WO2017219943A1

WO2017219943A1 - Composite petroleum coke-based activated carbon and preparation method therefor, and supercapacitor

Info

Publication number: WO2017219943A1
Application number: PCT/CN2017/088990
Authority: WO
Inventors: 赵永彬; 张在忠; 刘海波; 董士光; 胡兴华
Original assignee: 山东欧铂新材料有限公司
Priority date: 2016-06-20
Filing date: 2017-06-19
Publication date: 2017-12-28
Also published as: CN106082213A; CN106082213B

Abstract

Composite petroleum coke-based activated carbon and a preparation method therefor. Activated active sites can be formed on the surface of petroleum coke by means of the dipping, coking and pre-activating processes of an oxidizing medium, and accordingly the pore forming in the chemical activation part is facilitated, the use amount of alkali is reduced, the mesopore rate is increased, and the problem of difficulty in pore forming due to compactness of the surface of the petroleum coke is resolved. Graphene oxide is reduced into graphene, a conductive network is formed, so that the conductivity of the activated carbon is improved, and the internal resistance of the activated carbon is reduced. High-temperature heat treatment is jointly carried out, so that surface functional groups are reduced, and the stability of a super-capacitor carbon is improved. The prepared composite petroleum coke-based activated carbon has the advantages of being reasonable in pore size distribution, large in specific surface area, low in internal resistance, high in capacity, low in impurity and low in oxygen-containing functional group and can serve as super-capacitor carbon to obtain the supercapacitor having better performance.

Description

一种复合型石油焦基活性炭及其制备方法、超级电容器Composite petroleum coke-based activated carbon, preparation method thereof, super capacitor

本申请要求于2016年06月20日提交中国专利局、申请号为201610445275.5、发明名称为“一种复合型石油焦基活性炭及其制备方法、超级电容器”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims priority to Chinese Patent Application No. 201610445275.5, entitled "Compound-type petroleum coke-based activated carbon and its preparation method, supercapacitor", which is submitted to the Chinese Patent Office on June 20, 2016. The content is incorporated herein by reference.

技术领域Technical field

本发明属于活性炭材料技术领域，尤其涉及一种复合型石油焦基活性炭及其制备方法、超级电容器。The invention belongs to the technical field of activated carbon materials, in particular to a composite petroleum coke-based activated carbon, a preparation method thereof and a super capacitor.

背景技术Background technique

活性炭又称活性炭黑，是黑色粉末状或块状、颗粒状、蜂窝状的无定形碳，也有排列规整的晶体碳。活性炭中除碳元素外，还包含少量的氢元素与氧元素，这些元素一部分源于活性炭前体不完全碳化而残留在活性炭中，另一部分来源于活化试剂如水或氢氧化钠与活性炭表面反应形成羟基，羧基，羰基等基团。此外活性炭还存在一部分灰分，主要由残留在活性炭中的无机盐组成，如铁盐，钠盐，钾盐等。Activated carbon, also known as activated carbon black, is a black powder or block, granular, honeycomb amorphous carbon, but also has a regular arrangement of crystalline carbon. In addition to carbon, activated carbon also contains a small amount of hydrogen and oxygen. Some of these elements are derived from the incomplete carbonization of the activated carbon precursor and remain in the activated carbon. The other part is derived from the activation of reagents such as water or sodium hydroxide to form a surface with activated carbon. a group such as a hydroxyl group, a carboxyl group, a carbonyl group or the like. In addition, activated carbon also has a part of ash, which is mainly composed of inorganic salts remaining in activated carbon, such as iron salt, sodium salt, potassium salt and the like.

活性炭从原料上来分可以分为木质，煤质，石油焦和树脂活性炭；从制造方法上来分，分为化学法、物理法以及物理化学联合法活性炭。这些活性炭前体在活化炉中于高温，一定压力下与活化剂通过热解作用，高温炭化和活化反应形成活性炭。在此活化过程中，巨大的表面积和复杂的孔隙结构逐渐形成。活性炭含有大量微孔，具有巨大无比的表面积，能有效地去除色度、臭味，可去除二级出水中大多数有机污染物和某些无机物，包含某些有毒的重金属。而根据活性炭石墨化难易程度，又分为硬碳和软碳，通常来说以木质素、树脂为原料制备的为硬炭，以石油焦为原料制备的为软炭。Activated carbon can be divided into wood, coal, petroleum coke and resin activated carbon from the raw materials; from the manufacturing method, it is divided into chemical, physical and physical chemical combined activated carbon. These activated carbon precursors form activated carbon in an activation furnace at a high temperature, under a certain pressure, by pyrolysis with an activator, high temperature carbonization and activation reaction. During this activation process, large surface areas and complex pore structures are gradually formed. Activated carbon contains a large number of micropores, has a huge surface area, can effectively remove chromaticity and odor, and can remove most organic pollutants and certain inorganic substances in secondary effluent, including some toxic heavy metals. According to the difficulty of graphitization of activated carbon, it is divided into hard carbon and soft carbon. Generally, lignin and resin are used as raw materials for hard carbon, and petroleum coke is used as raw material for soft carbon.

随着世界对新能源技术的重视，超级电容器得到越来越多的应用。与锂电池相比，超级电容器有充放电速度快、功率密度高、寿命长、免维护、绿色环保等特点，虽然能量密度仍然远远低于锂电池，但在功率密度方面能够弥补锂电池的短板，成为锂电池及其它二次电池的有力补充，在通信、军事、新能源汽车、国家电网、港口机械等多个领域得到了成功的应用。With the world's emphasis on new energy technologies, supercapacitors are getting more and more applications. Compared with lithium batteries, supercapacitors have the characteristics of fast charge and discharge speed, high power density, long life, maintenance-free, and environmental protection. Although the energy density is still far lower than that of lithium batteries, they can make up for lithium batteries in terms of power density. The short board has become a powerful complement to lithium batteries and other secondary batteries, and has been successfully applied in many fields such as communications, military, new energy vehicles, national power grids, and port machinery.

超级电容器的储电能力主要取决于电极材料可用于储电的比表面积和电荷密集程度。从理论上说，电极表面积越大，电荷越密集，其容量就越大。由于多孔碳具有化学稳定性、高比表面积等特点，是目前超级电容器领域应用最广泛的材料，而活性炭又是最常用的超级电容器电极材料。The storage capacity of supercapacitors depends mainly on the specific surface area and electricity that the electrode material can be used to store electricity. The intensity of the load. Theoretically, the larger the surface area of the electrode, the denser the charge and the greater its capacity. Due to its chemical stability and high specific surface area, porous carbon is the most widely used material in the field of supercapacitors, and activated carbon is the most commonly used supercapacitor electrode material.

然而活性炭的比表面积，孔径分布，电导率，表面官能团，堆积密度等各项指标都会影响超级电容器的性能，因而制备高能量密度和高功率密度的电极材料一直是超级电容器领域的核心问题，这种电极材料需要有高的比表面积，合理的孔径分布以及良好的电导率。However, the specific surface area, pore size distribution, electrical conductivity, surface functional group, bulk density and other indicators of activated carbon will affect the performance of supercapacitors. Therefore, the preparation of electrode materials with high energy density and high power density has always been a core issue in the field of supercapacitors. Electrode materials require high specific surface area, reasonable pore size distribution, and good electrical conductivity.

但是目前商业用的超级电容炭仍然以微孔为主，中孔含量较低；内阻较高，制备超级电容器需要加入5～10％的导电炭黑用于形成导电网络；此外比容量仍然较低，能量密度与锂电池相比仍然相差较远。However, the current commercial supercapacitor carbon is still dominated by micropores, with low mesoporosity; high internal resistance. It is necessary to add 5-10% conductive carbon black to form a conductive network for the preparation of supercapacitors; Low, the energy density is still far from the lithium battery.

因此，如何得到一种活性炭材料，使其更适用于超级电容器电极材料，对于推动超级电容器的发展和活性炭材料的实际应用具有重要意义，也成为领域内前瞻性研究人员广泛关注的焦点之一。Therefore, how to obtain an activated carbon material to make it more suitable for supercapacitor electrode materials is of great significance for promoting the development of supercapacitors and the practical application of activated carbon materials, and has become one of the focuses of forward-looking researchers in the field.

发明内容Summary of the invention

有鉴于此，本发明要解决的技术问题在于提供一种改性的复合型石油焦基活性炭及其制备方法、超级电容器，本发明提供的石墨烯改性的复合型石油焦基活性炭，具有大比表面积，低内阻，高容量，低杂质及低含氧官能团等特点，能够作为超级电容炭，得到性能更好的超级电容器。In view of the above, the technical problem to be solved by the present invention is to provide a modified composite petroleum coke-based activated carbon, a preparation method thereof, and a super capacitor. The graphene-modified composite petroleum coke-based activated carbon provided by the present invention has a large It has the characteristics of specific surface area, low internal resistance, high capacity, low impurity and low oxygen content, and can be used as a supercapacitor carbon to obtain a supercapacitor with better performance.

