骤进行：通过自制纺纱设备在转速为3000rpm条件下纺织制备直径约为20μm的碳纳米管纱线；采用一步恒电位电镀法，以该碳纳米管纱线作为阴极，Ag/AgCl为参比电极，金属铂为对比电极，在含有0.2mol/LCo(CH3COO)2，0.5mol/L的NaCl的蒸馏水电镀液中电镀，在-0.8V恒电压条件下电镀3min，电镀完成后将该碳纳米管复合纱线在烘箱在200oC条件下在烘箱中加热2min，即得该碳纳米管纱线负载Co3O4复合电极材料。A preparation method of a carbon nanotube yarn flexible supercapacitor composite electrode material according to the present invention is specifically carried out as follows: a carbon nanotube yarn with a diameter of about 20 μm is spun and prepared by self-made spinning equipment at a speed of 3000 rpm; Using a one- step constant potential electroplating method, the carbon nanotube yarn is used as the cathode,Ag /AgCl is used as the reference electrode, and metal platinum is used as the reference electrode. Electroplating in the distilled water electroplating solution, electroplating under the condition of -0.8V constant voltage for 3min, after the electroplating is completed, the carbon nanotube composite yarn is heated in an oven at 200o C for 2min to obtain the carbon nanotube yarn Line- loadedCo3O4 composite electrode materials.
实施例5Example 5
本发明所述一种碳纳米管纱线柔韧超级电容器复合电极材料制备方法，具体按以下步骤进行：通过自制纺纱设备在转速为2000rpm条件下纺织制备直径约为25μm的碳纳米管纱线；采用一步恒电位电镀法，以该碳纳米管纱线作为阴极，Ag/AgCl为参比电极，金属铂为对比电极，在含有0.3mol/LNiSO4，0.2mol/L的NaCl的蒸馏水电镀液中电镀，在-1.0V恒电压条件下电镀2min，电镀完成后将该碳纳米管复合纱线物在150oC条件下在马弗炉中加热60min，即得该碳纳米管纱线负载NiO复合电极材料。A preparation method of a carbon nanotube yarn flexible supercapacitor composite electrode material according to the present invention is specifically carried out as follows: a carbon nanotube yarn with a diameter of about 25 μm is spun and prepared by self-made spinning equipment at a speed of 2000 rpm; Using a one-step constant potential electroplating method, using the carbon nanotube yarn as the cathode, Ag/AgCl as the reference electrode, and metal platinum as the contrast electrode, in a distilled water electroplating solution containing 0.3mol/LNiSO4 and 0.2mol/L NaCl Electroplating, electroplating under the condition of -1.0V constant voltage for 2min, after the electroplating is completed, the carbon nanotube composite yarn is heated in a muffle furnace at 150o C for 60min to obtain the carbon nanotube yarn loaded NiO composite electrode material.
为了验证本发明制备所得复合电极材料的性能，分别对实施例1～5所得的复合电极材料进行电性能测试和机械性能测试，具体结果如下：In order to verify the performance of the composite electrode material prepared by the present invention, the composite electrode materials obtained in Examples 1 to 5 were tested for electrical properties and mechanical properties, and the specific results were as follows:
1)机械性能测试方法为：将该电极材料组装成对称超级电容器后在反复180o弯曲100次后的电容量保持率。具体数据如表1所示:1) The mechanical performance test method is: after the electrode material is assembled into a symmetrical supercapacitor, the capacitance retention rate after repeated 180o bending 100 times. The specific data are shown in Table 1:
表1电极材料组装超级电容器在反复180o弯曲100次的电容量保持率Table 1 Capacitance retention rate of supercapacitors assembled with electrode materials after repeated 180o bending 100 times
2)电学性能测试方法为：将预先制备好的碳纳米管纱线复合材料作为柔韧电极，以PVA-H2SO4凝胶（5gPVA溶解于50mL摩尔浓度为1molL-1H2SO4中）作为电解质及隔膜，采用CHI660E电化学工作站，根据0.1Vs-1扫描速率下所得循环曲线，计算比电容量和能量密度。具体数据如表2所示：2) The electrical performance test method is: use the pre-prepared carbon nanotube yarn composite material as a flexible electrode, use PVA-H2SO4 gel (5gPVA dissolved in 50mL molar concentration of 1molL-1H2SO4) as the electrolyte and diaphragm, and use CHI660E The electrochemical workstation calculates the specific capacitance and energy density according to the cycle curve obtained at a scan rate of 0.1Vs-1. The specific data are shown in Table 2:
表2电极材料组装超级电容器的电容量和能量密度数据表Table 2 Capacitance and energy density data table of electrode material assembled supercapacitor
以上所述，仅为本发明的较佳实施例而已，并非对本发明作任何形式上的限制；凡本行业的普通技术人员均可按说明书所示和以上所述而顺畅地实施本发明；但是，凡熟悉本专业的技术人员在不脱离本发明技术方案范围内，可利用以上所揭示的技术内容而作出的些许更动、修饰与演变的等同变化，均为本发明的等效实施例；同时，凡依据本发明的实质技术对以上实施例所作的任何等同变化的更动、修饰与演变等，均仍属于本发明的技术方案的保护范围之内。The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any form; all those skilled in the art can smoothly implement the present invention as shown in the description and described above; but All the equivalent changes, modifications, and evolutions that can be made by those skilled in the art without departing from the scope of the technical solution of the present invention by utilizing the technical content disclosed above are all equivalent embodiments of the present invention; At the same time, any modification, modification and evolution of any equivalent changes made to the above embodiments based on the substantive technology of the present invention still fall within the protection scope of the technical solution of the present invention.
| Application Number | Priority Date | Filing Date | Title |
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| CN201510687692.6ACN105244188A (en) | 2015-10-22 | 2015-10-22 | A preparation method of carbon nanotube yarn flexible supercapacitor composite electrode material |
| Application Number | Priority Date | Filing Date | Title |
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| CN201510687692.6ACN105244188A (en) | 2015-10-22 | 2015-10-22 | A preparation method of carbon nanotube yarn flexible supercapacitor composite electrode material |
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| CN105244188Atrue CN105244188A (en) | 2016-01-13 |
| Application Number | Title | Priority Date | Filing Date |
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| CN201510687692.6APendingCN105244188A (en) | 2015-10-22 | 2015-10-22 | A preparation method of carbon nanotube yarn flexible supercapacitor composite electrode material |
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