CN106952690A - A kind of preparation method of the non-metallic electrode doped with manganese dioxide - Google Patents

Abstract

The present invention relates to a kind of process of preparing of non-metal electrode, and in particular to a kind of process of preparing of the non-metal electrode of dopping manganese dioxide.The present invention by a certain amount of concentration be 2% acetic acid, concentration is put into beaker for 3% lactic acid and chitosan, it is placed in heating stirring in the water-bath beaker of magnetic stirring apparatus, the scattered MWNCT aqueous dispersions of measured amounts are poured into beaker fully after dissolving, continue heating stirring to being sufficiently mixed, this mixed solution is placed in supersonic cell separating apparatus and disperseed, so that manganese dioxide carries out sufficiently mixing concussion absorption with multi-walled carbon nano-tubes, then uniformly it is cast in glass mold, it is placed in supersonic wave cleaning machine and shakes deaeration, non-metal electrode is obtained by drying box drying process again.The multi-walled carbon nano-tubes of the present invention has unique structure and surface nature, and such as high mechanical strength, specific surface area are big, hollow layer structure, superior chemically and thermally stability.

Description

Translated fromChinese

一种掺杂二氧化锰的非金属电极的制备方法A kind of preparation method of the non-metallic electrode doped with manganese dioxide

技术领域technical field

本发明涉及一种非金属电极的制备工艺方法，具体涉及一种掺杂二氧化锰的非金属电极的制备工艺方法。The invention relates to a preparation process method of a non-metal electrode, in particular to a preparation process method of a manganese dioxide-doped non-metal electrode.

背景技术Background technique

碳纳米管具有优异的电学、力学、热学和化学特性，在很多方面有着潜在的应用前景。随着碳纳米管管壁中石墨环排列的螺旋性和管径变化，碳纳米管会呈现金属性或半导体性。金属性碳纳米管，尤其是多壁碳纳米管，具有很高的电流承载能力、良好的导电、传热等性能，就目前而言，多壁碳纳米管的应用主要是与一些复合材料的合成以及制备，绝大多数属于医学、材料化学领域，还有一些用做吸附剂、传感器等，其中不乏有放射性和毒素等，一直都是学术界和工业界的热点。然而，在机械行业，一些柔性系统无法应用上述方法制备的电极，上述方法制备的电极绝大多数都是刚性的电极，无法参与到一些特定的柔性系统中。Carbon nanotubes have excellent electrical, mechanical, thermal and chemical properties, and have potential applications in many aspects. With the helicity of the arrangement of graphite rings in the carbon nanotube wall and the change of the tube diameter, the carbon nanotubes will exhibit metallic or semiconducting properties. Metallic carbon nanotubes, especially multi-walled carbon nanotubes, have high current carrying capacity, good electrical conductivity, heat transfer and other properties. For now, the application of multi-walled carbon nanotubes is mainly in combination with some composite materials. Synthesis and preparation, most of which belong to the fields of medicine and material chemistry, and some are used as adsorbents, sensors, etc., many of which are radioactive and toxins, have always been a hot spot in academia and industry. However, in the mechanical industry, some flexible systems cannot apply the electrodes prepared by the above method. Most of the electrodes prepared by the above method are rigid electrodes and cannot participate in some specific flexible systems.

本发明通过超声震荡工艺使二氧化锰颗粒吸附在多壁碳纳米管上，由于二氧化锰本身是优良的储能材料，有利于电子在电极膜中的储存，能提高电极膜的比电容，提高电极膜容纳电子的能力，为电驱动器提供较高的电场，提高电致动膜中离子的迁移速率以及迁移量，这也有利于电子和电致动膜中的离子交换，提高电驱动器的应变和相应速率，随着电致动膜中离子迁移量的再粘结面对的积累量的增加，电驱动器的输出力也随之增加，进而提高电驱动器的输出力密度。In the present invention, the manganese dioxide particles are adsorbed on the multi-walled carbon nanotubes through the ultrasonic oscillation process. Since the manganese dioxide itself is an excellent energy storage material, it is beneficial to the storage of electrons in the electrode film and can increase the specific capacitance of the electrode film. Improve the ability of the electrode film to accommodate electrons, provide a higher electric field for the electric drive, increase the migration rate and migration amount of ions in the electric drive film, which is also conducive to the ion exchange between electrons and the electric drive film, and improve the electric drive. The strain and the corresponding rate, as the accumulation of the rebonded surface of the ion mobility in the electro-actuated membrane increases, the output force of the electric actuator also increases, thereby increasing the output force density of the electric actuator.

