CN105161311A - Method for preparing titanium nitride/carbon composite materials - Google Patents
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Abstract
本发明一种氮化钛/碳复合材料的制备方法，将表面活性剂溶于溶剂中，然后加入有机钛源和无机盐，混合均匀，之后加入酚醛树脂乙醇溶液，最后加入有机硅源，在35~45℃水浴下充分搅拌形成均相溶液，随后倒入一个反应容器中，放在干燥箱中进行交联，从而得到透明的膜状物；将透明膜状物刮下，在管式炉中在氮气保护下进行焙烧，然后自然冷却到室温，即得到TiN/SiO2/C的复合物；将TiN/SiO2/C复合物加入到氢氧化钠溶液中，水浴搅拌，然后离心水洗，洗到流出液为中性，自然干燥，得到TiN/C复合纳米材料。本发明工艺简单、合成温度低。
A preparation method of a titanium nitride/carbon composite material of the present invention, the surfactant is dissolved in a solvent, then an organic titanium source and an inorganic salt are added, mixed evenly, then a phenolic resin ethanol solution is added, and an organic silicon source is added at last, Fully stir in a water bath at 35~45°C to form a homogeneous solution, then pour it into a reaction container, put it in a drying oven for cross-linking, and obtain a transparent film; scrape off the transparent film, and put it in a tube furnace Roasting under the protection of nitrogen, and then naturally cooling to room temperature, the TiN/SiO 2 /C composite is obtained; the TiN/SiO 2 /C composite is added to the sodium hydroxide solution, stirred in a water bath, and then centrifuged and washed with water. Wash until the effluent is neutral, and dry naturally to obtain a TiN/C composite nanomaterial. The invention has simple process and low synthesis temperature.
Description
技术领域 technical field
本发明属于无机材料合成的领域，涉及一种超级电容器的电极材料，具体来说是一种氮化钛/碳复合纳米材料的制备方法。 The invention belongs to the field of inorganic material synthesis, and relates to an electrode material for a supercapacitor, in particular to a method for preparing a titanium nitride/carbon composite nanomaterial.
背景技术 Background technique
随着便携式电子装置和混合动力汽车市场的快速发展，大力发展环境友好型的高性能储能器件成为了当今世界经济可持续发展的重要课题之一。目前市场上常见的传统储能装置为电池（包括碱锰、银锌等一次电池和铅酸、镍镉、镍氢、锂离子、聚合物等二次电池）和传统电容器，电池虽然能量密度相对较大但是储能时充电时间较长、功率密度相对较低，难以满足比如一些高能脉冲等特定的应用场合，而传统电容器虽然可以快速充放电、功率密度高但是它的能量密度又较低，其应用的范围正在不断缩小。 With the rapid development of the market of portable electronic devices and hybrid electric vehicles, vigorously developing environment-friendly high-performance energy storage devices has become one of the important issues for the sustainable development of the world economy. Common traditional energy storage devices currently on the market are batteries (including primary batteries such as alkaline manganese and silver zinc, and secondary batteries such as lead-acid, nickel-cadmium, nickel-metal hydride, lithium-ion, polymer, etc.) and traditional capacitors. Although the energy density of batteries is relatively Larger, but the charging time is longer when storing energy, and the power density is relatively low, which is difficult to meet specific applications such as some high-energy pulses. Although traditional capacitors can charge and discharge quickly and have high power density, their energy density is low. The scope of its application is constantly narrowing.
