CN108288547A - The preparation method of nitrogen phosphorus sulphur codope ordered mesoporous carbon material - Google Patents

The preparation method of nitrogen phosphorus sulphur codope ordered mesoporous carbon material Download PDF

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CN108288547A
CN108288547A CN201810032994.3A CN201810032994A CN108288547A CN 108288547 A CN108288547 A CN 108288547A CN 201810032994 A CN201810032994 A CN 201810032994A CN 108288547 A CN108288547 A CN 108288547A
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ordered mesoporous
nitrogen
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宋伟明
徐立洋
程晓宇
邓启刚
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Abstract

氮磷硫三元共掺杂有序介孔碳材料的制备方法,本发明涉及一种氮磷硫三元共掺杂有序介孔碳材料的制备方法，它为了解决现有的单一杂原子掺杂对介孔碳材料电容性能提高有限的问题。首先制备有序介孔二氧化硅模板(KIT‑6)；通过纳米灌注法将蔗糖、磷酸和氨基硫脲混合溶液与KIT‑6分散液在40℃～60℃搅拌陈化10 h～14 h。将得到的糊状复合物放置于烘箱中于70℃～90℃下干燥10 h～14 h，最后置于管式炉中在高纯氮气下(氮气流速为50 mL/s)于700℃～900℃热解1～3 h，加热速率为2℃/min。碳化后的复合材料浸没于HF溶液中并搅拌以除去二氧化硅模板，抽滤，用超纯水和乙醇各洗涤，并干燥后得氮磷硫三元共掺杂有序介孔碳材料（NPS‑OMC）。本发明通过模板采用纳米灌注制备氮磷硫三元共掺杂有序介孔碳材料，该材料电极的比电容可以达到了343 F/g。

A method for preparing nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous carbon materials. The present invention relates to a method for preparing nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous carbon materials. Doping has limited improvement on the capacitive performance of mesoporous carbon materials. First, the ordered mesoporous silica template (KIT‑6) was prepared; the mixed solution of sucrose, phosphoric acid and thiosemicarbazide and the KIT‑6 dispersion were aged for 10 h to 14 h at 40 °C to 60 °C by nanoperfusion method . The obtained paste compound was dried in an oven at 70°C to 90°C for 10 h to 14 h, and finally placed in a tube furnace under high-purity nitrogen (nitrogen flow rate of 50 mL/s) at 700°C to Pyrolysis at 900°C for 1 to 3 hours, with a heating rate of 2°C/min. The carbonized composite material was submerged in HF solution and stirred to remove the silica template, filtered with suction, washed with ultrapure water and ethanol, and dried to obtain a nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous carbon material ( NPS-OMC). The invention prepares nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous carbon materials through templates by nanometer perfusion, and the specific capacitance of electrodes of the materials can reach 343 F/g.

Description

氮磷硫三元共掺杂有序介孔碳材料的制备方法Preparation method of nitrogen, phosphorus and sulfur ternary co-doped ordered mesoporous carbon materials

技术领域technical field

本发明涉及一种氮磷硫三元共掺杂有序介孔碳材料的制备方法。The invention relates to a preparation method of nitrogen, phosphorus and sulfur ternary co-doped ordered mesoporous carbon materials.

背景技术Background technique

随着全球经济的快速发展，环境问题和能源危机日益恶化已严重威胁到人类的生存和社会的进步。因此，环境污染和能源供应已成为当今世界两大最急需解决的问题。环境污染和能源供应这两个领域有着密切的联系，通过可持续的、环境友好的技术开发可再生的新能源来替代化石燃料是一个全新的解决方案。With the rapid development of the global economy, environmental problems and energy crises have become increasingly serious threats to human survival and social progress. Therefore, environmental pollution and energy supply have become the two most urgent problems in the world today. The two fields of environmental pollution and energy supply are closely related, and it is a brand-new solution to develop renewable new energy sources to replace fossil fuels through sustainable and environmentally friendly technologies.

为了获得安全可再生的新能源和减少温室气体的排放，科学家们研发了储存能量的新材料和新方法。超级电容器以及先进的电池***已经被认为是非常有前景的储能装置，它们既能存储可再生能源也能减少对化石燃料的需求。特别是超级电容器，以其快速的充放电过程、高的比容量、长的循环寿命、简单的原理、高的功率密度和能量密度等已经成为高效、实用且环保的储能装置。目前，超级电容器主要应用于便携式电子设备、混合动力汽车、计算机终端、航空航天等领域。众所周知，超级电容器的电极材料对其电容性能起着决定性的作用，主要包括三类：过渡金属化合物、导电聚合物和多孔碳材料。其中，多孔碳材料以其长的循环寿命、高的功率密度、宽的工作电势窗口和低的成本作为先进的电极材料已广泛应用于商业的超级电容中。但是，纯碳基超级电容器的比电容较低，一般小于150 F/g，难以满足人类对能量密度的需求。因此，合成出兼具高能量密度、高功率密度、长循环稳定性、经济环保的电极材料仍是一项具有重要意义的课题。In order to obtain safe and renewable new energy sources and reduce greenhouse gas emissions, scientists have developed new materials and methods for energy storage. Supercapacitors, as well as advanced battery systems, have been considered as very promising energy storage devices that can both store renewable energy and reduce the demand for fossil fuels. In particular, supercapacitors have become efficient, practical and environmentally friendly energy storage devices due to their fast charging and discharging process, high specific capacity, long cycle life, simple principle, high power density and energy density. At present, supercapacitors are mainly used in portable electronic equipment, hybrid electric vehicles, computer terminals, aerospace and other fields. It is well known that the electrode materials of supercapacitors play a decisive role in their capacitive performance, mainly including three categories: transition metal compounds, conductive polymers and porous carbon materials. Among them, porous carbon materials have been widely used in commercial supercapacitors as advanced electrode materials due to their long cycle life, high power density, wide operating potential window, and low cost. However, the specific capacitance of pure carbon-based supercapacitors is low, generally less than 150 F/g, which is difficult to meet human needs for energy density. Therefore, it is still an important topic to synthesize electrode materials with high energy density, high power density, long-term cycle stability, economical and environmental protection.