本发明的制备方法得到的电极膜具有很高的韧性及强度，制作方法及操作过程简单，实验成本低廉，制备全过程绿色环保、无毒、无污染，对实验人员没有伤害。在仿生学、柔性机械等领域可以代替传统的复杂的机械结构，轻巧、灵便的特点使其可以简化机械系统，避免复杂的安装过程，具有十分重要的应用价值。The electrode film obtained by the preparation method of the present invention has high toughness and strength, the preparation method and operation process are simple, the experiment cost is low, and the whole preparation process is green, environmentally friendly, non-toxic and pollution-free, and does not harm experimenters. In the fields of bionics, flexible machinery, etc., it can replace traditional complex mechanical structures. Its light and handy features make it possible to simplify the mechanical system and avoid complicated installation processes, which has very important application value.

发明内容Contents of the invention

本发明的目的是提供一种掺杂二氧化锰的非金属电极膜的制备方法。The purpose of the present invention is to provide a method for preparing a non-metallic electrode film doped with manganese dioxide.

上述的目的可以通过以下技术方案实现：The above-mentioned purpose can be achieved through the following technical solutions:

包括如下步骤；Including the following steps;

将一定量的浓度为2％的醋酸、浓度为3％的乳酸以及壳聚糖放入烧杯中，置于磁力搅拌器的水浴烧杯中加热搅拌，充分溶解后量取一定量分散好的MWNCT水分散液倒入烧杯中，继续加热搅拌至充分混合，将此混合溶液置于超声波细胞分散仪中进行分散，使得二氧化锰与多壁碳纳米管进行充分的混合震荡吸附，然后均匀流延到玻璃模具中，放在超声波清洗机中震荡脱泡，再通过干燥箱干燥处理得到非金属电极：Put a certain amount of acetic acid with a concentration of 2%, lactic acid with a concentration of 3%, and chitosan into a beaker, heat and stir in a water bath beaker with a magnetic stirrer, and measure a certain amount of dispersed MWNCT water after fully dissolving Pour the dispersion liquid into a beaker, continue to heat and stir until fully mixed, and place the mixed solution in an ultrasonic cell disperser for dispersion, so that the manganese dioxide and multi-walled carbon nanotubes are fully mixed and oscillated for adsorption, and then evenly cast to In the glass mold, put it in an ultrasonic cleaning machine to shake and defoam, and then dry it in a drying oven to obtain a non-metallic electrode:

(1)多壁碳纳米管的二次分散：将多壁碳纳米管水分散液置于隔音箱升降台中间，选择Φ12型号的变幅杆，调节控制升降台升降的按钮，使变幅杆末端深入液面12mm-20mm,开启电源，设置工作时间为5min，超声时间为2s，间隔时间为1s，保护温度为60℃，关闭隔音箱，开启On按钮开始分散；共重复3-5次，每次分散中间将MNCT散热10min,得到均匀的多壁碳纳米管二次分散液；(1) Secondary dispersion of multi-walled carbon nanotubes: place the aqueous dispersion of multi-walled carbon nanotubes in the middle of the lifting platform of the soundproof box, select the horn of Φ12 type, and adjust the button for controlling the lifting of the lifting platform so that the horn The end goes deep into the liquid surface 12mm-20mm, turn on the power, set the working time to 5min, the ultrasonic time to 2s, the interval time to 1s, the protection temperature to 60°C, turn off the soundproof box, turn on the On button to start dispersing; repeat 3-5 times in total, Heat the MNCT for 10 minutes in the middle of each dispersion to obtain a uniform secondary dispersion of multi-walled carbon nanotubes;

