技术领域technical field
本发明涉及用于超级电容器的赝电容电极材料的制备方法。The invention relates to a preparation method of a pseudocapacitance electrode material for a supercapacitor.
背景技术Background technique
由于能源危机的加剧，开发新能源成为当今社会可持续发展的必然之路。与此同时，新型的能量储存器件也成为研发热点之一。超级电容器是一种高效的能量储存装置，具有高功率密度、长循环寿命、快速充放电的特征，是一类介于二次电池和传统电容器之间的新型储能器件。材料是超级电容器的核心部件，超级电容器的性能主要取决于其材料的性能。碳化钴赝电容电极材料具有电导率高、循环寿命好的优点，是一类潜在的高电导率赝电容电极材料，因此具有广阔的应用前景。Due to the aggravation of the energy crisis, the development of new energy has become an inevitable way for the sustainable development of today's society. At the same time, new energy storage devices have also become one of the research and development hotspots. Supercapacitor is an efficient energy storage device with high power density, long cycle life, and fast charging and discharging. It is a new type of energy storage device between secondary batteries and traditional capacitors. Materials are the core components of supercapacitors, and the performance of supercapacitors mainly depends on the properties of their materials. Cobalt carbide pseudocapacitive electrode materials have the advantages of high conductivity and good cycle life, and are a potential class of high conductivity pseudocapacitive electrode materials, so they have broad application prospects.
当前，在环境污染日益严重的社会背景下，作为清洁能源能量储存器件的超级电容器是极具潜力的研究热点，而对于超级电容器研究主要是围绕材料展开的。关于碳化钴的制备技术，目前有专利CN102534338B中公开的球磨法和扩散法，以及专利CN104874413A中公开的埃米尺度碳化物制备方法。公开的球磨法是通过在高纯度氩气保护下进行5～80小时的球磨，存在着操作繁杂，制备时间长和固体杂质难以去除的缺点。扩散法则是把反应物原料置于氩气气氛保护下进行500～800℃高温的烧结，存在制备温度高、成分均匀性差等缺点。CN104874413A中公开的埃米尺度碳化物制备方法，则首先把过渡金属前驱体配制成溶液，再加入作为碳源的离子交换树脂，混合搅拌均匀后将固、液两相分离，收集固相，最后将固相干燥、焙烧。该方法极大的提高了碳化物尺寸的精细程度，但是存在着操作繁杂，实验用时长，反应所需温度高以及不宜实现规模化生产的问题。相比较而言，本发明中的液相化学制备碳化钴的方法则具有简单易操作、反应温度低、制备时间短、产物纯度高、工艺可控性强等特点，是对已公开制备技术的重要革新和补充。At present, under the social background of increasingly serious environmental pollution, supercapacitors, as clean energy storage devices, are a research hotspot with great potential, and the research on supercapacitors mainly revolves around materials. Regarding the preparation technology of cobalt carbide, there are ball milling method and diffusion method disclosed in patent CN102534338B, and the preparation method of angstrom-scale carbide disclosed in patent CN104874413A. The disclosed ball milling method is performed under the protection of high-purity argon for 5 to 80 hours, and has the disadvantages of complicated operation, long preparation time and difficult removal of solid impurities. The diffusion method is to sinter the raw materials of the reactants under the protection of an argon atmosphere at a high temperature of 500-800 ° C, which has the disadvantages of high preparation temperature and poor composition uniformity. The method for preparing angstrom-scale carbides disclosed in CN104874413A first prepares the transition metal precursor into a solution, then adds an ion exchange resin as a carbon source, mixes and stirs evenly, separates the solid and liquid phases, collects the solid phase, and finally The solid phase was dried and calcined. This method greatly improves the fineness of carbide size, but there are problems such as complicated operation, long experiment time, high reaction temperature and unsuitable for large-scale production. In comparison, the liquid-phase chemical preparation method of cobalt carbide in the present invention has the characteristics of simple and easy operation, low reaction temperature, short preparation time, high product purity, strong process controllability, etc., which is an improvement on the disclosed preparation technology. Important innovations and additions.