碳基电极材料以产生双电层电容为主。目前研究最多的碳基超电极材料主要有活性炭(ACs)、石墨烯(Graphene)、碳纳米管(CNTs)、碳纳米纤维(CNFs)以及有序介孔碳(OMC)等。在各种碳材料中，有序介孔碳因具有均一的孔径和特殊的孔道而具有高的功率密度和良好的循环稳定性，被认为是一种十分有应用潜力的超级电容器电极材料。许多研究已经证明：多孔碳的孔径分布在电化学性能中起着重要作用。如果碳材料的孔径小于溶剂化离子，那么碳材料就难以被电解质浸润，进而就会限制电容值。有序介孔碳因具有均一和合适的孔径(2-50 nm)以及可以缩短电子传输路径的有序通道，因此导致了优异的电化学性能，被认为是非常有前景的超电材料。然而，由于单纯有序介孔碳具有较高的化学反应惰性和较差的表面润湿性等缺点，在作为超级电容器的电极材料时只有很少的活性位点可用于电荷存储，导致电化学电容性能不理想,这严重制约了它的实际应用。故而，对有序介孔碳材料进行物理化学改性成为有序介孔碳研究领域的热点内容。Carbon-based electrode materials are mainly used to generate electric double layer capacitance. At present, the most studied carbon-based superelectrode materials mainly include activated carbons (ACs), graphene (Graphene), carbon nanotubes (CNTs), carbon nanofibers (CNFs), and ordered mesoporous carbons (OMCs). Among various carbon materials, ordered mesoporous carbon has high power density and good cycle stability due to its uniform pore size and special channels, and is considered to be a very promising electrode material for supercapacitors. Many studies have demonstrated that the pore size distribution of porous carbon plays an important role in the electrochemical performance. If the pore size of the carbon material is smaller than the solvated ion, the carbon material is difficult to be wetted by the electrolyte, which will limit the capacitance value. Ordered mesoporous carbons are considered to be very promising superelectric materials due to their uniform and suitable pore size (2–50 nm) and ordered channels that can shorten electron transport paths, resulting in excellent electrochemical performance. However, due to the shortcomings of purely ordered mesoporous carbons such as high chemical reaction inertness and poor surface wettability, there are only few active sites available for charge storage when used as electrode materials for supercapacitors, resulting in electrochemical Capacitor performance is not ideal, which seriously restricts its practical application. Therefore, the physical and chemical modification of ordered mesoporous carbon materials has become a hot topic in the field of ordered mesoporous carbon research.

最近，非金属杂原子掺杂介孔碳材料在能量存储方面已经引起了极大的关注。例如，研究发现在碳骨架中掺入氮元素可显著提高比电容。这是因为氮元素的掺入能够：①通过法拉第氧化还原反应提高总的赝电容。②增加碳电极材料导电性，进而提高双层电容和伪电容的电容保持率。③改善碳电极材料对电解液的表面润湿性。因此，氮掺杂可以确保对存储电荷暴露表面的充分利用。各种形态的碳材料已经用氮掺杂处理，并表现出优异的电化学电容性能。目前用于掺杂的非金属杂原子包括氮(N)、磷(P)、硫(S)和硼(B)等。这些杂原子与碳原子通过共价键相连在碳材料中引入官能团，通过给电子或吸电子效应改变碳材料的物理化学性质。由于这些官能团与电解质间能产生法拉第反应，因此其能够通过赝电容效应增强总的比电容。其中，氮掺杂是增强比电容同时保持碳材料良好速率能力的最有效的方法。氮原子相对于碳原子具有供电子效应，因而能够提高碳材料的物理化学性质，比如表面极性，导电性和润湿性。因此，氮掺杂有序介孔碳材料已经受到了很大的关注。Recently, nonmetallic heteroatom-doped mesoporous carbon materials have attracted great attention for energy storage. For example, it was found that the incorporation of nitrogen into the carbon framework can significantly improve the specific capacitance. This is because the incorporation of nitrogen element can: ① improve the total pseudocapacitance through faradaic redox reaction. ② Increase the conductivity of carbon electrode materials, thereby improving the capacitance retention rate of double-layer capacitance and pseudo-capacitance. ③ Improve the surface wettability of the carbon electrode material to the electrolyte. Thus, nitrogen doping can ensure full utilization of the exposed surface for storing charges. Various morphological carbon materials have been treated with nitrogen doping and exhibit excellent electrochemical capacitive performance. Non-metallic heteroatoms currently used for doping include nitrogen (N), phosphorus (P), sulfur (S) and boron (B). These heteroatoms are connected to carbon atoms through covalent bonds to introduce functional groups into carbon materials, and change the physical and chemical properties of carbon materials through electron donating or electron withdrawing effects. Due to the faradaic reaction between these functional groups and the electrolyte, it can enhance the overall specific capacitance through the pseudocapacitive effect. Among them, nitrogen doping is the most effective method to enhance the specific capacitance while maintaining the good rate capability of carbon materials. Nitrogen atoms have an electron-donating effect relative to carbon atoms, which can improve the physicochemical properties of carbon materials, such as surface polarity, electrical conductivity, and wettability. Therefore, nitrogen-doped ordered mesoporous carbon materials have received great attention.

发明内容Contents of the invention

本发明的目的是要研究出一种制备氮磷硫三元共掺杂有序介孔碳材料的方法。从而解决单一杂原子掺杂对介孔碳材料电容性能提高有限的问题。The purpose of the present invention is to develop a method for preparing nitrogen, phosphorus and sulfur ternary co-doped ordered mesoporous carbon materials. In this way, the problem of limited improvement of the capacitive performance of mesoporous carbon materials by single heteroatom doping is solved.