超级电容器即电化学电容器的出现使上述的问题得到了解决。超级电容器具有功率密度大、使用寿命长、充放电速度快等优点。此外超级电容器可与其它高能量密度的储能装置匹配成混合储能器件，如同锂离子电池组合或燃料电池联用，应用在低排放量的混合电动汽车中。其中影响电化学电容器的电化学性能是它的电极材料，因此寻找高性能的电极材料是研究的重点。现在应用在电化学电容器上的材料包括碳基材料、金属氧化物材料、导电聚合物材料和复合材料。因为碳基材料具有良好的导电性和较高的机械强度，但是碳基材料提供的主要是双电层电容，其电容量优先，而金属氧化物和导电聚合物其电容量要比碳基材料的高很多，因此将两种不同的材料结合组成复合材料使其具有更好的电容性能。（谢小英，张辰，杨全红.超级电容器电极材料研究进展[J].化学工业与工程.2014,01,013,63-71;李英.二氧化锰及二氧化锰/氧化石墨烯复合电极的超电容性能[D].天津：天津大学，2012；钱陆明.超级电容器电极用新型杂化碳材料的制备[D].南京：南京理工大学，2013）。 The emergence of supercapacitors, that is, electrochemical capacitors, has solved the above problems. Supercapacitors have the advantages of high power density, long service life, and fast charging and discharging. In addition, supercapacitors can be matched with other high-energy-density energy storage devices to form hybrid energy storage devices, such as lithium-ion battery combinations or fuel cells, used in low-emission hybrid electric vehicles. Among them, the electrochemical performance of electrochemical capacitors is affected by its electrode materials, so finding high-performance electrode materials is the focus of research. Materials currently used in electrochemical capacitors include carbon-based materials, metal oxide materials, conductive polymer materials, and composite materials. Because carbon-based materials have good electrical conductivity and high mechanical strength, but carbon-based materials mainly provide electric double layer capacitance, and their capacitance is preferred, while metal oxides and conductive polymers have higher capacitance than carbon-based materials. is much higher, so combining two different materials to form a composite material makes it have better capacitance performance. (Xie Xiaoying, Zhang Chen, Yang Quanhong. Research progress on supercapacitor electrode materials[J]. Chemical Industry and Engineering. 2014, 01, 013, 63-71; Li Ying. Supercapacitance of manganese dioxide and manganese dioxide/graphene oxide composite electrodes Performance [D]. Tianjin: Tianjin University, 2012; Qian Luming. Preparation of new hybrid carbon materials for supercapacitor electrodes [D]. Nanjing: Nanjing University of Science and Technology, 2013).
过渡金属氮化物TiN具有高熔点、高硬度、优良的化学稳定性和耐腐蚀性，因此成为切削工具、耐磨部件的优选材料，同时常被用作复合材料中的增强相等。朱福兴等采用电解法制备氮化钛，具体方法是在钛可溶阳极点解制备金属钛的过程中，在阴极通入氮气，氮气与阴极产生的钛反应生成氮化钛，之后分离电解质和氮化钛，即得到氮化钛产品。其中点解的温度为650~850℃，分离电解质的过程中需要用到蒸馏、水洗和酸洗等的步骤。蒸馏的温度为950~1000℃。虽然他能采取一步制备得到氮化钛，但是合成的步骤比较麻烦，而且蒸馏所需的温度也比较高，一般的装置不能满足要求，因此这种方法还是存在很大的缺陷（朱福兴，穆天柱，邓斌，何安西，程晓哲，马尚润，陈兵，郑权，张瑶.制备氮化钛的方法，中国，CN104498982A.2015-04-08.）。 Transition metal nitride TiN has high melting point, high hardness, excellent chemical stability and corrosion resistance, so it becomes the preferred material for cutting tools and wear-resistant parts, and is often used as reinforcement in composite materials. Zhu Fuxing and others used electrolysis to prepare titanium nitride. The specific method was to pass nitrogen gas into the cathode during the process of preparing titanium metal by spot decomposition of titanium soluble anode. The nitrogen gas reacted with the titanium generated by the cathode to form titanium nitride, and then separated the electrolyte and nitrogen. Titanium, that is, titanium nitride products. The temperature of point solution is 650~850°C, and steps such as distillation, water washing and pickling are required in the process of separating the electrolyte. The temperature of distillation is 950~1000℃. Although he can prepare titanium nitride in one step, the synthesis steps are cumbersome, and the temperature required for distillation is relatively high, and the general equipment cannot meet the requirements, so this method still has great defects (Zhu Fuxing, Mu Tian Zhu, Deng Bin, He Anxi, Cheng Xiaozhe, Ma Shangrun, Chen Bing, Zheng Quan, Zhang Yao. Method for preparing titanium nitride, China, CN104498982A.2015-04-08.).