本发明提供了一种复合型石油焦基活性炭的制备方法，包括以下步骤：The invention provides a preparation method of a composite petroleum coke-based activated carbon, comprising the following steps:

A)将经过氧化性介质处理后的石油焦颗粒，在第一气体的条件下进行焦化后，得到活性炭前体；A) the petroleum coke particles treated by the oxidizing medium are coked under the condition of the first gas to obtain an activated carbon precursor;

B)将上述步骤得到的活性炭前体与碱混合后，在第二气体的条件下进行预活化，然后在第三气体的条件下进行活化，再洗涤后得到活性炭分散液；B) after the activated carbon precursor obtained in the above step is mixed with a base, pre-activated under the condition of the second gas, and then activated under the condition of the third gas, and then washed to obtain an activated carbon dispersion;

C)将上述步骤得到的活性炭分散液与氧化石墨烯溶液混合后干燥，再在保护性气体的条件下进行热处理后，得到复合型石油焦基活性炭。C) The activated carbon dispersion obtained in the above step is mixed with a graphene oxide solution, dried, and then heat-treated under a protective gas condition to obtain a composite petroleum coke-based activated carbon.

优选的，所述氧化性介质包括双氧水、硝酸溶液、次氯酸溶液、高氯酸溶液、高铁酸钾溶液、高铁酸钠溶液、高锰酸钾溶液和锰酸钾水溶液中的一种或多种；Preferably, the oxidizing medium comprises one or more of hydrogen peroxide, nitric acid solution, hypochlorous acid solution, perchloric acid solution, potassium ferrate solution, sodium ferrate solution, potassium permanganate solution and potassium manganate solution. Species

所述石油焦包括蜂窝焦、海绵焦、弹丸焦和针状焦中的一种或多种；所述石油焦颗粒的粒径为5～150μm；The petroleum coke includes one or more of a honeycomb coke, a sponge coke, a projectile coke, and a needle coke; The petroleum coke particles have a particle size of 5 to 150 μm;

所述处理的时间为2～24h，所述处理的温度为0～80℃。The treatment time is 2 to 24 hours, and the treatment temperature is 0 to 80 °C.

优选的，所述第一气体包括空气、氧气、氢气、氮气、惰性气体、二氧化碳和水蒸气中的一种或多种；Preferably, the first gas comprises one or more of air, oxygen, hydrogen, nitrogen, an inert gas, carbon dioxide, and water vapor;

所述焦化的温度为350～700℃，所述焦化的时间为1～6小时。The coking temperature is 350 to 700 ° C, and the coking time is 1 to 6 hours.

优选的，所述活性炭前体与碱的质量比为1：(0.5～5)；Preferably, the mass ratio of the activated carbon precursor to the base is 1: (0.5 to 5);

所述碱包括氢氧化钾、氢氧化钠、氢氧化锂和氢氧化钙其中一种或多种；The base includes one or more of potassium hydroxide, sodium hydroxide, lithium hydroxide and calcium hydroxide;

所述碱为颗粒状碱，所述颗粒状碱的粒径为10～300μm。The base is a particulate alkali, and the granular base has a particle diameter of 10 to 300 μm.

优选的，所述第二气体包括空气、氢气、氮气和惰性气体中的一种或多种；Preferably, the second gas comprises one or more of air, hydrogen, nitrogen and an inert gas;

所述预活化的温度为350～500℃，所述预活化的时间为1～4小时；The preactivation temperature is 350 to 500 ° C, and the preactivation time is 1 to 4 hours;

所述第三气体包括氢气、氮气和惰性气体中的一种或多种；The third gas includes one or more of hydrogen, nitrogen, and an inert gas;

所述活化的温度为700～950℃，所述活化的时间为0.5～4小时。The activation temperature is 700 to 950 ° C, and the activation time is 0.5 to 4 hours.

优选的，所述步骤C)具体为：Preferably, the step C) is specifically:

将上述步骤得到的活性炭分散液、氧化石墨烯溶液和氮源混合后干燥，再进行热处理后，得到复合型石油焦基活性炭；The activated carbon dispersion liquid, the graphene oxide solution and the nitrogen source obtained in the above steps are mixed and dried, and then heat-treated to obtain a composite petroleum coke-based activated carbon;

所述氮源包括三聚氰胺和/或尿素；The nitrogen source comprises melamine and/or urea;

所述氧化石墨烯溶液中氧化石墨烯的质量占所述活性炭分散液中活性炭质量的比例为0.05％～1％；The ratio of the mass of the graphene oxide in the graphene oxide solution to the mass of the activated carbon in the activated carbon dispersion is 0.05% to 1%;

所述氮源的质量占所述活性炭分散液中活性炭质量的比例为1％～5％。The ratio of the mass of the nitrogen source to the mass of the activated carbon in the activated carbon dispersion is from 1% to 5%.

优选的，所述保护性气体包括氢气、氨气、氮气和惰性气体中的一种或多种；Preferably, the protective gas comprises one or more of hydrogen, ammonia, nitrogen and an inert gas;

所述热处理的温度为700～1000℃，所述热处理的时间为1～4小时。The heat treatment temperature is 700 to 1000 ° C, and the heat treatment time is 1 to 4 hours.

优选的，所述热处理后还包括破碎、筛选和磁选步骤；Preferably, after the heat treatment, the steps of crushing, screening and magnetic separation are further included;

所述破碎后的粒径为6～10μm。The particle size after the crushing is 6 to 10 μm.

本发明提供了一种复合型石油焦基活性炭，所述复合型石油焦基活性炭由石油焦、氧化石墨烯和氮源经过复合后得到。The invention provides a composite petroleum coke-based activated carbon obtained by compounding petroleum coke, graphene oxide and nitrogen source.

本发明还提供了一种超级电容器，包含上述技术方案任意一项所制备的复合型石油焦基活性炭或上述技术方案所述的复合型石油焦基活性炭。The present invention also provides a supercapacitor comprising the composite petroleum coke-based activated carbon prepared by any one of the above technical solutions or the composite petroleum coke-based activated carbon according to the above technical solution.

本发明提供了一种复合型石油焦基活性炭的制备方法，包括以下步骤，首先将经过氧化性介质处理后的石油焦颗粒，在第一气体的条件下进行焦化后，得到活性炭前体；随后将上述步骤得到的活性炭前体与碱混合后，在第二气体的条件下进行预活化，然后在第三气体的条件下进行活化，再洗涤后得到活性炭分散液；最后将上述步骤得到的活性炭分散液与氧化石墨烯溶液混合后干燥，再在保护性气体的条件下进行热处理后，得到复合型石油焦基活性炭。与现有技术相比，本发明针对现有的活性炭主要以微孔为主，孔径分布不合理；制备过程中所用的碱比例较高；制备的活性炭性能仍然无法满足对容量方面的要求；制备的活性炭内阻较大等问题。本发明通过氧化介质浸渍及焦化、预活化过程，可以在石油焦表面形成活化的活性点，有利于化学活化部分造孔，降低碱使用量，增加中孔率，克服石油焦表面致密，造孔较困难的问题；利用氧化石墨烯还原为石墨烯，形成导电网络，改善了活性炭的电导率，降低其内阻；共同进行高温热处理降低了表面官能团，改善了超级电容炭的稳定性。实验结果表明，本发明制备的复合型石油焦基活性炭具有合理孔径分布，大比表面积，低内阻，高容量，低杂质及低含氧官能团的优点，能够作为超级电容炭，得到性能更好的超级电容器。The invention provides a preparation method of a composite petroleum coke-based activated carbon, comprising the following steps: First, the petroleum coke particles treated by the oxidizing medium are coked under the condition of the first gas to obtain an activated carbon precursor; then the activated carbon precursor obtained by the above step is mixed with the alkali, and then under the condition of the second gas. Pre-activation, and then activation under the third gas condition, and then washing to obtain activated carbon dispersion; finally, the activated carbon dispersion obtained in the above step is mixed with the graphene oxide solution, dried, and then under protective gas conditions. After the heat treatment, a composite petroleum coke-based activated carbon is obtained. Compared with the prior art, the present invention is mainly directed to micropores, and the pore size distribution is unreasonable; the proportion of alkali used in the preparation process is high; the performance of the prepared activated carbon still cannot meet the capacity requirements; The internal resistance of activated carbon is large and so on. The invention can form an activated active point on the surface of petroleum coke by immersion and coking and pre-activation process of oxidizing medium, which is beneficial to chemical activation of partial pore formation, reduction of alkali usage, increase of mesoporosity, overcoming the surface of petroleum coke, and pore formation. More difficult problems; the use of graphene oxide to reduce graphene, forming a conductive network, improving the electrical conductivity of activated carbon, reducing its internal resistance; jointly high temperature heat treatment reduces surface functional groups and improves the stability of supercapacitor carbon. The experimental results show that the composite petroleum coke-based activated carbon prepared by the invention has the advantages of reasonable pore size distribution, large specific surface area, low internal resistance, high capacity, low impurity and low oxygen-containing functional groups, and can be used as super capacitor carbon to obtain better performance. Supercapacitor.