(2)壳聚糖溶液的制备：取5ml浓度为2％的醋酸、5ml浓度为3％的乳酸以及0.1g壳聚糖放在烧杯中，水浴加热搅拌，加热温度为50-70℃，直至充分溶解；(2) Preparation of chitosan solution: get 5ml concentration of 2% acetic acid, 5ml concentration of 3% lactic acid and 0.1g chitosan in a beaker, heat and stir in a water bath, and the heating temperature is 50-70°C until fully dissolved;

(3)量取20ml质量分数为10％的多壁碳纳米管水分散液置于200ml的烧杯中，加入80ml蒸馏水将其质量分数稀释成2％。称取0.2g二氧化锰倒入上述烧杯中并将其置于超声波细胞分散仪中，与步骤(1)相同进行分散，制备出二氧化锰/多壁碳纳米管比例为0.1的混合溶液；(3) Measure 20 ml of 10% multi-walled carbon nanotube aqueous dispersion into a 200 ml beaker, add 80 ml of distilled water to dilute the mass fraction to 2%. Weigh 0.2g manganese dioxide and pour it into the above-mentioned beaker and place it in an ultrasonic cell disperser, disperse the same as step (1), and prepare a mixed solution whose ratio of manganese dioxide/multi-walled carbon nanotubes is 0.1;

(4)取10ml步骤(3)获得的溶液加入步骤(2)获得的壳聚糖溶液中，水浴加热搅拌，温度为50-70℃，充分混合后均匀流延到玻璃模具中，放入超声波清洗机中震荡脱泡，然后放入干燥箱中干燥4-6h，其中干燥温度为80℃，真空度为零。(4) Take 10ml of the solution obtained in step (3) and add it to the chitosan solution obtained in step (2), heat and stir in a water bath at a temperature of 50-70°C, mix well and cast it into a glass mold evenly, and put it into an ultrasonic wave Shake and defoam in a washing machine, and then put it into a drying oven for 4-6 hours to dry, wherein the drying temperature is 80°C and the vacuum degree is zero.

通过以上实验方案可以看出，本发明主要拥有以下优点：As can be seen from the above experimental scheme, the present invention mainly possesses the following advantages:

1.本发明中的壳聚糖(chitosan)在自然界广泛存在，在特定的条件下，壳聚糖能发生水解、烷基化、酰基化、羧甲基化、磺化、硝化、卤化、氧化、还原、缩合和络合等化学反应，可生成各种具有不同性能的壳聚糖衍生物。壳聚糖分子中带有游离的氨基，在酸性溶液中易成盐，呈阳离子性质。壳聚糖随其分子中含氨基数量的增多，其氨基特性越显著，具有许多生物学特性及加工特性。这种天然高分子的生物官能性和相容性、血液相容性、安全性、微生物降解性等优良性能被各行各业广泛关注，成为了医药、食品、化工、化妆品、水处理、金属提取及回收、生化和生物医学工程等诸多领域的宠儿，是目前各大领域的研究热点之一。1. Chitosan (chitosan) in the present invention exists widely in nature, and under specific conditions, chitosan can undergo hydrolysis, alkylation, acylation, carboxymethylation, sulfonation, nitration, halogenation, oxidation , Reduction, condensation and complexation and other chemical reactions can generate various chitosan derivatives with different properties. There are free amino groups in chitosan molecules, which are easy to form salts in acidic solutions and are cationic in nature. With the increase of the number of amino groups in the chitosan molecule, its amino characteristics are more significant, and it has many biological and processing characteristics. The excellent properties of this natural polymer, such as biofunctionality, compatibility, blood compatibility, safety, and microbial degradability, have attracted wide attention from all walks of life, and it has become an important product in medicine, food, chemical industry, cosmetics, water treatment, and metal extraction. It is the darling of many fields such as recycling, biochemistry and biomedical engineering, and it is one of the research hotspots in various fields at present.