RomuloR.M.等利用阴极笼等离子体沉积技术制备得到了TiN，就是利用常规的具有两同心阴极笼的等离子体反应器，在最大电压为1500V，电流为2A的情况下，在阴极笼放置两个厚度为2.0mm的两个钛片，之后在制备的过程中通入N2/H2(80%N2)混合气，处理温度保持在400℃，制备得到氮化钛。虽然通过这种方法得到了氮化钛，但是要在高的电压的情况下，不是太安全，因此还有待进一步改善（RomuloR.M.deSousa,PatriciaS.Sato,BartolomeuC.Viana,ClodomiroAlvesJr,AkioNishimoto,PedroA.P.Nascente.CathodiccageplasmadepositionofTiNandTiO2thinfilmsonsiliconsubstrates.J.Vac.Sci.Technol.A33(4),Jul/Aug2015）。 RomuloR.M. et al. prepared TiN by cathode cage plasma deposition technology, which is to use a conventional plasma reactor with two concentric cathode cages. Under the condition of a maximum voltage of 1500V and a current of 2A, two cathode cages are placed. Two titanium sheets with a thickness of 2.0mm were passed through N 2 /H 2 (80%N 2 ) mixed gas during the preparation process, and the treatment temperature was kept at 400°C to prepare titanium nitride. Although titanium nitride has been obtained by this method, it is not too safe under the condition of high voltage, so it needs to be further improved (RomuloR.M.deSousa, PatriciaS.Sato, BartolomeuC.Viana, ClodomiroAlvesJr, AkioNishimoto, PedroA .P.Nascente.CathodiccageplasmapositionofTiNandTiO2thinfilmsonsiliconsubstrates.J.Vac.Sci.Technol.A33(4),Jul/Aug2015).
鲁元等以二氧化钛和碳粉为原料，采用碳热还原法制备得到了多孔氮化钛。具体步骤是把二氧化钛和碳黑以摩尔比为1：2的比例配好，然后将配好的粉料与磨球放入混料罐，以无水乙醇为介质用行星球磨机湿混24h，之后烘干，用200目的筛网过筛，之后放在模具中压成长方形，然后放在0.5MPa的氮气压力下进行烧结，烧结的温度为1600~1750℃，得到了高气孔率的氮化钛。但是实验中烧结温度较高，不能满足日常的制备需要（鲁元，龚楠，荆强征，李京京，炱柯.碳热还原法制备多孔氮化钛陶瓷[J].陶瓷学报，2009，32（2），177-182）。 Lu Yuan et al prepared porous titanium nitride by carbothermal reduction method using titanium dioxide and carbon powder as raw materials. The specific steps are to mix titanium dioxide and carbon black with a molar ratio of 1:2, then put the prepared powder and grinding balls into the mixing tank, and use absolute ethanol as the medium to wet mix with a planetary ball mill for 24 hours, then Dry it, sieve it with a 200-mesh screen, put it in a mold, press it into a rectangle, and then sinter it under a nitrogen pressure of 0.5MPa. The sintering temperature is 1600~1750°C, and titanium nitride with high porosity is obtained. . However, the sintering temperature in the experiment is too high, which cannot meet the daily preparation needs (Lu Yuan, Gong Nan, Jing Qiangzheng, Li Jingjing, Qi Ke. Preparation of porous titanium nitride ceramics by carbothermal reduction[J]. Ceramic Journal, 2009, 32 (2), 177-182).
综上所述，以前制备得到TiN粉末，有的是经过机械研磨，然后再经过高温焙烧得到的，也有经过点解等方法实现目的，但是总的来说高温焙烧需要的温度都在1000℃以上，一般的管式炉不能满足实验的要求，而且经过物理研磨过程需要的设备要求较高，不易操作，而且电解过程需要的设备的要求都很高等特点。因此需要寻找一种操作简便，可以在低温下焙烧就得到TiN纳米粒子。 To sum up, some of the TiN powders prepared in the past were mechanically ground and then roasted at high temperature, and some of them were obtained by point solution and other methods. The tube furnace cannot meet the requirements of the experiment, and the equipment required for the physical grinding process is relatively high, it is not easy to operate, and the equipment required for the electrolysis process is very demanding. Therefore, it is necessary to find a method that is easy to operate and can be calcined at a low temperature to obtain TiN nanoparticles.
发明内容 Contents of the invention
针对现有技术中的上述技术问题，本发明提供了一种氮化钛/碳复合纳米材料的制备方法，所述的这种氮化钛/碳复合纳米材料的制备方法解决了现有技术中的制备氮化钛/碳复合纳米材料工艺复杂、对设备的要求高的技术问题。 Aiming at the above-mentioned technical problems in the prior art, the present invention provides a method for preparing titanium nitride/carbon composite nanomaterials, which solves the problems in the prior art. The preparation of titanium nitride/carbon composite nanomaterials is a technical problem with complex processes and high requirements for equipment.