本发明氮磷硫三元共掺杂有序介孔碳材料的制备方法按下列步骤实现：The preparation method of nitrogen, phosphorus and sulfur ternary co-doped ordered mesoporous carbon material of the present invention is realized according to the following steps:

一、采用水热合成法合成有序介孔二氧化硅模板 (KIT-6)；1. Synthesis of ordered mesoporous silica template (KIT-6) by hydrothermal synthesis method;

二、（1）干燥的KIT-6 在去离子水中超声处理得均匀分散液；于此同时将蔗糖、磷酸和氨基硫脲加入到去离子水中搅拌得到均匀的溶液。(2) 将后者转移到前者中并在通风橱中于40℃～60℃下继续搅拌10 h～14 h。(3) 将得到的糊状复合物放置于烘箱中于70℃～90℃下干燥10 h～14 h，然后把剩余的固体研磨成粉末。(4) 把该复合材料粉末置于管式炉中在高纯氮气下于700℃～900℃热解1～3 h，加热速率为2 ℃/min。(5) 把碳化后的复合材料浸没于HF溶液中并搅拌以除去二氧化硅模板。(6) 抽滤，用超纯水和乙醇各洗涤，并干燥后得氮磷硫三元共掺杂有序介孔碳（NPS-OMC）。2. (1) The dried KIT-6 is ultrasonically treated in deionized water to obtain a uniform dispersion; at the same time, add sucrose, phosphoric acid and thiosemicarbazide to deionized water and stir to obtain a uniform solution. (2) Transfer the latter to the former and continue stirring for 10 h to 14 h in a fume hood at 40°C to 60°C. (3) Place the obtained paste compound in an oven at 70°C to 90°C to dry for 10 h to 14 h, and then grind the remaining solid into powder. (4) Pyrolyze the composite material powder in a tube furnace at 700°C-900°C for 1-3 h under high-purity nitrogen gas, and the heating rate is 2°C/min. (5) Submerge the carbonized composite in HF solution and stir to remove the silica template. (6) Suction filtration, washing with ultrapure water and ethanol, and drying to obtain nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous carbon (NPS-OMC).

本发明将氮磷硫三元共掺杂有序介孔碳材料粉末与聚四氟乙烯 (PTFE) 溶液混合，搅拌成浆液，然后均匀涂抹在泡沫镍上，压制成片，得到氮磷硫三元共掺杂有序介孔碳材料超级电容器电极。The present invention mixes nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous carbon material powder with polytetrafluoroethylene (PTFE) solution, stirs to form a slurry, and then evenly smears it on foamed nickel, and presses it into sheets to obtain nitrogen, phosphorus, and sulfur three Elemental co-doped ordered mesoporous carbon materials for supercapacitor electrodes.

本发明采用聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物与正硅酸乙酯水热形成有序介孔二氧化硅膜版（KIT-6），通过纳米灌注方法合成了有序性良好的氮磷硫三元共掺杂有序介孔碳。二氧化硅膜版及蔗糖、磷酸和氨基硫脲的作用主要包括：The present invention adopts polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and tetraethyl orthosilicate to form ordered mesoporous silica membrane plate (KIT-6) through hydrothermal Nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous carbons with good order were synthesized by perfusion method. The functions of silica stencil and sucrose, phosphoric acid and thiosemicarbazide mainly include:

1、二氧化硅模板主要为合成有序介孔碳材料提供孔道结构，使经过模板灌注的碳材料能够得以保持有序介孔结构；2、蔗糖作为合成氮磷硫三元共掺杂有序介孔碳的碳源可以与硬模板KIT-6形成良好的兼容性，使灌注程度更加完全；3、磷酸作为合成氮磷硫三元共掺杂有序介孔碳的磷源可以为材料本身提供法拉第赝电容，使材料的电容性能提高；4、氨基硫脲作为合成氮磷硫三元共掺杂有序介孔碳的氮源与硫源，可以提升材料本身的润湿且提高材料的法拉第赝电容。1. The silica template mainly provides a pore structure for the synthesis of ordered mesoporous carbon materials, so that the carbon materials perfused by the template can maintain an ordered mesoporous structure; The carbon source of mesoporous carbon can form good compatibility with the hard template KIT-6, so that the degree of perfusion is more complete; 3. Phosphoric acid can be used as a phosphorus source for the synthesis of nitrogen, phosphorus and sulfur ternary co-doped ordered mesoporous carbon for the material itself Provide Faraday pseudocapacitance to improve the capacitance performance of the material; 4. Thiosemicarbazide is used as the nitrogen source and sulfur source for the synthesis of nitrogen, phosphorus and sulfur ternary co-doped ordered mesoporous carbon, which can improve the wetting of the material itself and improve the Faraday pseudocapacitor.

同时氮磷硫三元共掺杂有序介孔碳具有较高的比表面积，可以为电容反应提供更多的反应活性位点，进一步提高材料的电容，而其有序的介孔结构可以缩短导电粒子运输的路径，从而提高材料的电化学性能。At the same time, nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous carbon has a high specific surface area, which can provide more reactive sites for capacitive reactions, further improving the capacitance of the material, and its ordered mesoporous structure can shorten the Pathways for the transport of conductive particles, thereby enhancing the electrochemical performance of materials.

本发明在电解液浓度为6 mol/L的KOH溶液的情况下，该氮磷硫三元共掺杂有序介孔碳的比电容可以达到了343 F/g。In the present invention, in the case of a KOH solution with an electrolyte concentration of 6 mol/L, the specific capacitance of the nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous carbon can reach 343 F/g.