2.本发明的多壁碳纳米管具有独特的结构和表面性质,如机械强度高、比表面积大、中空层状结构、优越的化学和热学稳定性等。而且多壁碳纳米管不仅在微电子元器件、场发射材料、催化等领域应用潜能广阔,而且在纳米科学与技术领域也是很有前途的吸附材料。2. The multi-walled carbon nanotubes of the present invention have unique structure and surface properties, such as high mechanical strength, large specific surface area, hollow layered structure, superior chemical and thermal stability, and the like. Moreover, multi-walled carbon nanotubes not only have broad application potential in the fields of microelectronic components, field emission materials, and catalysis, but also are promising adsorption materials in the field of nanoscience and technology.

3.本发明的二氧化锰在自然界广泛存在，是优良的储能材料。作为一种半导体，具有较大的比表面积以及较高的电化学性能。其制备原料广泛，价格低廉，对环境污染小等特点，受到各行各业的青睐。3. The manganese dioxide of the present invention widely exists in nature and is an excellent energy storage material. As a semiconductor, it has a large specific surface area and high electrochemical performance. It has a wide range of raw materials, low price, and little environmental pollution, and is favored by all walks of life.

4.本发明是一种掺杂多壁碳纳米管和二氧化锰的非金属电极的制备工艺方法，实验稳定性好，反应过程缓慢、温和，不发生排斥、剧烈的化学反应。4. The present invention is a preparation process of a non-metallic electrode doped with multi-walled carbon nanotubes and manganese dioxide, which has good experimental stability, slow and mild reaction process, and no repelling and violent chemical reactions.

5.本发明具体涉及壳聚糖溶液的制备、多壁碳纳米管和二氧化锰溶液的二次分散，制备全过程绿色环保、无毒、无污染，对实验人员无危害。5. The present invention specifically relates to the preparation of chitosan solution, the secondary dispersion of multi-walled carbon nanotubes and manganese dioxide solution. The whole preparation process is green, non-toxic, non-polluting and harmless to experimenters.

6.配方易于控制，制备的操作比较简单，实验用料易于获得，价格低廉，具有较好的经济效益。获得的电极膜性能优异，应用领域更为广泛。6. The formula is easy to control, the preparation operation is relatively simple, the experimental materials are easy to obtain, the price is low, and it has good economic benefits. The obtained electrode film has excellent performance and wider application fields.

具体实施方式detailed description

实施例1：Example 1:

一种掺杂二氧化锰的非金属电极的制备方法，该方法包括如下步骤：A preparation method of a non-metallic electrode doped with manganese dioxide, the method comprising the steps of:

将一定量的浓度为2％的醋酸、浓度为3％的乳酸以及壳聚糖放入烧杯中，置于磁力搅拌器的水浴烧杯中加热搅拌，充分溶解后量取一定量分散好的MNCT水分散液倒入烧杯中，继续加热搅拌至充分混合，将此混合溶液置于超声波细胞分散仪中进行分散，使得二氧化锰与多壁碳纳米管进行充分的混合震荡吸附，然后均匀流延到玻璃模具中，放在超声波清洗机中震荡脱泡，再通过干燥箱干燥处理得到性能较优的电极膜。Put a certain amount of acetic acid with a concentration of 2%, lactic acid with a concentration of 3%, and chitosan into a beaker, heat and stir in a water bath beaker with a magnetic stirrer, and measure a certain amount of dispersed MNCT water after fully dissolving. Pour the dispersion liquid into a beaker, continue to heat and stir until fully mixed, and place the mixed solution in an ultrasonic cell disperser for dispersion, so that the manganese dioxide and multi-walled carbon nanotubes are fully mixed and oscillated for adsorption, and then evenly cast to In the glass mold, put it in an ultrasonic cleaning machine to shake and defoam, and then dry it in a drying oven to obtain an electrode film with better performance.