附图说明DRAWINGS

图1为本发明制备的复合型石油焦基活性炭的电镜照片；1 is an electron micrograph of a composite petroleum coke-based activated carbon prepared by the present invention;

图2为本发明实施例1制备的复合型石油焦基活性炭的电镜照片；2 is an electron micrograph of a composite petroleum coke-based activated carbon prepared in Example 1 of the present invention;

图3为本发明实施例1制备的复合型石油焦基活性炭的孔径分布图。3 is a pore size distribution diagram of a composite petroleum coke-based activated carbon prepared in Example 1 of the present invention.

具体实施方式detailed description

为了进一步理解本发明，下面结合实施例对本发明优选实施方案进行描述，但是应当理解，这些描述只是为了进一步说明本发明的特征和优点，而不是对发明权利要求的限制。For a better understanding of the invention, the preferred embodiments of the invention are described in the accompanying claims,

本发明所有原料，对其来源没有特别限制，在市场上购买的或按照本领域技术人员熟知的常规方法制备的即可。All the raw materials of the present invention are not particularly limited in their source, and are commercially available or prepared according to a conventional method well known to those skilled in the art.

本发明所有原料，对其纯度没有特别限制，本发明优选采用分析纯或电容器领域使用的常规纯度。The purity of all the raw materials of the present invention is not particularly limited, and the present invention preferably employs a conventional purity used in the field of analytically pure or capacitors.

A)将经过氧化性介质处理后的石油焦颗粒，在第一气体的条件下进行焦化后，得到活性炭前体；A) the petroleum coke particles treated by the oxidizing medium are subjected to coke under the conditions of the first gas After the activation, the activated carbon precursor is obtained;

本发明首先将经过氧化性介质处理后的石油焦颗粒，在第一气体的条件下进行焦化后，得到活性炭前体。In the present invention, the petroleum coke particles treated by the oxidizing medium are first coked under the conditions of the first gas to obtain an activated carbon precursor.

本发明对所述石油焦的具体选择没有特别限制，以本领域技术人员熟知的石油焦即可，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明所述石油焦优选包括蜂窝焦、海绵焦、弹丸焦和针状焦中的一种或多种，更优选为蜂窝焦、弹丸焦或针状焦，最优选为针状焦。本发明对所述石油焦的品质没有特别限制，以本领域技术人员熟知的石油焦品质即可，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明所述石油焦优选为含碳量大于等于90％，含硫量小于等于0.5％的石油焦。本发明对所述石油焦颗粒的粒径没有特别限制，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明所述石油焦颗粒的粒径优选为5～150μm，更优选为20～120μm更优选为40～100μm，最优选为60～80μm。The specific selection of the petroleum coke of the present invention is not particularly limited, and the petroleum coke which is well known to those skilled in the art can be used, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements, and the present invention The petroleum coke preferably comprises one or more of honeycomb coke, sponge coke, projectile coke and needle coke, more preferably honeycomb coke, projectile coke or needle coke, most preferably needle coke. The quality of the petroleum coke of the present invention is not particularly limited, and the petroleum coke quality known to those skilled in the art can be used. Those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements. The petroleum coke is preferably petroleum coke having a carbon content of 90% or more and a sulfur content of 0.5% or less. The particle size of the petroleum coke particles is not particularly limited, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements. The particle size of the petroleum coke particles of the present invention is preferably 5 to 150 μm. It is more preferably 20 to 120 μm, still more preferably 40 to 100 μm, and most preferably 60 to 80 μm.

本发明对所述氧化性介质的具体选择没有特别限制，以本领域技术人员熟知的氧化性介质即可，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明所述氧化性介质优选包括双氧水、硝酸溶液、次氯酸溶液、高氯酸溶液、高铁酸钾溶液、高铁酸钠溶液、高锰酸钾溶液和锰酸钾水溶液中的一种或多种，更优选为双氧水、硝酸溶液、次氯酸溶液、高氯酸溶液、高铁酸钾溶液、高铁酸钠溶液、高锰酸钾溶液或锰酸钾水溶液。本发明对所述氧化性介质的浓度没有特别限制，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整。The specific selection of the oxidizing medium in the present invention is not particularly limited, and the oxidizing medium is well known to those skilled in the art, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements, and the present invention The oxidizing medium preferably comprises one or more of hydrogen peroxide, nitric acid solution, hypochlorous acid solution, perchloric acid solution, potassium ferrate solution, sodium ferrate solution, potassium permanganate solution and potassium manganate solution. More preferably, it is a hydrogen peroxide solution, a nitric acid solution, a hypochlorous acid solution, a perchloric acid solution, a potassium ferrate solution, a sodium ferrate solution, a potassium permanganate solution, or an aqueous potassium manganate solution. The concentration of the oxidizing medium in the present invention is not particularly limited, and those skilled in the art can select and adjust according to actual production conditions, product requirements, and quality requirements.

本发明对所述处理的具体条件没有特别限制，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明所述处理的时间优选为2～24h，更优选为6～20h，更优选为10～16h，最优选为12～14h；所述处理的温度优选为0～80℃，更优选为10～70℃，更优选为20～60℃，最优选为30～50℃。本发明对所述处理的具体方式没有特别限制，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明所述处理优选为浸渍、浸泡、喷洒或涂刷，以及之后的洗涤和干燥等，更优选为浸泡以及之后的洗涤和干燥。本发明上述具体步骤的过程和条件没有特别限制，以本领域技术人员熟知的相应的过程和条件即可。The specific conditions of the treatment of the present invention are not particularly limited, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements. The processing time of the present invention is preferably 2-24 hours, more preferably 6 ～20h, more preferably 10-16h, most preferably 12-14h; The temperature is preferably 0 to 80 ° C, more preferably 10 to 70 ° C, still more preferably 20 to 60 ° C, and most preferably 30 to 50 ° C. The specific manner of the treatment of the present invention is not particularly limited, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements, and the treatment according to the present invention is preferably dipping, immersing, spraying or painting, and Subsequent washing and drying, etc., are more preferably soaking and subsequent washing and drying. The procedures and conditions of the above specific steps of the present invention are not particularly limited, and may be the corresponding processes and conditions well known to those skilled in the art.

本发明对所述第一气体没有特别限制，以本领域技术人员熟知的保护性气体即可，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明所述第一气体优选包括空气、氧气、氢气、氮气、惰性气体、二氧化碳和水蒸气中的一种或多种，更优选为空气、氧气、氢气、氮气、惰性气体、二氧化碳或水蒸气。本发明对所述惰性气体没有特别限制，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明具体优选为氩气。The first gas is not particularly limited, and the protective gas is well known to those skilled in the art, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements. The gas preferably comprises one or more of air, oxygen, hydrogen, nitrogen, an inert gas, carbon dioxide and water vapor, more preferably air, oxygen, hydrogen, nitrogen, an inert gas, carbon dioxide or water vapor. The inert gas of the present invention is not particularly limited, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements, and the present invention is particularly preferably argon gas.

本发明对所述焦化的条件没有特别限制，以本领域技术人员熟知的石油焦焦化的条件即可，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明所述焦化的温度优选为350～700℃，更优选为400～650℃，更优选为450～600℃，最优选为500～550℃；所述焦化的时间优选为1～6小时，更优选为2～5小时，最优选为3～4小时。本发明对所述焦化的设备没有特别限制，以本领域技术人员熟知的石油焦焦化的设备即可，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明所述焦化的设备优选为焦化炉。The conditions of the coking in the present invention are not particularly limited, and the conditions of petroleum coke coking which are well known to those skilled in the art may be used, and those skilled in the art may select and adjust according to actual production conditions, product requirements and quality requirements, and the present invention The coking temperature is preferably 350 to 700 ° C, more preferably 400 to 650 ° C, still more preferably 450 to 600 ° C, most preferably 500 to 550 ° C; the coking time is preferably 1 to 6 hours, more preferably 2 to 5 hours, most preferably 3 to 4 hours. The apparatus for the coking of the present invention is not particularly limited, and the petroleum coke coking device well known to those skilled in the art may be used, and those skilled in the art may select and adjust according to actual production conditions, product requirements and quality requirements, and the present invention The coking unit is preferably a coker.