附图说明Description of drawings

图1为实施例一步骤一得到的有序介孔二氧化硅KIT-6的XRD图；Fig. 1 is the XRD pattern of the ordered mesoporous silica KIT-6 obtained in step 1 of Example 1;

图2为实施例一步骤一得到的有序介孔二氧化硅KIT-6的TEM图；Fig. 2 is the TEM picture of the ordered mesoporous silica KIT-6 obtained in step 1 of embodiment 1;

图3为实施例一得到的氮磷硫三元共掺杂有序介孔碳材料的XRD图；Figure 3 is the XRD pattern of the nitrogen, phosphorus and sulfur ternary co-doped ordered mesoporous carbon material obtained in Example 1;

图4为实施例一得到的氮磷硫三元共掺杂有序介孔碳材料的物理吸附-脱附与孔径分布图；Fig. 4 is the physical adsorption-desorption and pore size distribution diagram of the nitrogen, phosphorus and sulfur ternary co-doped ordered mesoporous carbon material obtained in Example 1;

图5为实施例一得到的氮磷硫三元共掺杂有序介孔碳材料的TEM图；5 is a TEM image of the nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous carbon material obtained in Example 1;

图6为实施例一得到的氮磷硫三元共掺杂有序介孔碳材料的SEM图；6 is an SEM image of the nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous carbon material obtained in Example 1;

图7为实施例一得到的氮磷硫三元共掺杂有序介孔碳材料的EDS图；7 is an EDS diagram of the nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous carbon material obtained in Example 1;

图8为实施例一得到的氮磷硫三元共掺杂有序介孔碳材料的XPS图；Fig. 8 is the XPS diagram of the nitrogen, phosphorus and sulfur ternary co-doped ordered mesoporous carbon material obtained in Example 1;

图9为实例一、二、三中氮磷硫三元共掺杂有序介孔碳材料的循环伏安曲线图；Fig. 9 is a cyclic voltammetry curve diagram of nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous carbon materials in Examples 1, 2, and 3;

图10为实例一、二、三中氮磷硫三元共掺杂有序介孔碳材料的恒电流充放电曲线图。Fig. 10 is a constant current charge-discharge curve diagram of nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous carbon materials in Examples 1, 2, and 3.

具体实施方式Detailed ways

具体实施方式一：本实施方式氮磷硫三元共掺杂有序介孔碳材料的制备方法按下列步骤实施：Specific Embodiment 1: In this embodiment, the preparation method of nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous carbon materials is implemented according to the following steps:

一、采用水热合成法合成有序介孔二氧化硅模板 (KIT-6)；1. Synthesis of ordered mesoporous silica template (KIT-6) by hydrothermal synthesis method;

二、（1）干燥的KIT-6 在去离子水中超声处理得均匀分散液；于此同时将蔗糖、磷酸和氨基硫脲加入到去离子水中搅拌得到均匀的溶液，且质量比，m(KIT-6)：m(蔗糖)：m(磷酸)：m(氨基硫脲) = 8: 8:(2~1):(2~1)。(2) 将后者转移到前者中并在通风橱中于40℃下继续搅拌12h。(3) 将得到的糊状复合物放置于烘箱中于80℃下干燥12h，然后把干燥后的固体研磨成粉末。(4) 把该复合材料粉末置于管式炉中在高纯氮气(50 ml/s)下于800℃热解2h，加热速率为2 ℃/min。(5) 把碳化后的复合材料浸没于100 mL 质量分数为5%的HF溶液中并搅拌24 h除去二氧化硅模板。(6) 抽滤，用超纯水和乙醇各洗涤至pH=7，并干燥后得氮磷硫三元共掺杂有序介孔碳（NPS-OMC）。2. (1) Dry KIT-6 is ultrasonically treated in deionized water to obtain a uniform dispersion; at the same time, add sucrose, phosphoric acid and thiosemicarbazide to deionized water and stir to obtain a uniform solution, and the mass ratio, m(KIT -6): m (sucrose): m (phosphoric acid): m (thiosemicarbazide) = 8: 8: (2~1): (2~1). (2) Transfer the latter to the former and continue stirring for 12 h at 40 °C in a fume hood. (3) Place the obtained paste compound in an oven to dry at 80°C for 12 hours, and then grind the dried solid into powder. (4) Pyrolyze the composite powder in a tube furnace at 800 °C for 2 h under high-purity nitrogen (50 ml/s), with a heating rate of 2 °C/min. (5) The carbonized composite was immersed in 100 mL of 5% HF solution and stirred for 24 h to remove the silica template. (6) Suction filtration, washing with ultrapure water and ethanol to pH = 7, and drying to obtain nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous carbon (NPS-OMC).

本实施方式通过纳米灌注方法将碳源、氮源、磷源、硫源分别灌注到有序介孔二氧化硅模板（KIT-6），碳化后再将硅模板除去，得到氮磷硫三元共掺杂有序介孔碳纳米材料。In this embodiment, the carbon source, nitrogen source, phosphorus source, and sulfur source are respectively infused into the ordered mesoporous silica template (KIT-6) through the nano-infusion method, and the silicon template is removed after carbonization to obtain a nitrogen, phosphorus, and sulfur ternary Co-doped ordered mesoporous carbon nanomaterials.

具体实施方式二：本实施方式与具体实施方式一至四之一不同的是步骤二热解温度为700℃，其它步骤及参数与具体实施方式一至四之一相同。Embodiment 2: This embodiment differs from Embodiment 1 to Embodiment 4 in that the pyrolysis temperature in Step 2 is 700° C., and other steps and parameters are the same as Embodiment 1 to Embodiment 4.

具体实施方式三：本实施方式与具体实施方式一至五之一不同的是步骤二热解温度为900℃，其它步骤及参数与具体实施方式一至五之一相同。Embodiment 3: This embodiment differs from Embodiment 1 to Embodiment 1 in that the pyrolysis temperature in Step 2 is 900° C., and other steps and parameters are the same as Embodiment 1 to Embodiment 5.

具体实施方式四：本实施方式与具体实施方式一至六之一不同的是步骤二在通风橱中60℃下搅拌12 h，其它步骤及参数与具体实施方式一至六之一相同。Embodiment 4: This embodiment is different from Embodiment 1 to Embodiment 6 in that step 2 is stirred in a fume hood at 60° C. for 12 h, and other steps and parameters are the same as Embodiment 1 to Embodiment 6.