发明内容Contents of the invention
本发明的目的是提供一种用于赝电容电极材料的高电导率碳化钴的制备方法。The purpose of the present invention is to provide a method for preparing high-conductivity cobalt carbide used for pseudocapacitive electrode materials.
本发明是用于赝电容电极材料的高电导率碳化钴的制备方法，其步骤：采用液相化学法，把原料乙酰丙酮钴和油胺溶于有机溶剂十八烯中，并以氩气或氮气作为惰性保护气体，在370℃温度下反应制备出碳化钴，其具体操作步骤：The present invention is a preparation method of high-conductivity cobalt carbide used for pseudocapacitive electrode materials, the steps of which are: using a liquid-phase chemical method, dissolving raw materials cobalt acetylacetonate and oleylamine in an organic solvent octadecene, and using argon or Nitrogen is used as an inert protective gas, and cobalt carbide is prepared by reaction at a temperature of 370 ° C. The specific operation steps are as follows:
（1）秤取原料乙酰丙酮钴、油胺和有机溶剂十八烯，并置于反应容器中，加入搅拌磁子；(1) Weigh the raw materials cobalt acetylacetonate, oleylamine and organic solvent octadecene, put them in a reaction vessel, and add a stirring magnet;
（2）用真空泵机组将容器中的空气抽出，并配合其他仪器并将其密封，使容器中达到并保持低于1kPa的真空状态；(2) Use a vacuum pump unit to pump out the air in the container, and cooperate with other instruments to seal it, so that the container can reach and maintain a vacuum state below 1kPa;
（3）向容器内通入惰性保护气体，用质量流量计控制氩气的流量为40 mL/min；(3) Pass an inert protective gas into the container, and use a mass flow meter to control the flow of argon to 40 mL/min;
（4）对容器继续进行排气和预热30min；(4) Continue to exhaust and preheat the container for 30 minutes;
（5）将容器置于加热仪器，加热到370℃时进行保温，时间持续5～9小时；(5) Put the container in a heating device and heat it up to 370°C for 5 to 9 hours;
（6）待样品自然冷却后，用有机溶剂清洗离心，干燥后即得到用于赝电容电极材料的高电导率碳化钴。(6) After the sample is naturally cooled, it is washed and centrifuged with an organic solvent, and after drying, a high-conductivity cobalt carbide used as a pseudocapacitive electrode material is obtained.
本发明是对于材料中过渡金属碳化物之一的高电导率碳化钴制备方法，该方法是对高电导率碳化钴制备的新探索，是一种全新的高电导率碳化钴的制备方法。与传统的机械合金化和高温固相制备方法相比，液相化学制备方法条件温和，制备时间短，操作简单，易于控制，特别是反应在有机体系和惰性气体氛围中进行，容易获得纯度更高的材料。The invention relates to a method for preparing high-conductivity cobalt carbide, which is one of transition metal carbides in materials. The method is a new exploration for the preparation of high-conductivity cobalt carbide, and is a brand-new method for preparing high-conductivity cobalt carbide. Compared with the traditional mechanical alloying and high-temperature solid-phase preparation methods, the liquid-phase chemical preparation method has mild conditions, short preparation time, simple operation, and easy control. Especially, the reaction is carried out in an organic system and an inert gas atmosphere, and it is easy to obtain higher purity high material.