本发明随后将上述步骤得到的活性炭前体与碱混合后，在第二气体的条件下进行预活化，然后在第三气体的条件下进行活化，再洗涤后得到活性炭分散液。According to the present invention, the activated carbon precursor obtained in the above step is mixed with a base, pre-activated under the conditions of the second gas, and then activated under the conditions of the third gas, and then washed to obtain an activated carbon dispersion.

本发明对所述碱没有特别限制，以本领域技术人员熟知的石油焦活化用碱即可，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明所述碱优选包括氢氧化钾、氢氧化钠、氢氧化锂和氢氧化钙其中一种或多种，更优选为氢氧化钾、氢氧化钠、氢氧化锂或氢氧化钙，更优选为氢氧化钾、氢氧化钠或氢氧化钙，最优选为氢氧化钾。本发明对所述碱没有其他特别限制，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明为方便混合，所述碱优选为颗粒状碱，所述颗粒状碱的粒径优选为10～300μm，更优选为50～250μm，更优选为100～200μm，最优选为130～170μm。本发明对所述碱的用量没有特别限制，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明所述活性炭前体与碱的质量比优选为1：(0.5～5)，更优选为1：(1～4.5)，更优选为1：(1.5～4)，最优选为1：(2～3.5)。本发明对所述混合没有特别限制，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明优选为混料机混合。The base is not particularly limited in the present invention, and the base for petroleum coke activation well known to those skilled in the art may be used, and those skilled in the art may select and adjust according to actual production conditions, product requirements and quality requirements, and the alkali of the present invention. Preferably, it comprises one or more of potassium hydroxide, sodium hydroxide, lithium hydroxide and calcium hydroxide, more preferably potassium hydroxide, sodium hydroxide, lithium hydroxide or calcium hydroxide, more preferably potassium hydroxide, Sodium hydroxide or calcium hydroxide is most preferably potassium hydroxide. The invention does not have the base Other specific restrictions, those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements. For convenient mixing, the base is preferably a granular base, and the granular base preferably has a particle diameter of 10 ～300 μm, more preferably 50 to 250 μm, still more preferably 100 to 200 μm, and most preferably 130 to 170 μm. The amount of the base to be used in the present invention is not particularly limited, and those skilled in the art can select and adjust according to the actual production conditions, product requirements and quality requirements. The mass ratio of the activated carbon precursor to the base of the present invention is preferably 1: (0.5) ～5) is more preferably 1: (1 to 4.5), still more preferably 1: (1.5 to 4), and most preferably 1: (2 to 3.5). The present invention is not particularly limited to the mixing, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements, and the present invention preferably mixes with a mixer.

本发明对所述第二气体没有特别限制，以本领域技术人员熟知的保护性气体即可，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明所述第二气体优选包括空气、氢气、氮气和惰性气体中的一种或多种，更优选为空气、氢气、氮气或氩气。本发明对所述预活化的条件没有特别限制，以本领域技术人员熟知的石油焦预活化的条件即可，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明所述预活化的温度优选为350～500℃，更优选为375～475℃，更优选为400～450℃，最优选为410～440℃；所述预活化的时间优选为1～4小时，更优选为1.5～3.5小时，最优选为2～3小时。The second gas is not particularly limited, and the protective gas is well known to those skilled in the art. Those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements. The two gases preferably comprise one or more of air, hydrogen, nitrogen and an inert gas, more preferably air, hydrogen, nitrogen or argon. The pre-activation conditions of the present invention are not particularly limited, and the conditions of pre-activation of petroleum coke which are well known to those skilled in the art may be used, and those skilled in the art may select and adjust according to actual production conditions, product requirements and quality requirements. The preactivation temperature of the invention is preferably from 350 to 500 ° C, more preferably from 375 to 475 ° C, still more preferably from 400 to 450 ° C, most preferably from 410 to 440 ° C; and the preactivation time is preferably from 1 to 4 hours. It is more preferably 1.5 to 3.5 hours, and most preferably 2 to 3 hours.

本发明对所述第三气体没有特别限制，以本领域技术人员熟知的保护性气体即可，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明所述第三气体优选包括氢气、氮气和惰性气体中的一种或多种，更优选为氢气、氮气或氩气。本发明对所述活化的条件没有特别限制，以本领域技术人员熟知的石油焦活化的条件即可，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明所述活化的温度优选为700～950℃，更优选为725～925℃，更优选为750～900℃，最优选为800～850℃；所述活化的时间优选为0.5～4小时，更优选为1～3.5小时，更优选为1.5～3小时，最优选为2～2.5小时。本发明对所述预活化和活化的设备没有特别限制，以本领域技术人员熟知的石油焦预活化和活化的设备即可，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明所述预活化和活化的设备优选为坩埚。The third gas is not particularly limited in the present invention, and the protective gas is well known to those skilled in the art, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements. The three gases preferably comprise one or more of hydrogen, nitrogen and an inert gas, more preferably hydrogen, nitrogen or argon. The conditions of the activation of the present invention are not particularly limited, and the conditions of petroleum coke activation well known to those skilled in the art may be used, and those skilled in the art may select and adjust according to actual production conditions, product requirements and quality requirements, and the present invention The activation temperature is preferably 700 to 950 ° C, more preferably 725 to 925 ° C, still more preferably 750 to 900 ° C, most preferably 800 to 850 ° C; the activation time is preferably 0.5 to 4 hours, more preferably It is 1 to 3.5 hours, more preferably 1.5 to 3 hours, and most preferably 2 to 2.5 hours. The apparatus for pre-activation and activation of the present invention is not particularly limited, and the equipment for pre-activation and activation of petroleum coke which is well known to those skilled in the art may be used, and those skilled in the art may select according to actual production conditions, product requirements and quality requirements. And adjustment, this The device for preactivation and activation of the invention is preferably hydrazine.

本发明对所述洗涤的步骤没有特别限制，以本领域技术人员熟知的石油焦活化后的洗涤步骤即可，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明所述洗涤的具体步骤优选依次包括自然降温、水洗、酸洗和水洗，更具体优选为自然降温，水洗至中性，酸洗，再水洗至中性。本发明所述酸洗用酸优选为盐酸、硝酸和磷酸中的一种或多种；所述洗涤的温度优选为20～100℃，更优选为40～80℃，最优选为50～100℃。本发明对所述干燥的步骤没有特别限制，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整。本发明对所述活性炭分散液的浓度没有特别限制，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明所述活性炭分散液的固含量优选为1％～10％，更优选为2％～9％，更优选为3％～8％，最优选为5％～6％。The washing step of the present invention is not particularly limited, and the washing step after the petroleum coke activation is well known to those skilled in the art, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements. The specific steps of the washing according to the invention preferably include natural cooling, water washing, pickling and water washing, and more specifically, natural cooling, water washing to neutral, pickling, and washing to neutral. The acid for pickling according to the present invention is preferably one or more of hydrochloric acid, nitric acid and phosphoric acid; the temperature of the washing is preferably from 20 to 100 ° C, more preferably from 40 to 80 ° C, most preferably from 50 to 100 ° C. . The drying step of the present invention is not particularly limited, and those skilled in the art can select and adjust according to actual production conditions, product requirements, and quality requirements. The concentration of the activated carbon dispersion liquid in the present invention is not particularly limited, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements, and the solid content of the activated carbon dispersion liquid of the present invention is preferably 1% to 10%. % is more preferably 2% to 9%, still more preferably 3% to 8%, and most preferably 5% to 6%.

本发明通过氧化介质浸渍及焦化、预活化过程，可以在石油焦表面形成活化的活性点，有利于化学活化部分造孔，降低碱使用量，增加中孔率，有效的克服了石油焦表面致密，造孔比较困难的问题。The invention can form an activated active point on the surface of petroleum coke by immersion and coking and pre-activation process of oxidizing medium, which is beneficial to chemical activation of partial pore formation, reduction of alkali usage, increase of mesoporosity, and effective overcoming of petroleum coke surface compaction. It is a difficult problem to make holes.

本发明最后将上述步骤得到的活性炭分散液与氧化石墨烯溶液混合后干燥，再在保护性气体的条件下进行热处理后，得到复合型石油焦基活性炭。In the final invention, the activated carbon dispersion obtained in the above step is mixed with the graphene oxide solution, dried, and then heat-treated under a protective gas condition to obtain a composite petroleum coke-based activated carbon.