具体实施方式五：本实施方式与具体实施方式一至七之一不同的是步骤二在通风橱中70℃下搅拌12 h，其它步骤及参数与具体实施方式一至七之一相同。Embodiment 5: This embodiment is different from Embodiment 1 to Embodiment 7 in that step 2 is stirred in a fume hood at 70° C. for 12 h, and other steps and parameters are the same as Embodiment 1 to Embodiment 7.

具体实施方式六：本实施方式与具体实施方式一至八之一不同的是步骤二在800℃下焙烧处理3 h。其它步骤及参数与具体实施方式一至八之一相同。Embodiment 6: This embodiment is different from Embodiment 1 to Embodiment 8 in that step 2 is calcined at 800° C. for 3 h. Other steps and parameters are the same as those in Embodiments 1 to 8.

实施例一：Embodiment one:

一、采用水热合成法合成有序介孔二氧化硅模板 (KIT-6)；1. Synthesis of ordered mesoporous silica template (KIT-6) by hydrothermal synthesis method;

二、（1）干燥的KIT-6 (1.0 g)在15 mL DI水中超声处理1 h得均匀分散液；于此同时将1.0 g蔗糖、0.25 g磷酸和0.25 g氨基硫脲加入到15 mL DI水中搅拌1 h得到均匀的溶液。(2) 将后者转移到前者中并在通风橱中于50℃下继续搅拌12 h。(3) 将得到的糊状复合物放置于烘箱中于80℃下干燥12 h，然后把剩余的固体研磨成粉末。(4) 把该复合材料粉末置于管式炉中在高纯氮气 (50 mL/s) 下于800℃热解2 h，加热速率为2 ℃/min。(5) 把碳化后的复合材料浸没于100 mL 质量分数为5%的HF溶液中并搅拌24 h以除去二氧化硅模板。(6) 抽滤，用超纯水和乙醇各洗涤3次，并于100℃下干燥12 h后得氮磷硫三元共掺杂有序介孔碳（NPS-OMC）。2. (1) Dry KIT-6 (1.0 g) was sonicated in 15 mL DI water for 1 h to obtain a uniform dispersion; at the same time, 1.0 g sucrose, 0.25 g phosphoric acid and 0.25 g thiosemicarbazide were added to 15 mL DI water Stir in water for 1 h to obtain a homogeneous solution. (2) Transfer the latter to the former and continue stirring for 12 h at 50 °C in a fume hood. (3) Place the obtained paste compound in an oven to dry at 80°C for 12 h, and then grind the remaining solid into powder. (4) The composite material powder was pyrolyzed in a tube furnace at 800 °C for 2 h under high-purity nitrogen (50 mL/s), and the heating rate was 2 °C/min. (5) The carbonized composite material was immersed in 100 mL of 5% HF solution and stirred for 24 h to remove the silica template. (6) Suction filtration, washing with ultrapure water and ethanol three times each, and drying at 100°C for 12 h to obtain nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous carbon (NPS-OMC).

实施例二：Embodiment two:

一、采用水热合成法合成有序介孔二氧化硅模板 (KIT-6)；1. Synthesis of ordered mesoporous silica template (KIT-6) by hydrothermal synthesis method;

二、（1）干燥的KIT-6 (1.0 g)在15 mL DI水中超声处理1 h得均匀分散液；于此同时将1.0 g蔗糖、0.33 g磷酸和0.33 g氨基硫脲加入到15 mL DI水中搅拌1 h得到均匀的溶液。(2) 将后者转移到前者中并在通风橱中于50℃下继续搅拌12 h。(3) 将得到的糊状复合物放置于烘箱中于80℃下干燥12 h，然后把剩余的固体研磨成粉末。(4) 把该复合材料粉末置于管式炉中在高纯氮气 (50 mL/s) 下于800℃热解2 h，加热速率为2 ℃/min。(5) 把碳化后的复合材料浸没于100 mL 质量分数为5%的HF溶液中并搅拌24 h以除去二氧化硅模板。(6) 抽滤，用超纯水和乙醇各洗涤3次，并于100℃下干燥12 h后得氮磷硫三元共掺杂有序介孔碳（NPS-OMC）。2. (1) Dry KIT-6 (1.0 g) was sonicated in 15 mL DI water for 1 h to obtain a uniform dispersion; at the same time, 1.0 g sucrose, 0.33 g phosphoric acid and 0.33 g thiosemicarbazide were added to 15 mL DI water Stir in water for 1 h to obtain a homogeneous solution. (2) Transfer the latter to the former and continue stirring for 12 h at 50 °C in a fume hood. (3) Place the obtained paste compound in an oven to dry at 80°C for 12 h, and then grind the remaining solid into powder. (4) The composite material powder was pyrolyzed in a tube furnace at 800 °C for 2 h under high-purity nitrogen (50 mL/s), and the heating rate was 2 °C/min. (5) The carbonized composite material was immersed in 100 mL of 5% HF solution and stirred for 24 h to remove the silica template. (6) Suction filtration, washing with ultrapure water and ethanol three times each, and drying at 100°C for 12 h to obtain nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous carbon (NPS-OMC).