具体实施方式detailed description
本发明是用于赝电容电极材料的高电导率碳化钴的制备方法，其步骤：采用液相化学法，把原料乙酰丙酮钴和油胺溶于有机溶剂十八烯中，并以氩气或氮气作为惰性保护气体，在370℃温度下反应制备出碳化钴，其具体操作步骤：The present invention is a preparation method of high-conductivity cobalt carbide used for pseudocapacitive electrode materials. The steps are: adopting a liquid phase chemical method, dissolving raw materials cobalt acetylacetonate and oleylamine in an organic solvent octadecene, and using argon or Nitrogen is used as an inert protective gas, and cobalt carbide is prepared by reaction at a temperature of 370 ° C. The specific operation steps are as follows:
（1）秤取原料乙酰丙酮钴、油胺和有机溶剂十八烯，并置于反应容器中，加入搅拌磁子；(1) Weigh the raw materials cobalt acetylacetonate, oleylamine and organic solvent octadecene, put them in a reaction vessel, and add a stirring magnet;
（2）用真空泵机组将容器中的空气抽出，并配合其他仪器并将其密封，使容器中达到并保持低于1kPa的真空状态；(2) Use a vacuum pump unit to pump out the air in the container, and cooperate with other instruments to seal it, so that the container can reach and maintain a vacuum state below 1kPa;
（3）向容器内通入惰性保护气体，用质量流量计控制氩气的流量为40 mL/min；(3) Pass an inert protective gas into the container, and use a mass flow meter to control the flow of argon to 40 mL/min;
（4）对容器继续进行排气和预热30min；(4) Continue to exhaust and preheat the container for 30 minutes;
（5）将容器置于加热仪器，加热到370℃时进行保温，时间持续5～9小时；(5) Put the container in a heating device and heat it up to 370°C for 5 to 9 hours;
（6）待样品自然冷却后，用有机溶剂清洗离心，干燥后即得到用于赝电容电极材料的高电导率碳化钴。(6) After the sample is naturally cooled, it is washed and centrifuged with an organic solvent, and after drying, a high-conductivity cobalt carbide used as a pseudocapacitive electrode material is obtained.
以下为高电导率碳化钴制备的具体实施实例，但是本发明并不局限于这些实施例。The following are specific implementation examples for the preparation of high-conductivity cobalt carbide, but the present invention is not limited to these examples.
实施例1：Example 1:
(1) 首先称取0.5g乙酰丙酮钴，10ml油胺和5ml十八烯，加入三口烧瓶中，并加入与电热套配套的搅拌磁子；(1) First weigh 0.5g cobalt acetylacetonate, 10ml oleylamine and 5ml octadecene, add them into a three-necked flask, and add the stirring magnet matched with the electric heating mantle;
(2) 用一个橡皮塞，一个冷凝管和两个二通抽气头将三口烧瓶密封；(2) Seal the three-necked flask with a rubber stopper, a condenser tube and two two-way extraction heads;
(3) 用两级罗茨泵+液环泵将容器中的空气抽出，使容器内达到并保持低于1 kPa的真空状态；(3) Use a two-stage Roots pump + liquid ring pump to pump out the air in the container, so that the container can reach and maintain a vacuum state below 1 kPa;
(4) 向三口烧瓶内通入氩气，进行反应保护，用质量流量计控制氩气的流量为40 mL/s；(4) Pass argon into the three-necked flask for reaction protection, and use a mass flow meter to control the flow of argon to 40 mL/s;
(5) 对三口烧瓶排气和预热30min，预热温度为50℃；(5) Exhaust and preheat the three-necked flask for 30 minutes, and the preheating temperature is 50°C;
(6) 用电热套将容器继续加热，直至370 ℃时进行保温，时间持续8小时30分钟。(6) Continue heating the container with an electric heating mantle until it reaches 370°C for 8 hours and 30 minutes.
待样品自然冷却后，用有机溶剂正己烷清洗并离心3次，在烘箱内30℃干燥6个小时后即得到用于赝电容电极材料的高电导率碳化钴。After the sample was naturally cooled, it was washed with the organic solvent n-hexane and centrifuged three times, and dried in an oven at 30°C for 6 hours to obtain high-conductivity cobalt carbide for pseudocapacitive electrode materials.