本发明所述氧化石墨烯溶液优选为单层氧化石墨烯溶液，所述单层率优选高于等于95％。本发明对所述单层氧化石墨烯溶液的来源没有特别限制，以本领域技术人员熟知的单层氧化石墨烯溶液的来源即可，可以市售购得也可以按照常规的制备方法制备。本发明对所述氧化石墨烯的加入量没有特别限制，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明所述氧化石墨烯溶液中氧化石墨烯的质量占所述活性炭分散液中活性炭质量的比例优选为0.05％～1％，更优选为0.1％～0.9％，更优选为0.3％～0.7％，最优选为0.4％～0.6％。本发明对所述氧化石墨烯的片径没有特别限制，以本领域技术人员熟知的氧化石墨烯的片径即可，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明所述氧化石墨烯的平均片径优选为1～50μm，更优选为5～45μm，更优选为10～40μm，最优选为20～30μm。 The graphene oxide solution of the present invention is preferably a single layer graphene oxide solution, and the monolayer ratio is preferably higher than or equal to 95%. The source of the single-layer graphene oxide solution of the present invention is not particularly limited, and may be commercially available as a source of a single-layer graphene oxide solution well known to those skilled in the art, and may be commercially available or prepared according to a conventional preparation method. The amount of the graphene oxide added in the present invention is not particularly limited, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements, and the quality of graphene oxide in the graphene oxide solution of the present invention accounts for The proportion of the mass of the activated carbon in the activated carbon dispersion is preferably from 0.05% to 1%, more preferably from 0.1% to 0.9%, still more preferably from 0.3% to 0.7%, most preferably from 0.4% to 0.6%. The chip diameter of the graphene oxide is not particularly limited in the present invention, and the chip diameter of the graphene oxide well known to those skilled in the art may be used, and those skilled in the art may select and adjust according to actual production conditions, product requirements and quality requirements. The average particle diameter of the graphene oxide of the present invention is preferably from 1 to 50 μm, more preferably from 5 to 45 μm, still more preferably from 10 to 40 μm, and most preferably from 20 to 30 μm.

本发明对所述混合没有特别限制，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明所述混合优选为超声搅拌；所述混合的时间优选为0.5～2h，更优选为1～1.5h。本发明对所述干燥没有特别限制，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明所述干燥优选为喷雾干燥。The mixing of the present invention is not particularly limited, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements. The mixing according to the present invention is preferably ultrasonic stirring; the mixing time is preferably 0.5 to 2 hours. More preferably, it is 1 to 1.5 hours. The drying of the present invention is not particularly limited, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements, and the drying according to the present invention is preferably spray drying.

本发明对所述保护性气体没有特别限制，以本领域技术人员熟知的保护性气体即可，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明所述保护性气体优选包括氢气、氨气、氮气和惰性气体中的一种或多种，更优选为氢气、氨气、氮气和氩气中的一种或两种。本发明对所述热处理的条件没有特别限制，以本领域技术人员熟知的石油焦制备活性炭的热处理步骤即可，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明所述热处理的温度优选为700～1000℃，更优选为750～950℃，更优选为800～900℃，最优选为830～870℃；所述热处理的时间优选为1～4小时，更优选为1.5～3.5小时，最优选为2～3小时。The protective gas is not particularly limited in the present invention, and the protective gas is well known to those skilled in the art, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements, and the protection according to the present invention. The gas preferably includes one or more of hydrogen, ammonia, nitrogen, and an inert gas, and more preferably one or both of hydrogen, ammonia, nitrogen, and argon. The heat treatment conditions of the present invention are not particularly limited, and the heat treatment step of preparing activated carbon by petroleum coke well known to those skilled in the art may be used, and those skilled in the art may select and adjust according to actual production conditions, product requirements and quality requirements. The heat treatment temperature of the invention is preferably 700 to 1000 ° C, more preferably 750 to 950 ° C, still more preferably 800 to 900 ° C, most preferably 830 to 870 ° C; and the heat treatment time is preferably 1 to 4 hours, more It is preferably 1.5 to 3.5 hours, and most preferably 2 to 3 hours.

本发明通过将石油焦活性炭和氧化石墨烯复合并喷雾干燥，使得活性炭表面均匀包裹一层氧化石墨烯，在随后的高温还原热处理过程中，使得氧化石墨烯还原为石墨烯，改善了活性炭的电导率，降低其内阻；此外经过高温处理降低了表面官能团，改善了超级电容炭的稳定性。The invention combines and sprays the petroleum coke activated carbon and the graphene oxide to uniformly coat a layer of graphene oxide on the surface of the activated carbon, and reduces the graphene oxide to graphene in the subsequent high-temperature reduction heat treatment, thereby improving the conductance of the activated carbon. Rate, reduce its internal resistance; in addition, high temperature treatment reduces surface functional groups and improves the stability of supercapacitor carbon.

本发明为进一步提高复合型石油焦基活性炭作为超级电容器炭的特性，提升电极材料的性能，所述步骤C)具体优选为，将上述步骤得到的活性炭分散液、氧化石墨烯溶液和氮源混合后干燥，再进行热处理后，得到复合型石油焦基活性炭，即复合型石油焦基氮掺杂活性炭。In order to further improve the characteristics of the composite petroleum coke-based activated carbon as the supercapacitor carbon and improve the performance of the electrode material, the step C) is specifically preferably: mixing the activated carbon dispersion liquid, the graphene oxide solution and the nitrogen source obtained in the above step. After drying, heat treatment is performed to obtain a composite petroleum coke-based activated carbon, that is, a composite petroleum coke-based nitrogen-doped activated carbon.

本发明对所述氮源(含氮前体)没有特别限制，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明所述氮源优选为小分子含氮化合物(含氮小分子)，更优选为三聚氰胺和/或尿素，更优选为三聚氰胺或尿素，最优选为三聚氰胺。本发明对所述氮源的加入量没有特别限制，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明所述氮源的质量占所述活性炭分散液中活性炭质量的比例优选为1％～5％，更优选为1.5％～4.5％，更优选为2％～4％，最优选为2.5％～3.5％。 The nitrogen source (nitrogen-containing precursor) of the present invention is not particularly limited, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements, and the nitrogen source of the present invention is preferably a small molecule nitrogen-containing compound. (nitrogen-containing small molecule), more preferably melamine and/or urea, more preferably melamine or urea, most preferably melamine. The amount of the nitrogen source added in the present invention is not particularly limited, and those skilled in the art can select and adjust according to the actual production conditions, product requirements and quality requirements, and the quality of the nitrogen source of the present invention accounts for the activated carbon in the activated carbon dispersion. The proportion of the mass is preferably from 1% to 5%, more preferably from 1.5% to 4.5%, still more preferably from 2% to 4%, most preferably from 2.5% to 3.5%.

本发明通过将石油焦活性炭、氧化石墨烯和氮源的复合并喷雾干燥，使得活性炭表面均匀包裹一层氧化石墨烯，同时三聚氰胺也进入活性炭孔道；在随后的高温还原热处理过程中，一方面使得氧化石墨烯还原为石墨烯，改善了活性炭的电导率，降低其内阻；另一方面使得三聚氰胺在活性炭表面分解对活性炭进行氮掺杂，而氮掺杂则能极大地改善活性炭表面官能团分布，提升储能效率；此外经过高温处理降低了表面官能团，改善了超级电容炭的稳定性。The invention combines and sprays the petroleum coke activated carbon, graphene oxide and nitrogen source to make the surface of the activated carbon uniformly coat a layer of graphene oxide, and the melamine also enters the activated carbon channel; in the subsequent high temperature reduction heat treatment process, on the one hand The reduction of graphene oxide to graphene improves the electrical conductivity of activated carbon and reduces its internal resistance. On the other hand, melamine is decomposed on the surface of activated carbon to nitrogen doping the activated carbon, while nitrogen doping can greatly improve the functional group distribution on the surface of activated carbon. Improve energy storage efficiency; in addition, high temperature treatment reduces surface functional groups and improves the stability of supercapacitor carbon.

本发明为提高最后产品的品质，所述热处理后还优选包括破碎、筛选和磁选步骤；本发明对所述破碎、筛选和磁选步骤的具体过程和条件没有特别限制，本领域技术人员可以根据实际生产情况、产品要求及质量要求进行选择和调整，本发明所述破碎后的粒径优选为6～10μm，更优选为7～9μm。In order to improve the quality of the final product, the heat treatment further preferably includes a crushing, screening and magnetic separation step; the specific process and conditions of the crushing, screening and magnetic separation steps are not particularly limited, and those skilled in the art may The particle size after the crushing according to the present invention is preferably 6 to 10 μm, and more preferably 7 to 9 μm, depending on actual production conditions, product requirements, and quality requirements.