本发明的一种氮化钛/碳复合材料的制备方法，包括以下步骤： A kind of preparation method of titanium nitride/carbon composite material of the present invention, comprises the following steps:
（1）、将表面活性剂溶于溶剂中，然后加入有机钛源和无机盐，搅拌混合均匀，之后加入质量百分比浓度为15~25%的酚醛树脂乙醇溶液，最后加入有机硅源，在35~45℃水浴下充分搅拌形成均相溶液，随后倒入一个反应容器中，放在35~45℃鼓风干燥箱15~30h，然后放到80~110℃鼓风干燥箱中进行交联，从而得到透明的膜状物； (1) Dissolve the surfactant in the solvent, then add organic titanium source and inorganic salt, stir and mix evenly, then add phenolic resin ethanol solution with a concentration of 15-25% by mass, and finally add organic silicon source, at 35 Fully stir in a water bath at ~45°C to form a homogeneous solution, then pour it into a reaction container, put it in a blast drying oven at 35~45°C for 15~30 hours, and then put it in a blast drying oven at 80~110°C for cross-linking. Thereby obtaining a transparent film;
上述所用的表面活性剂、溶剂、有机钛源、无机盐、硅源、酚醛树脂溶液的质量比为1.0:10~30:1.5~5:1~4:0.3~4:0.8~3； The mass ratio of the surfactant, solvent, organic titanium source, inorganic salt, silicon source, and phenolic resin solution used above is 1.0:10~30:1.5~5:1~4:0.3~4:0.8~3;
所述的表面活性剂为EO20PO70EO20、EO106PO70EO106、或者EO132PO60EO132中的一种或两种以上的混合物； The surfactant is one or a mixture of two or more of EO 20 PO 70 EO 20 , EO 106 PO 70 EO 106 , or EO 132 PO 60 EO 132 ;
所述溶剂为乙醇、水、甲酸、乙二醇、或者甲醚中两种或两种以上的混合物； The solvent is ethanol, water, formic acid, ethylene glycol, or a mixture of two or more in methyl ether;
所述有机钛源为柠檬酸钛； The organic titanium source is titanium citrate;
所述无机盐为六水合硝酸镍、九水合硝酸铁、或者六水合硝酸钴中的一种或两种及以上混合物； The inorganic salt is one or two or more mixtures of nickel nitrate hexahydrate, iron nitrate nonahydrate, or cobalt nitrate hexahydrate;
所述的有机硅源为正硅酸四乙酯、正硅酸四甲酯、正硅酸四丙酯、或者正硅酸四丁酯中的一种或两种以上组成的混合物； The organosilicon source is tetraethyl orthosilicate, tetramethyl orthosilicate, tetrapropyl orthosilicate, or one or a mixture of two or more of tetrabutyl orthosilicate;
（2）、将步骤（1）中得到的透明膜状物刮下，在管式炉中在氮气保护下升温至700~900℃进行焙烧1~3小时，然后自然冷却到室温，即得到TiN/SiO2/C的复合物； (2) Scrape off the transparent membrane obtained in step (1), heat up to 700-900°C in a tube furnace under the protection of nitrogen for 1-3 hours, and then cool naturally to room temperature to obtain TiN /SiO 2 /C compound;
（3）、将步骤（2）得到的TiN/SiO2/C复合物加入到0.2~2mol/L的氢氧化钠溶液中，其中TiN/SiO2/C和浓度为0.2~2mol/L的氢氧化钠溶液的用量，按TiN/SiO2/C：浓度为0.2~2mol/L的氢氧化钠溶液为1g：10~30ml的比例计算，35~45℃水浴搅拌10~40min，然后离心水洗，洗到流出液为中性，然后自然干燥，得到TiN/C复合纳米材料。 (3) Add the TiN/SiO 2 /C compound obtained in step (2) into 0.2~2mol/L sodium hydroxide solution, in which TiN/SiO 2 /C and hydrogen with a concentration of 0.2~2mol/L The amount of sodium oxide solution is calculated according to the ratio of TiN/SiO 2 /C: 0.2~2mol/L sodium hydroxide solution is 1g: 10~30ml, stirred in a water bath at 35~45°C for 10~40min, and then centrifuged and washed with water. Wash until the effluent is neutral, and then dry naturally to obtain a TiN/C composite nanomaterial.