实施例2：Example 2:
(1) 首先称取0.5g乙酰丙酮钴，10ml油胺和5ml十八烷，加入三口烧瓶中，并加入与电热套配套的搅拌磁子；(1) First weigh 0.5g cobalt acetylacetonate, 10ml oleylamine and 5ml octadecane, add them to a three-necked flask, and add the stirring magnet matched with the electric heating mantle;
(2) 用一个橡皮塞，一个冷凝管和两个二通抽气头将三口烧瓶密封；(2) Seal the three-necked flask with a rubber stopper, a condenser tube and two two-way extraction heads;
(3) 用两级罗茨泵+液环泵将容器中的空气抽出，使容器内达到并保持低于1 kPa的真空状态；(3) Use a two-stage Roots pump + liquid ring pump to pump out the air in the container, so that the container can reach and maintain a vacuum state below 1 kPa;
(4) 向三口烧瓶内通入氩气，进行反应保护，用质量流量计控制氩气的流量为40 mL/s；(4) Pass argon into the three-necked flask for reaction protection, and use a mass flow meter to control the flow of argon to 40 mL/s;
(5) 对三口烧瓶排气和预热30min，预热温度为50℃；(5) Exhaust and preheat the three-necked flask for 30 minutes, and the preheating temperature is 50°C;
(6) 用电热套将容器继续加热，直至370 ℃时进行保温，时间持续8小时30分钟。(6) Continue heating the container with an electric heating mantle until it reaches 370°C for 8 hours and 30 minutes.
待样品自然冷却后，用有机溶剂正己烷清洗并离心3次，在烘箱内30℃干燥6个小时后即得到用于赝电容电极材料的高电导率碳化钴。After the sample was naturally cooled, it was washed with the organic solvent n-hexane and centrifuged three times, and dried in an oven at 30°C for 6 hours to obtain high-conductivity cobalt carbide for pseudocapacitive electrode materials.
| Application Number | Priority Date | Filing Date | Title |
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| CN201710088604.XACN106887345B (en) | 2017-02-20 | 2017-02-20 | The preparation method of high conductivity cobalt carbide for fake capacitance electrode material |
| Application Number | Priority Date | Filing Date | Title |
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| CN201710088604.XACN106887345B (en) | 2017-02-20 | 2017-02-20 | The preparation method of high conductivity cobalt carbide for fake capacitance electrode material |
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| CN106887345Atrue CN106887345A (en) | 2017-06-23 |
| CN106887345B CN106887345B (en) | 2018-11-13 |
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| CN201710088604.XAExpired - Fee RelatedCN106887345B (en) | 2017-02-20 | 2017-02-20 | The preparation method of high conductivity cobalt carbide for fake capacitance electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101954480A (en)* | 2010-11-08 | 2011-01-26 | 华东理工大学 | Method for preparing carbon-coated core-shell nanoparticles continuously |
| CN102534338A (en)* | 2011-12-27 | 2012-07-04 | 彩虹集团公司 | Cobalt carbide material for hydrogen storage and preparation method thereof |
| CN103540822A (en)* | 2012-07-17 | 2014-01-29 | 北汽福田汽车股份有限公司 | Cobalt carbide material for hydrogen storage as well as preparation method thereof and hydrogen storage electrode and battery prepared from material and battery |
| CN104874413A (en)* | 2015-05-08 | 2015-09-02 | 江苏大学 | A kind of angstrom scale carbide and its preparation method |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101954480A (en)* | 2010-11-08 | 2011-01-26 | 华东理工大学 | Method for preparing carbon-coated core-shell nanoparticles continuously |
| CN102534338A (en)* | 2011-12-27 | 2012-07-04 | 彩虹集团公司 | Cobalt carbide material for hydrogen storage and preparation method thereof |
| CN103540822A (en)* | 2012-07-17 | 2014-01-29 | 北汽福田汽车股份有限公司 | Cobalt carbide material for hydrogen storage as well as preparation method thereof and hydrogen storage electrode and battery prepared from material and battery |
| CN104874413A (en)* | 2015-05-08 | 2015-09-02 | 江苏大学 | A kind of angstrom scale carbide and its preparation method |
| Publication number | Publication date |
|---|---|
| CN106887345B (en) | 2018-11-13 |
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