实施例三：Embodiment three:

一、采用水热合成法合成有序介孔二氧化硅模板 (KIT-6)；1. Synthesis of ordered mesoporous silica template (KIT-6) by hydrothermal synthesis method;

二、（1）干燥的KIT-6 (1.0 g)在15 mL DI水中超声处理1 h得均匀分散液；于此同时将1.0 g蔗糖、0.17 g磷酸和0.17 g氨基硫脲加入到15 mL DI水中搅拌1 h得到均匀的溶液。(2) 将后者转移到前者中并在通风橱中于50℃下继续搅拌12 h。(3) 将得到的糊状复合物放置于烘箱中于80℃下干燥12 h，然后把剩余的固体研磨成粉末。(4) 把该复合材料粉末置于管式炉中在高纯氮气 (氮气流速为50 mL/s) 下于800℃热解2 h，加热速率为2 ℃/min。(5) 把碳化后的复合材料浸没于100 mL 质量分数为5%的HF溶液中并搅拌24 h以除去二氧化硅模板。(6) 抽滤，用超纯水和乙醇各洗涤3次，并于100℃下干燥12 h后得氮磷硫三元共掺杂有序介孔碳（NPS-OMC）。2. (1) Dry KIT-6 (1.0 g) was sonicated in 15 mL DI water for 1 h to obtain a uniform dispersion; at the same time, 1.0 g sucrose, 0.17 g phosphoric acid and 0.17 g thiosemicarbazide were added to 15 mL DI water Stir in water for 1 h to obtain a homogeneous solution. (2) Transfer the latter to the former and continue stirring for 12 h at 50 °C in a fume hood. (3) Place the obtained paste compound in an oven to dry at 80°C for 12 h, and then grind the remaining solid into powder. (4) The composite material powder was pyrolyzed in a tube furnace at 800 °C for 2 h under high-purity nitrogen (nitrogen flow rate of 50 mL/s), and the heating rate was 2 °C/min. (5) The carbonized composite material was immersed in 100 mL of 5% HF solution and stirred for 24 h to remove the silica template. (6) Suction filtration, washing with ultrapure water and ethanol three times each, and drying at 100°C for 12 h to obtain nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous carbon (NPS-OMC).

本实施例步骤一水热方法制备有序介孔二氧化硅模板（KIT-6）的过程如下：The process of preparing ordered mesoporous silica template (KIT-6) by hydrothermal method in step 1 of this example is as follows:

取6.0 g聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物 (P123) 溶解于217.0 g去离子水与11.8 g盐酸（HCl）中，在35℃搅拌下缓慢加入6.0 g正丁醇（BuOH）和正硅酸乙酯（TEOS）且TEOS : P-123 : HCl : H2O:BuOH = 1 : 0.017 : 1.83 : 195 : 1.31。混合溶液在35℃下搅拌24 h，之后转移到反应釜中，在100℃下反应24 h。样品抽滤后得到白色粉末，在80℃干燥12 h后转移到马弗炉中，经550℃焙烧6 h。得到有序介孔二氧化硅模板（KIT-6）。Dissolve 6.0 g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) in 217.0 g of deionized water and 11.8 g of hydrochloric acid (HCl), and slowly add it under stirring at 35°C 6.0 g n-butanol (BuOH) and tetraethyl orthosilicate (TEOS) and TEOS : P-123 : HCl : H 2 O:BuOH = 1 : 0.017 : 1.83 : 195 : 1.31. The mixed solution was stirred at 35 °C for 24 h, then transferred to a reaction kettle, and reacted at 100 °C for 24 h. The white powder was obtained after suction filtration of the sample, which was dried at 80 °C for 12 h, transferred to a muffle furnace, and calcined at 550 °C for 6 h. An ordered mesoporous silica template (KIT-6) was obtained.

实施例中得到的氮磷硫三元共掺杂有序介孔碳材料的晶型由X射线衍射仪(XRD,RigakuD/max-Ⅱ) 进行表征；形貌与微观结构是采用扫描电子显微镜分析(SEM，S-3400)和透射电子显镜(TEM, H-7650)进行表征；材料元素分布由能谱仪 (EDS，S-3400)进行表征；材料表面价态信息由X射线光电子能谱分析(XPS，250Xi) 进行表征；材料比表面积等孔道信息由物理吸附分析仪(BET，AUTOSORB-1) 进行表征。The crystal form of the nitrogen, phosphorus and sulfur ternary co-doped ordered mesoporous carbon material obtained in the examples is characterized by X-ray diffractometer (XRD, RigakuD/max-II); the morphology and microstructure are analyzed by scanning electron microscopy (SEM, S-3400) and transmission electron microscopy (TEM, H-7650) were used to characterize; material element distribution was characterized by energy spectrometer (EDS, S-3400); material surface valence information was obtained by X-ray photoelectron spectroscopy Analysis (XPS, 250Xi) was used for characterization; material specific surface area and other pore information were characterized by physical adsorption analyzer (BET, AUTOSORB-1).

图1是实施一得到的有序介孔二氧化硅模板 (KIT-6)的XRD图，从图中可以清晰地看出在2θ＝0.8°和1.2°两处有明显的特征衍射峰出现，分别对应（211）和（220）晶面。这说明高温热解去除表面活性剂P123之后所得到的KIT-6具有高度有序的孔道结构。图2为实施例一中有序介孔二氧化硅模板 (KIT-6)的TEM图。从图中可以明显地看出KIT-6硅模板具有高度有序的3D孔道结构，这与图1中XRD的表征结果一致。Figure 1 is the XRD pattern of the ordered mesoporous silica template (KIT-6) obtained in the first implementation. It can be clearly seen from the figure that there are obvious characteristic diffraction peaks at 2θ=0.8° and 1.2°. Corresponding to (211) and (220) crystal planes, respectively. This shows that the KIT-6 obtained after removing the surfactant P123 by high temperature pyrolysis has a highly ordered pore structure. Figure 2 is a TEM image of the ordered mesoporous silica template (KIT-6) in Example 1. It can be clearly seen from the figure that the KIT-6 silicon template has a highly ordered 3D channel structure, which is consistent with the XRD characterization results in Figure 1.

图3为实施例一中氮磷硫三元共掺杂有序介孔碳材料的XRD图，从图中可以清晰地看出在2θ＝0.8°和1.2°两处有明显的特征衍射峰出现，分别对应（211）和（220）晶面。但与图1中的KIT-6硅模板的（220）晶面的特征峰相比较，氮磷硫三元共掺杂有序介孔碳的（220）晶面的特征衍射峰趋于平滑，表明高温热处理在一段程度上会导致材料的骨架发生收缩。Figure 3 is the XRD pattern of the nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous carbon material in Example 1. It can be clearly seen from the figure that there are obvious characteristic diffraction peaks at 2θ=0.8° and 1.2° , corresponding to the (211) and (220) crystal planes, respectively. However, compared with the characteristic peaks of the (220) crystal plane of the KIT-6 silicon template in Figure 1, the characteristic diffraction peaks of the (220) crystal plane of nitrogen, phosphorus and sulfur ternary co-doped ordered mesoporous carbon tend to be smoother, It shows that the high temperature heat treatment can lead to shrinkage of the skeleton of the material to some extent.