本发明提供了一种复合型石油焦基活性炭，所述复合型石油焦基活性炭由石油焦、氧化石墨烯和氮源经过复合后得到。本发明对所述复合没有特别限制，以本领域技术人员熟知的复合的概念即可，可以为包覆、半包覆、喷涂、掺杂、粘合或嵌入中的一种或多种。The invention provides a composite petroleum coke-based activated carbon obtained by compounding petroleum coke, graphene oxide and nitrogen source. The present invention is not particularly limited to the compounding, and may be a composite concept well known to those skilled in the art, and may be one or more of coating, semi-coating, spraying, doping, bonding or embedding.

参见图1，图1为本发明制备的复合型石油焦基活性炭的电镜照片。Referring to Fig. 1, Fig. 1 is an electron micrograph of a composite petroleum coke-based activated carbon prepared by the present invention.

本发明上述步骤提供了一种复合型石油焦基活性炭及其制备方法，本发明通过氧化介质浸渍及焦化、预活化过程，可以在石油焦表面形成活化的活性点，有利于化学活化部分造孔，降低碱使用量，增加中孔率；通过石墨烯改性形成导电网络，降低活性炭内阻；通过氮源复合高温处理，增加表面氮含量，增加电容炭容量性能；共同进行高温热处理降低了表面官能团，改善了超级电容炭的稳定性。本发明制备的复合型石油焦基活性炭具有合理孔径分布，大比表面积，低内阻，高容量，低杂质及低含氧官能团的优点，能够作为超级电容炭，得到性能更好的超级电容器。The above steps of the present invention provide a composite petroleum coke-based activated carbon and a preparation method thereof. The invention can form an activated active point on the surface of petroleum coke by immersion in an oxidizing medium, coking and pre-activation process, and is beneficial to chemically activated partial pore-forming. , reduce the amount of alkali used, increase the mesoporosity; form a conductive network by graphene modification, reduce the internal resistance of activated carbon; increase the surface nitrogen content by nitrogen source composite high temperature treatment, increase the capacity performance of the capacitor carbon; jointly perform high temperature heat treatment to reduce the surface Functional groups improve the stability of supercapacitor carbon. The composite petroleum coke-based activated carbon prepared by the invention has the advantages of reasonable pore size distribution, large specific surface area, low internal resistance, high capacity, low impurity and low oxygen-containing functional groups, and can be used as a supercapacitor carbon to obtain a supercapacitor with better performance.

实验结果表明，本发明制备的复合型石油焦基活性炭比表面积为1800～3500m²/g，中孔率为55～75％，平均粒径为7～10μm，含氮量为1.3％～2.5％，金属杂质<100ppm，低阻值，有机系质量比电容高达220F/g，而且循环稳定性好。The experimental results show that the composite petroleum coke-based activated carbon prepared by the invention has a specific surface area of 1800-3500 m ² /g, a mesoporosity of 55-75%, an average particle diameter of 7-10 μm, and a nitrogen content of 1.3%-2.5%. , metal impurities <100ppm, low resistance, organic mass ratio capacitance up to 220F / g, and good cycle stability.

本发明还提供了一种超级电容器，包含上述技术方案任意一项所制备的复合型石油焦基活性炭或上述技术方案所述的复合型石油焦基活性炭。本发明对所述超级电容器的定义没有特别限制，以本领域技术人员熟知的超级电容器的定义即可。The present invention also provides a supercapacitor comprising the composite petroleum coke-based activated carbon prepared by any one of the above technical solutions or the composite petroleum coke-based activated carbon according to the above technical solution. Pair of the invention The definition of the supercapacitor is not particularly limited, and may be defined by a supercapacitor well known to those skilled in the art.

为了进一步说明本发明，以下结合实施例对本发明提供的一种复合型石油焦基活性炭及其制备方法、超级电容器进行详细描述，但是应当理解，这些实施例是在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，只是为进一步说明本发明的特征和优点，而不是对本发明权利要求的限制，本发明的保护范围也不限于下述的实施例。In order to further illustrate the present invention, a composite petroleum coke-based activated carbon, a preparation method thereof, and a supercapacitor provided by the present invention are described in detail below with reference to the embodiments, but it should be understood that these embodiments are based on the technical solution of the present invention. The detailed description of the present invention and the specific operation of the present invention are provided to illustrate the features and advantages of the present invention, and the scope of the present invention is not limited to the embodiments described below.

实施例1Example 1

取100g优质石油焦粉碎成8～12μm的颗粒，加入500mL 30％的双氧水，加热至50℃浸渍2h，过滤，洗涤，干燥；于空气下加热至450℃保持45min，自然冷却，加入100g粉末状的KOH并均匀混合。将此混合物加入金属镍坩埚，于氮气气氛下以10～20℃/min的速度升温至450℃并保持3h；然后以10～20℃/min的速度升温至750℃活化1h，自然降至室温。将产物溶于水中，反复洗涤至中性，然后加入6M的盐酸回流2h，过滤，去离子水洗涤至中性；加入去离子水配成5％的水分散液；向此分散液中加入固含量0.5g的单层氧化石墨烯溶液(0.5％，100mL)及0.5g三聚氰胺，超声搅拌1h，喷雾干燥。将所得固体粉末加入回转炉中，在10％氢气-氮气混合气下升温至800℃并保持2h，降温，磁选，得到超级电容炭。Take 100g of high-quality petroleum coke into granules of 8～12μm, add 500mL of 30% hydrogen peroxide, heat to 50°C for 2h, filter, wash and dry; heat to 450°C under air for 45min, naturally cool, add 100g powder KOH and mix evenly. The mixture was added to a metal nickel crucible, and the temperature was raised to 450 ° C at a rate of 10 to 20 ° C / min under a nitrogen atmosphere for 3 h; then, the temperature was raised to 750 ° C at a rate of 10 to 20 ° C / min for 1 h, and naturally lowered to room temperature. . The product was dissolved in water, washed repeatedly to neutral, then refluxed with 6 M hydrochloric acid for 2 h, filtered, washed with deionized water until neutral; deionized water was added to form a 5% aqueous dispersion; solid was added to the dispersion A 0.5 g single layer graphene oxide solution (0.5%, 100 mL) and 0.5 g melamine were ultrasonically stirred for 1 h and spray dried. The obtained solid powder was placed in a rotary kiln, and heated to 800 ° C under a 10% hydrogen-nitrogen mixed gas for 2 h, cooled, and magnetically selected to obtain a supercapacitor carbon.

参见图2，图2为本发明实施例1制备的复合型石油焦基活性炭的电镜照片。Referring to FIG. 2, FIG. 2 is an electron micrograph of a composite petroleum coke-based activated carbon prepared in Example 1 of the present invention.

参见图3，图3为本发明实施例1制备的复合型石油焦基活性炭的孔径分布图。Referring to FIG. 3, FIG. 3 is a pore size distribution diagram of a composite petroleum coke-based activated carbon prepared in Example 1 of the present invention.

对上述实施例1制备的复合型石油焦基活性炭进行检测，活性炭的比表面积为1850m²/g，中孔率为55％，平均粒径为8.6μm，含氮量为2.1％，金属杂质<100ppm。 The composite petroleum coke-based activated carbon prepared in the above Example 1 was tested. The specific surface area of the activated carbon was 1850 m ² /g, the mesoporosity was 55%, the average particle diameter was 8.6 μm, the nitrogen content was 2.1%, and the metal impurities were < 100ppm.

将此活性炭与粘结剂SBR与CMC混合匀浆，均匀涂布在铝箔上，经干燥、碾压、冲片后组装成超级电容器(有机系，2.7V)，在电流密度为2A/g时，质量比电容为153F/g。The activated carbon and the binders SBR and CMC were mixed and homogenized, uniformly coated on an aluminum foil, and dried, laminated, and punched to assemble into a supercapacitor (organic system, 2.7 V) at a current density of 2 A/g. The mass ratio capacitance is 153F/g.