(1)多壁碳纳米管的二次分散：将多壁碳纳米管水分散液置于隔音箱升降台中间，选择Φ12型号的变幅杆，调节控制升降台升降的按钮，使变幅杆末端深入液面约20mm,开启电源，设置工作时间为5min，超声时间为2s，间隔时间为1s，保护温度为60℃，关闭隔音箱，开启On按钮开始分散；共重复5，每次分散中间将MNCT散热10min,得到均匀的多壁碳纳米管二次分散液。(1) Secondary dispersion of multi-walled carbon nanotubes: place the aqueous dispersion of multi-walled carbon nanotubes in the middle of the lifting platform of the soundproof box, select the horn of Φ12 type, and adjust the button for controlling the lifting of the lifting platform so that the horn The end is about 20mm deep into the liquid surface, turn on the power, set the working time to 5min, the ultrasonic time to 2s, the interval time to 1s, and the protection temperature to 60°C, turn off the soundproof box, and turn on the On button to start dispersing; repeat 5 times in total, in the middle of each dispersing The MNCT was cooled for 10 minutes to obtain a uniform secondary dispersion of multi-walled carbon nanotubes.

(2)壳聚糖溶液的制备：取5ml浓度为2％的醋酸、5ml浓度为3％的乳酸以及0.1g壳聚糖放在烧杯中，水浴加热搅拌，加热温度为60℃，直至充分溶解。(2) Preparation of chitosan solution: 5ml concentration of 2% acetic acid, 5ml concentration of 3% lactic acid and 0.1g chitosan are placed in a beaker, heated and stirred in a water bath, and the heating temperature is 60°C until fully dissolved .

(3)量取20ml质量分数为10％的多壁碳纳米管水分散液置于200ml的烧杯中，加入80ml蒸馏水将其质量分数稀释成2％。称取0.2g二氧化锰倒入上述烧杯中并将其置于超声波细胞分散仪中，类似步骤(1)进行分散，制备出二氧化锰/多壁碳纳米管比例为0.1的混合溶液。(3) Measure 20 ml of 10% multi-walled carbon nanotube aqueous dispersion into a 200 ml beaker, add 80 ml of distilled water to dilute the mass fraction to 2%. Weigh 0.2 g of manganese dioxide and pour it into the above beaker and place it in an ultrasonic cell disperser, and disperse similarly to step (1) to prepare a mixed solution with a ratio of manganese dioxide/multi-walled carbon nanotubes of 0.1.

(4)取10ml步骤(3)获得的溶液加入步骤(2)获得的壳聚糖溶液中，水浴加热搅拌，温度为60℃，充分混合后均匀流延到玻璃模具中，放入超声波清洗机中震荡脱泡，然后放入干燥箱中干燥5h，其中干燥温度为80℃，真空度为零。(4) Take 10ml of the solution obtained in step (3) and add it to the chitosan solution obtained in step (2), heat and stir in a water bath at a temperature of 60°C, mix well and evenly cast it into a glass mold, put it into an ultrasonic cleaner Shake in medium to defoam, and then put it in a drying oven to dry for 5 hours, where the drying temperature is 80°C and the vacuum degree is zero.

Claims (1)