图4为实施例一中氮磷硫三元共掺杂有序介孔碳材料的氮气吸附-脱附等温曲线图及内嵌由吸附分支得到的BJH孔径分布曲线。材料的氮气吸-脱附等温线为IV型吸附曲线且在中压区(P/P0=0.4-0.8)出现了由毛细凝聚现象引起的H1型滞后环，对应合成碳材料的介孔结构。由计算得出氮磷硫三元共掺杂有序介孔碳材料的比表面积为637 m2/g，平均孔径为1.9 nm。材料较大的比表面积可以为电化学反应提供更多的活性位点，提高材料的比电容。Fig. 4 is the nitrogen adsorption-desorption isotherm curve of nitrogen, phosphorus and sulfur ternary co-doped ordered mesoporous carbon material in Example 1 and the embedded BJH pore size distribution curve obtained from the adsorption branch. The nitrogen adsorption-desorption isotherm of the material is a type IV adsorption curve, and in the medium pressure region (P/P 0 =0.4-0.8), a H1-type hysteresis loop caused by capillary condensation appears, corresponding to the mesoporous structure of the synthetic carbon material . According to the calculation, the specific surface area of nitrogen, phosphorus and sulfur ternary co-doped ordered mesoporous carbon material is 637 m 2 /g, and the average pore diameter is 1.9 nm. The larger specific surface area of the material can provide more active sites for electrochemical reactions and increase the specific capacitance of the material.

图5为实施例一中氮磷硫三元共掺杂有序介孔碳材料的TEM图。图5清晰地显示出了呈现有序的条纹，说明材料具有较高的有序度，为典型的3D介孔结构。从图像中还可清楚地观察到在碳材料中存在大量开放的均匀孔道，其是KIT-6模板3D介观结构的反相复制。与图4氮气吸附-脱附和图2 KIT-6的TEM所表征的结果一致。FIG. 5 is a TEM image of the nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous carbon material in Example 1. FIG. Figure 5 clearly shows the ordered stripes, indicating that the material has a high degree of order and is a typical 3D mesoporous structure. It can also be clearly observed from the images that there are a large number of open uniform channels in the carbon material, which is the inverse replication of the 3D mesoscopic structure of the KIT-6 template. It is consistent with the results characterized by nitrogen adsorption-desorption in Figure 4 and TEM of KIT-6 in Figure 2.

图6为实施例一中氮磷硫三元共掺杂有序介孔碳材料的SEM图。从中显示出氮磷硫三元共掺杂有序介孔碳颗粒之间相对比较独立，颗粒分布均匀。FIG. 6 is an SEM image of the nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous carbon material in Example 1. FIG. It shows that nitrogen, phosphorus and sulfur ternary co-doped ordered mesoporous carbon particles are relatively independent, and the particle distribution is uniform.

图7为实施例一中氮磷硫三元共掺杂有序介孔碳材料中碳、氮、磷、硫元素的EDS图。从图中可以清晰地观察到碳、氮、磷、硫元素呈现均匀的分布状态。这说明氮、磷、硫元素均匀地掺杂进入了有序介孔碳材料之中。7 is an EDS diagram of carbon, nitrogen, phosphorus, and sulfur elements in the nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous carbon material in Example 1. FIG. It can be clearly observed from the figure that carbon, nitrogen, phosphorus, and sulfur elements are in a uniform distribution state. This shows that nitrogen, phosphorus, and sulfur elements are uniformly doped into the ordered mesoporous carbon material.

图8为实施例一中氮磷硫三元共掺杂有序介孔碳材料的XPS全谱图，从图中可以观察到碳、氮、磷、硫、氧的峰型存在，这说明氮、磷、硫元素确实掺杂进入了有序介孔碳材料之中。这与图7 EDS所的结果一致。Figure 8 is the XPS full spectrum of the nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous carbon material in Example 1. From the figure, it can be observed that the peaks of carbon, nitrogen, phosphorus, sulfur, and oxygen exist, which shows that nitrogen , phosphorus, and sulfur elements are indeed doped into the ordered mesoporous carbon materials. This is consistent with the results shown in Figure 7 EDS.

应用实施例：将5mg氮磷硫三元共掺杂有序介孔碳材料粉末与5 wt%的聚四氟乙烯（PTFE）溶液混合，搅拌成浆液，然后均匀涂抹在1×10 cm的泡沫镍上，压制成片，得到氮磷硫三元共掺杂有序介孔碳材料超级电容器电极。Application example: Mix 5 mg of nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous carbon material powder with 5 wt% polytetrafluoroethylene (PTFE) solution, stir to form a slurry, and then evenly spread it on a 1×10 cm foam Nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon material supercapacitor electrodes are obtained by pressing into sheets.

该应用实施例以***电极为参比电极，铂电极为辅助电极，用CHI660E电化学工作站（上海辰华）对氮磷硫三元共掺杂有序介孔碳材料电极进行了循环伏安特性曲线、恒电流充放电和交流阻抗等电性能测试。In this application example, the mercury oxide electrode is used as the reference electrode, and the platinum electrode is used as the auxiliary electrode. The CHI660E electrochemical workstation (Shanghai Chenhua) is used to conduct cyclic voltammetry on the nitrogen, phosphorus and sulfur ternary co-doped ordered mesoporous carbon material electrode Electrical performance tests such as characteristic curve, constant current charge and discharge, and AC impedance.