实施例2Example 2

取100g优质石油焦粉碎成50～100μm的颗粒，加入500mL 1M的硝酸并回流6h，过滤，洗涤，干燥；将物料于空气下加热至350℃保持60min，自然冷却。向物料中加入溶于乙醇中的50gKOH，均匀混合并加热除去溶剂。将此混合物加入金属镍坩埚，于氮气气氛下以10～20℃/min的速度升温至500℃并保持1h；然后以10～20℃/min的速度升温至850℃活化1h，自然降至室温。将产物溶于水中，反复洗涤至中性，然后加入6M的盐酸回流2h，过滤，去离子水洗涤至中性；加入去离子水配成5％的水分散液；向此分散液中加入固含量0.2g的单层氧化石墨烯溶液(0.5％，100mL)及2.0g三聚氰胺，超声搅拌1h，喷雾干燥。将所得固体粉末加入回转炉中，在10％氨气-氩气混合气下升温至850℃并保持1.5h，降温，通过球磨机二次粉碎至8～10μm，磁选，得到超级电容炭。100 g of high-quality petroleum coke was pulverized into 50-100 μm particles, 500 mL of 1 M nitric acid was added and refluxed for 6 h, filtered, washed and dried; the material was heated to 350 ° C under air for 60 min, and naturally cooled. To the material was added 50 g of KOH dissolved in ethanol, uniformly mixed and heated to remove the solvent. The mixture was added to a metal nickel crucible, and the temperature was raised to 500 ° C at a rate of 10 to 20 ° C / min under nitrogen atmosphere for 1 h; then, the temperature was raised to 850 ° C at a rate of 10 to 20 ° C / min for 1 h, and naturally lowered to room temperature. . The product was dissolved in water, washed repeatedly to neutral, then refluxed with 6 M hydrochloric acid for 2 h, filtered, washed with deionized water until neutral; deionized water was added to form a 5% aqueous dispersion; solid was added to the dispersion A 0.2 g single layer graphene oxide solution (0.5%, 100 mL) and 2.0 g melamine were ultrasonically stirred for 1 h and spray dried. The obtained solid powder was placed in a rotary kiln, heated to 850 ° C under a mixture of 10% ammonia-argon gas for 1.5 h, cooled, and secondarily pulverized by a ball mill to 8 to 10 μm to be magnetically selected to obtain a supercapacitor carbon.

对上述实施例2制备的复合型石油焦基活性炭进行检测，活性炭的比表面积为1650m²/g，中孔率为62％，平均粒径为8.5μm，含氮量为2.1％，金属杂质<100ppm。The composite petroleum coke-based activated carbon prepared in the above Example 2 was tested. The specific surface area of the activated carbon was 1650 m ² /g, the mesoporosity was 62%, the average particle diameter was 8.5 μm, the nitrogen content was 2.1%, and the metal impurities were < 100ppm.

将此活性炭与粘结剂SBR与CMC混合匀浆，均匀涂布在铝箔上，经干燥、碾压、冲片后组装成超级电容器(有机系，2.7V)，在电流密度为2A/g时，质量比电容为140F/g。The activated carbon and the binders SBR and CMC were mixed and homogenized, uniformly coated on an aluminum foil, and dried, laminated, and punched to assemble into a supercapacitor (organic system, 2.7 V) at a current density of 2 A/g. The mass ratio capacitance is 140F/g.

实施例3Example 3

取100g优质石油焦粉碎成100～150μm的颗粒，加入500mL水，加入氢氧化钾调pH值大于11并加入20g高铁酸钾，室温搅拌24h，小心向其中加入100mL 2M盐酸，过滤，洗涤，干燥；将物料于空气下加热至550℃保持120min，自然冷却，加入200g粉末状的NaOH-KOH(1:1)并均匀混合。将此混合物加入金属镍坩埚，于氮气气氛下以10～20℃/min的速度升温至400℃并保持3h；然后以10～20℃/min的速度升温至800℃活化1h，自然降至室温。将产物溶于水中，反复洗涤至中性，然后加入6M的盐酸回流2h，过滤，去离子水洗涤至中性；加入去离子水配成5％的水分散液；向此分散液中加入固含量0.2g的单层氧化石墨烯溶液(0.5％，100mL)及1.0g三聚氰胺，超声搅拌1h，喷雾干燥。将所得固体粉末加入回转炉中，在10％氨气-氮气混合气下升温至800℃并保持2h，降温，通过球磨机二次粉碎至8～10μm，磁选，得到超级电容炭。Take 100g of high-quality petroleum coke into 100~150μm particles, add 500mL water, add potassium hydroxide to adjust the pH value to more than 11 and add 20g potassium ferrate, stir at room temperature for 24h, carefully add 100mL 2M hydrochloric acid, filter, wash and dry The material was heated to 550 ° C under air for 120 min, cooled naturally, and 200 g of powdered NaOH-KOH (1:1) was added and uniformly mixed. The mixture was added to a metal nickel crucible, and the temperature was raised to 400 ° C at a rate of 10 to 20 ° C / min under nitrogen atmosphere for 3 h; then, the temperature was raised to 800 ° C at a rate of 10 to 20 ° C / min for 1 h, and naturally lowered to room temperature. . The product was dissolved in water, washed repeatedly to neutral, then added with 6 M hydrochloric acid reflux for 2 h, filtered, washed with deionized water Neutral; add deionized water to form a 5% aqueous dispersion; add 0.2g of a single layer graphene oxide solution (0.5%, 100mL) and 1.0g of melamine to the dispersion, ultrasonically stir for 1h, spray dry. The obtained solid powder was placed in a rotary kiln, heated to 800 ° C under a 10% ammonia-nitrogen mixed gas for 2 h, cooled, and secondarily pulverized by a ball mill to 8 to 10 μm to be magnetically selected to obtain a supercapacitor carbon.

对上述实施例3制备的复合型石油焦基活性炭进行检测，活性炭的比表面积为2650m²/g，中孔率为65％，平均粒径为9.1μm，含氮量为1.4％，金属杂质<100ppm。The composite petroleum coke-based activated carbon prepared in the above Example 3 was tested. The specific surface area of the activated carbon was 2650 m ² /g, the mesoporosity was 65%, the average particle diameter was 9.1 μm, the nitrogen content was 1.4%, and the metal impurities were < 100ppm.

将此活性炭与粘结剂SBR与CMC混合匀浆，均匀涂布在铝箔上，经干燥、碾压、冲片后组装成超级电容器(有机系，2.7V)，在电流密度为2A/g时，质量比电容为186F/g。The activated carbon and the binders SBR and CMC were mixed and homogenized, uniformly coated on an aluminum foil, and dried, laminated, and punched to assemble into a supercapacitor (organic system, 2.7 V) at a current density of 2 A/g. The mass ratio capacitance is 186F/g.

实施例4Example 4

取100g优质石油焦粉碎成25～50μm的颗粒，加入500mL水，加入硫酸调pH值小于2并加入20g高锰酸钾，80℃搅拌12h，冷却，向其中加入100mL2M盐酸及10mL 30％的双氧水，过滤，洗涤，干燥；将物料于氮气下加热至600℃保持180min，自然冷却，加入250g粉末状的KOH并均匀混合。将此混合物加入金属镍坩埚，于氩气气氛下以10～20℃/min的速度升温至450℃并保持3h；然后以10～20℃/min的速度升温至760℃活化3h，自然降至室温。将产物溶于水中，反复洗涤至中性，然后加入6M的盐酸回流2h，过滤，去离子水洗涤至中性；加入去离子水配成5％的水分散液；向此分散液中加入固含量0.7g的单层氧化石墨烯溶液(0.5％，100mL)及3.0g三聚氰胺，超声搅拌1h，喷雾干燥。将所得固体粉末加入回转炉中，在10％氢气-氮气混合气下升温至780℃并保持2h，降温，通过球磨机二次粉碎至8～10μm，磁选，得到超级电容炭。Take 100g of high-quality petroleum coke into 25~50μm particles, add 500mL water, add sulfuric acid to adjust the pH value to less than 2 and add 20g potassium permanganate, stir at 80 °C for 12h, cool, add 100mL 2M hydrochloric acid and 10mL 30% hydrogen peroxide , filtration, washing, drying; the material was heated to 600 ° C under nitrogen for 180 min, cooled naturally, 250 g of powdered KOH was added and uniformly mixed. The mixture was added to a metal nickel crucible, and heated to 450 ° C at a rate of 10 to 20 ° C / min under an argon atmosphere for 3 h; then heated to 760 ° C at a rate of 10 to 20 ° C / min for 3 h, naturally reduced to Room temperature. The product was dissolved in water, washed repeatedly to neutral, then refluxed with 6 M hydrochloric acid for 2 h, filtered, washed with deionized water until neutral; deionized water was added to form a 5% aqueous dispersion; solid was added to the dispersion A 0.7 g single layer graphene oxide solution (0.5%, 100 mL) and 3.0 g melamine were ultrasonically stirred for 1 h and spray dried. The obtained solid powder was placed in a rotary kiln, heated to 780 ° C under a 10% hydrogen-nitrogen mixed gas for 2 h, cooled, and secondarily pulverized by a ball mill to 8 to 10 μm to be magnetically selected to obtain a supercapacitor carbon.