Translated fromChinese

1.一种掺杂二氧化锰的非金属电极的制备方法，包括如下步骤；1. A preparation method of a non-metallic electrode doped with manganese dioxide, comprising the following steps;将一定量的浓度为2％的醋酸、浓度为3％的乳酸以及壳聚糖放入烧杯中，置于磁力搅拌器的水浴烧杯中加热搅拌，充分溶解后量取一定量分散好的MWNCT水分散液倒入烧杯中，继续加热搅拌至充分混合，将此混合溶液置于超声波细胞分散仪中进行分散，使得二氧化锰与多壁碳纳米管进行充分的混合震荡吸附，然后均匀流延到玻璃模具中，放在超声波清洗机中震荡脱泡，再通过干燥箱干燥处理得到非金属电极，其特征在于：Put a certain amount of acetic acid with a concentration of 2%, lactic acid with a concentration of 3%, and chitosan into a beaker, heat and stir in a water bath beaker with a magnetic stirrer, and measure a certain amount of dispersed MWNCT water after fully dissolving Pour the dispersion liquid into a beaker, continue to heat and stir until fully mixed, and place the mixed solution in an ultrasonic cell disperser for dispersion, so that the manganese dioxide and multi-walled carbon nanotubes are fully mixed and oscillated for adsorption, and then evenly cast to The glass mold is placed in an ultrasonic cleaning machine to vibrate and defoam, and then dried in a drying oven to obtain a non-metallic electrode, which is characterized in that:(1)多壁碳纳米管的二次分散：将多壁碳纳米管水分散液置于隔音箱升降台中间，选择Φ12型号的变幅杆，调节控制升降台升降的按钮，使变幅杆末端深入液面12mm-20mm,开启电源，设置工作时间为5min，超声时间为2s，间隔时间为1s，保护温度为60℃，关闭隔音箱，开启On按钮开始分散；共重复3-5次，每次分散中间将MNCT散热10min,得到均匀的多壁碳纳米管二次分散液；(1) Secondary dispersion of multi-walled carbon nanotubes: place the aqueous dispersion of multi-walled carbon nanotubes in the middle of the lifting platform of the soundproof box, select the horn of Φ12 type, and adjust the button for controlling the lifting of the lifting platform so that the horn The end goes deep into the liquid surface 12mm-20mm, turn on the power, set the working time to 5min, the ultrasonic time to 2s, the interval time to 1s, the protection temperature to 60°C, turn off the soundproof box, turn on the On button to start dispersing; repeat 3-5 times in total, Heat the MNCT for 10 minutes in the middle of each dispersion to obtain a uniform secondary dispersion of multi-walled carbon nanotubes;(2)壳聚糖溶液的制备：取5ml浓度为2％的醋酸、5ml浓度为3％的乳酸以及0.1g壳聚糖放在烧杯中，水浴加热搅拌，加热温度为50-70℃，直至充分溶解；(2) Preparation of chitosan solution: get 5ml concentration of 2% acetic acid, 5ml concentration of 3% lactic acid and 0.1g chitosan in a beaker, heat and stir in a water bath, and the heating temperature is 50-70°C until fully dissolved;(3)量取20ml质量分数为10％的多壁碳纳米管水分散液置于200ml的烧杯中，加入80ml蒸馏水将其质量分数稀释成2％。称取0.2g二氧化锰倒入上述烧杯中并将其置于超声波细胞分散仪中，与步骤(1)相同进行分散，制备出二氧化锰/多壁碳纳米管比例为0.1的混合溶液；(3) Measure 20 ml of 10% multi-walled carbon nanotube aqueous dispersion into a 200 ml beaker, add 80 ml of distilled water to dilute the mass fraction to 2%. Weigh 0.2g manganese dioxide and pour it into the above-mentioned beaker and place it in an ultrasonic cell disperser, disperse the same as step (1), and prepare a mixed solution whose ratio of manganese dioxide/multi-walled carbon nanotubes is 0.1;(4)取10ml步骤(3)获得的溶液加入步骤(2)获得的壳聚糖溶液中，水浴加热搅拌，温度为50-70℃，充分混合后均匀流延到玻璃模具中，放入超声波清洗机中震荡脱泡，然后放入干燥箱中干燥4-6h，其中干燥温度为80℃，真空度为零。(4) Take 10ml of the solution obtained in step (3) and add it to the chitosan solution obtained in step (2), heat and stir in a water bath at a temperature of 50-70°C, mix well and cast it into a glass mold evenly, and put it into an ultrasonic wave Shake and defoam in a washing machine, and then put it into a drying oven for 4-6 hours to dry, wherein the drying temperature is 80°C and the vacuum degree is zero.