图9是实施例一、二、三中的氮磷硫三元共掺杂有序介孔碳材料电极在1 mV/s扫描速率及6 mol/LKOH电解溶液下的循环伏安曲线。从图中明显看出，氮磷硫三元共掺杂有序介孔碳材料电极的CV曲线最接近于理想电容器的矩形形状，说明所制备的氮磷硫三元共掺杂有序介孔碳材料作为超级电容器电极时具有非常小的电阻，对称性、可逆性良好，因此可以视为超级电容器的理想电极材料；在实例二中增加氮、磷、硫的掺杂量，其比电容反而变小，由此可见并不是氮、磷、硫的掺杂量越多越好；在实例三中减少氮、磷、硫的掺杂量，其比电容变小，由此可见较少的氮、磷、硫掺杂量并不能显著地增加材料的法拉第赝电容。Fig. 9 is the cyclic voltammetry curves of the nitrogen, phosphorus and sulfur ternary co-doped ordered mesoporous carbon electrode in Examples 1, 2 and 3 at a scan rate of 1 mV/s and 6 mol/L KOH electrolytic solution. It is obvious from the figure that the CV curve of nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous carbon electrode is closest to the rectangular shape of an ideal capacitor, indicating that the prepared nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous When carbon materials are used as supercapacitor electrodes, they have very small resistance, good symmetry and reversibility, so they can be regarded as ideal electrode materials for supercapacitors; increasing the doping amount of nitrogen, phosphorus and sulfur in Example 2, the specific capacitance is reversed. It can be seen that the doping amount of nitrogen, phosphorus, and sulfur is not the more the better; in example three, the doping amount of nitrogen, phosphorus, and sulfur is reduced, and the specific capacitance becomes smaller, so it can be seen that less nitrogen , phosphorus, and sulfur doping can not significantly increase the Faradaic pseudocapacitance of the material.

图10是实施例一、二、三中氮磷硫三元共掺杂有序介孔碳的恒电流充放电曲线。从图中可以看出恒电流充放电曲线的充电时间段和放电时间段基本接近，这说明复合后的电极材料具有良好的循环利用行。且恒电流充放电曲线具有一定的对称性，表明该电极材料的可逆性较好。与图9中循环伏安曲线图所表现的电化学性能一致：过多或过少的氮、磷、硫掺杂量均会影响材料的法拉第赝电容。从图中可以明显看到在电解液（KOH电解液）浓度为6mol/L时，实施例一中的氮磷硫三元共掺杂有序介孔碳材料的比电容达到了343 F/g。Fig. 10 is the galvanostatic charge and discharge curves of nitrogen, phosphorus and sulfur ternary co-doped ordered mesoporous carbon in Examples 1, 2 and 3. It can be seen from the figure that the charging time period and the discharging time period of the galvanostatic charge-discharge curve are basically close, which shows that the composite electrode material has good recycling performance. And the galvanostatic charge-discharge curve has a certain symmetry, indicating that the electrode material has good reversibility. It is consistent with the electrochemical performance shown in the cyclic voltammetry curve in Figure 9: too much or too little nitrogen, phosphorus, and sulfur doping will affect the Faraday pseudocapacitance of the material. It can be clearly seen from the figure that when the concentration of the electrolyte (KOH electrolyte) is 6mol/L, the specific capacitance of the nitrogen, phosphorus, and sulfur ternary co-doped ordered mesoporous carbon material in Example 1 reaches 343 F/g .

Claims (7)

1. the preparation method of nitrogen phosphorus sulphur codope ordered mesoporous carbon material, it is characterised in that be to follow these steps to realize：
One, using hydrothermal synthesis method synthesizing ordered mesoporous silica dioxide template (KIT-6)；
Two,（1）Dry KIT-6 is ultrasonically treated to obtain uniform dispersion in deionized water；Simultaneously by sucrose, phosphoric acid and Thiosemicarbazides, which is add to deionized water, stirs to get uniform solution；(2) mixing of sucrose, phosphoric acid and thiosemicarbazides is molten Liquid is added in KIT-6 dispersion liquids and stirring is aged 10~14h at 40~60 DEG C in draught cupboard；(3) paste that will be obtained Compound is positioned in baking oven at 70~90 DEG C dry 10~14 h, grind into powder；(4) composite powder is set (nitrogen flow rate is 50 mL/s) is pyrolyzed 1~3 h, the rate of heat addition 2 in 700~900 DEG C under high pure nitrogen in tube furnace ℃/min；(5) composite material after carbonization is immersed in a certain amount of 5% HF solution and is stirred to remove silica template； (6) it filters, is respectively washed with ultra-pure water and ethyl alcohol, and nitrogen phosphorus sulphur codope ordered mesopore carbon is obtained after drying（NPS-OMC）.
2. the preparation method of nitrogen phosphorus sulphur codope ordered mesoporous carbon material according to claim 1, it is characterised in that step Each material mass ratio is m (KIT-6) in rapid two：M (sucrose)：M (phosphoric acid)：M (thiosemicarbazides)=8: 8:(2~1):(2~1).
3. the preparation method of nitrogen phosphorus sulphur codope ordered mesoporous carbon material according to claim 1, it is characterised in that step Mixture Aging Temperature is 40~60 DEG C in rapid two.
4. the preparation method of nitrogen phosphorus sulphur codope ordered mesoporous carbon material according to claim 1, it is characterised in that step Mixture digestion time is 10~14h in rapid two.
5. the preparation method of nitrogen phosphorus sulphur codope ordered mesoporous carbon material according to claim 1, it is characterised in that Step 2 paste compound drying temperature is 70~90 DEG C, and drying time is 10~14 h.
6. the preparation method of nitrogen phosphorus sulphur codope ordered mesoporous carbon material according to claim 1, it is characterised in that Step 2 pyrolysis temperature is 700 DEG C~900 DEG C.
7. the preparation method of nitrogen phosphorus sulphur codope ordered mesoporous carbon material according to claim 1, it is characterised in that It is 2 DEG C/min that step 2, which is pyrolyzed heating rate,..
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