对上述实施例4制备的复合型石油焦基活性炭进行检测，活性炭的比表面积为3150m²/g，中孔率为70％，平均粒径为9.2μm，含氮量为2.2％，金属杂质<100ppm。 The composite petroleum coke-based activated carbon prepared in the above Example 4 was tested. The specific surface area of the activated carbon was 3150 m ² /g, the mesoporosity was 70%, the average particle diameter was 9.2 μm, the nitrogen content was 2.2%, and the metal impurities were < 100ppm.

将此活性炭与粘结剂SBR与CMC混合匀浆，均匀涂布在铝箔上，经干燥、碾压、冲片后组装成超级电容器(有机系，2.7V)，在电流密度为2A/g时，质量比电容为225F/g。The activated carbon and the binders SBR and CMC were mixed and homogenized, uniformly coated on an aluminum foil, and dried, laminated, and punched to assemble into a supercapacitor (organic system, 2.7 V) at a current density of 2 A/g. The mass ratio capacitance is 225F/g.

以上对本发明提供的一种复合型石油焦基活性炭及其制备方法、超级电容器进行了详细的介绍，本文中应用了具体个例对本发明的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本发明的方法及其核心思想，包括最佳方式，并且也使得本领域的任何技术人员都能够实践本发明，包括制造和使用任何装置或***，和实施任何结合的方法。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。本发明专利保护的范围通过权利要求来限定，并可包括本领域技术人员能够想到的其他实施例。如果这些其他实施例具有不是不同于权利要求文字表述的结构要素，或者如果它们包括与权利要求的文字表述无实质差异的等同结构要素，那么这些其他实施例也应包含在权利要求的范围内。 The composite petroleum coke-based activated carbon provided by the present invention, the preparation method thereof and the supercapacitor are described in detail. The principle and the embodiment of the present invention are described in the following. The description of the above embodiment is only The methodologies and core concepts of the present invention, including the best mode, are also to be understood by those skilled in the art, including making and using any device or system, and performing any combination. It should be noted that those skilled in the art can make various modifications and changes to the present invention without departing from the spirit and scope of the invention. The scope of the invention is defined by the claims, and may include other embodiments that are apparent to those skilled in the art. Such other embodiments are intended to be included within the scope of the appended claims.

Claims

一种复合型石油焦基活性炭的制备方法，其特征在于，包括以下步骤：A method for preparing a composite petroleum coke-based activated carbon, comprising the steps of:

A)将经过氧化性介质处理后的石油焦颗粒，在第一气体的条件下进行焦化后，得到活性炭前体；A) the petroleum coke particles treated by the oxidizing medium are coked under the condition of the first gas to obtain an activated carbon precursor;

B)将上述步骤得到的活性炭前体与碱混合后，在第二气体的条件下进行预活化，然后在第三气体的条件下进行活化，再洗涤后得到活性炭分散液；B) after the activated carbon precursor obtained in the above step is mixed with a base, pre-activated under the condition of the second gas, and then activated under the condition of the third gas, and then washed to obtain an activated carbon dispersion;

C)将上述步骤得到的活性炭分散液与氧化石墨烯溶液混合后干燥，再在保护性气体的条件下进行热处理后，得到复合型石油焦基活性炭。C) The activated carbon dispersion obtained in the above step is mixed with a graphene oxide solution, dried, and then heat-treated under a protective gas condition to obtain a composite petroleum coke-based activated carbon.
根据权利要求1所述的制备方法，其特征在于，所述氧化性介质包括双氧水、硝酸溶液、次氯酸溶液、高氯酸溶液、高铁酸钾溶液、高铁酸钠溶液、高锰酸钾溶液和锰酸钾水溶液中的一种或多种；The preparation method according to claim 1, wherein the oxidizing medium comprises hydrogen peroxide solution, nitric acid solution, hypochlorous acid solution, perchloric acid solution, potassium ferrate solution, sodium ferrate solution, potassium permanganate solution. And one or more of an aqueous solution of potassium manganate;

所述石油焦包括蜂窝焦、海绵焦、弹丸焦和针状焦中的一种或多种；所述石油焦颗粒的粒径为5～150μm；The petroleum coke includes one or more of a honeycomb coke, a sponge coke, a projectile coke, and a needle coke; the petroleum coke particles have a particle diameter of 5 to 150 μm;

所述处理的时间为2～24h，所述处理的温度为0～80℃。The treatment time is 2 to 24 hours, and the treatment temperature is 0 to 80 °C.
根据权利要求1所述的制备方法，其特征在于，所述第一气体包括空气、氧气、氢气、氮气、惰性气体、二氧化碳和水蒸气中的一种或多种；The preparation method according to claim 1, wherein the first gas comprises one or more of air, oxygen, hydrogen, nitrogen, an inert gas, carbon dioxide, and water vapor;

所述焦化的温度为350～700℃，所述焦化的时间为1～6小时。The coking temperature is 350 to 700 ° C, and the coking time is 1 to 6 hours.
根据权利要求1所述的制备方法，其特征在于，所述活性炭前体与碱的质量比为1：(0.5～5)；The preparation method according to claim 1, wherein the mass ratio of the activated carbon precursor to the base is 1: (0.5 to 5);

所述碱包括氢氧化钾、氢氧化钠、氢氧化锂和氢氧化钙其中一种或多种；The base includes one or more of potassium hydroxide, sodium hydroxide, lithium hydroxide and calcium hydroxide;

所述碱为颗粒状碱，所述颗粒状碱的粒径为10～300μm。The base is a particulate alkali, and the granular base has a particle diameter of 10 to 300 μm.
根据权利要求1所述的制备方法，其特征在于，所述第二气体包括空气、氢气、氮气和惰性气体中的一种或多种；The preparation method according to claim 1, wherein the second gas comprises one or more of air, hydrogen, nitrogen, and an inert gas;

所述预活化的温度为350～500℃，所述预活化的时间为1～4小时；The preactivation temperature is 350 to 500 ° C, and the preactivation time is 1 to 4 hours;

所述第三气体包括氢气、氮气和惰性气体中的一种或多种；The third gas includes one or more of hydrogen, nitrogen, and an inert gas;

所述活化的温度为700～950℃，所述活化的时间为0.5～4小时。The activation temperature is 700 to 950 ° C, and the activation time is 0.5 to 4 hours.
根据权利要求1所述的制备方法，其特征在于，所述步骤C)具体为：The preparation method according to claim 1, wherein the step C) is specifically:

将上述步骤得到的活性炭分散液、氧化石墨烯溶液和氮源混合后干燥，再进行热处理后，得到复合型石油焦基活性炭；The activated carbon dispersion obtained in the above step, the graphene oxide solution and the nitrogen source are mixed and dried, and then After the heat treatment, a composite petroleum coke-based activated carbon is obtained;

所述氮源包括三聚氰胺和/或尿素；The nitrogen source comprises melamine and/or urea;

所述氧化石墨烯溶液中氧化石墨烯的质量占所述活性炭分散液中活性炭质量的比例为0.05％～1％；The ratio of the mass of the graphene oxide in the graphene oxide solution to the mass of the activated carbon in the activated carbon dispersion is 0.05% to 1%;

所述氮源的质量占所述活性炭分散液中活性炭质量的比例为1％～5％。The ratio of the mass of the nitrogen source to the mass of the activated carbon in the activated carbon dispersion is from 1% to 5%.
根据权利要求1所述的制备方法，其特征在于，所述保护性气体包括氢气、氨气、氮气和惰性气体中的一种或多种；The preparation method according to claim 1, wherein the protective gas comprises one or more of hydrogen, ammonia, nitrogen, and an inert gas;

所述热处理的温度为700～1000℃，所述热处理的时间为1～4小时。The heat treatment temperature is 700 to 1000 ° C, and the heat treatment time is 1 to 4 hours.
根据权利要求1所述的制备方法，其特征在于，所述热处理后还包括破碎、筛选和磁选步骤；The preparation method according to claim 1, wherein the heat treatment further comprises a crushing, screening and magnetic separation step;

所述破碎后的粒径为6～10μm。The particle size after the crushing is 6 to 10 μm.
一种复合型石油焦基活性炭，其特征在于，所述复合型石油焦基活性炭由石油焦、氧化石墨烯和氮源经过复合后得到。A composite petroleum coke-based activated carbon characterized in that the composite petroleum coke-based activated carbon is obtained by compounding petroleum coke, graphene oxide and a nitrogen source.
一种超级电容器，其特征在于，包含权利要求1～8任意一项所制备的复合型石油焦基活性炭或权利要求9所述的复合型石油焦基活性炭。 A supercapacitor comprising the composite petroleum coke-based activated carbon prepared according to any one of claims 1 to 8 or the composite petroleum coke-based activated carbon according to claim 9.