进一步的，所述的柠檬酸钛的制备步骤如下； Further, the preparation steps of described titanium citrate are as follows;
将100mmol钛酸四丁酯溶解在50ml乙醇溶剂中制备得到A溶液，将100mmol柠檬酸溶解在100ml乙醇溶剂中制备得到B溶液，之后B溶液在快速搅拌下缓慢地滴入溶液A中，并且在40℃水浴下搅拌2h，然后40℃减压蒸发1h，获得的溶胶重新溶于蒸馏水中配成1M柠檬酸钛水溶液，密度约为1g/ml。 Dissolve 100mmol tetrabutyl titanate in 50ml ethanol solvent to prepare A solution, and dissolve 100mmol citric acid in 100ml ethanol solvent to prepare B solution, then B solution is slowly dropped into solution A under rapid stirring, and in Stir in a water bath at 40°C for 2h, then evaporate under reduced pressure at 40°C for 1h, and redissolve the obtained sol in distilled water to prepare a 1M titanium citrate aqueous solution with a density of about 1g/ml.
进一步的，步骤（2）中所述的升温，首先按速率1℃/min从室温升到300℃，然后再按速率为5℃/min升至700～900℃。 Further, the temperature increase described in step (2) is firstly raised from room temperature to 300°C at a rate of 1°C/min, and then raised to 700-900°C at a rate of 5°C/min.
进一步的，步骤（1）中所用的表面活性剂、溶剂、有机钛源、无机盐、硅源、酚醛树脂溶液的质量比为1：10：1.5：1：0.3：0.8；所述的表面活性剂为EO20PO70EO20；所述的有机硅源为正硅酸四乙酯；所述的有机钛源为柠檬酸钛；所述的无机盐为六水合硝酸镍；所述的溶剂为乙二醇和水。 Further, the mass ratio of the surfactant, solvent, organic titanium source, inorganic salt, silicon source, and phenolic resin solution used in step (1) is 1:10:1.5:1:0.3:0.8; the surface active The agent is EO 20 PO 70 EO 20 ; the organic silicon source is tetraethyl orthosilicate; the organic titanium source is titanium citrate; the inorganic salt is nickel nitrate hexahydrate; the solvent is glycol and water.
进一步的，步骤（1）中所用的表面活性剂、溶剂、有机钛源、无机盐、硅源、酚醛树脂溶液的质量比为1：20：3：2.5：2.2：1.9；所述的表面活性剂为EO106PO70EO106；所述的有机硅源为正硅酸四甲酯；所述的有机钛源为柠檬酸钛；所述的无机盐为九水合硝酸铁；所述的溶剂为乙醇和水。 Further, the mass ratio of the surfactant, solvent, organic titanium source, inorganic salt, silicon source, and phenolic resin solution used in step (1) is 1:20:3:2.5:2.2:1.9; the surface active The agent is EO 106 PO 70 EO 106 ; the organic silicon source is tetramethyl orthosilicate; the organic titanium source is titanium citrate; the inorganic salt is ferric nitrate nonahydrate; the solvent is ethanol and water.
进一步的，步骤（1）中所用的表面活性剂、溶剂、有机钛源、无机盐、硅源、酚醛树脂溶液的质量比为1：30：5：4：4：3；所述的表面活性剂为EO132PO60EO132；所述的有机硅源为正硅酸四丙酯；所述的有机钛源为柠檬酸钛；所述的无机盐为六水合硝酸钴；所述的溶剂为甲醇和水。 Further, the mass ratio of the surfactant, solvent, organic titanium source, inorganic salt, silicon source, and phenolic resin solution used in step (1) is 1:30:5:4:4:3; the surface active The agent is EO 132 PO 60 EO 132 ; the organic silicon source is tetrapropyl orthosilicate; the organic titanium source is titanium citrate; the inorganic salt is cobalt nitrate hexahydrate; the solvent is methanol and water.
本发明还提供了通过上述的制备方法获得的氮化钛/碳复合纳米材料在制作超级电容器的电极材料中的用途。 The present invention also provides the use of the titanium nitride/carbon composite nanomaterial obtained by the above preparation method in making electrode materials for supercapacitors.
本发明将表面活性剂、有机钛源、无机盐、硅源和碳源按照一定的比例溶解在溶剂中，在一定温度下，通过有机-无机协同作用，并进一步在高温氮气气氛下碳化，获得氮化钛/二氧化硅/碳的复合物，用碱溶液除去二氧化硅。由于在制备过程中加入了作为硬模板剂的硅源，可以阻止高温焙烧过程中孔道的塌陷，从而制备得到具有高比表面积的氮化钛/碳纳米材料。最终得到的氮化钛/碳复合纳米材料的比表面积为383~514m2/g、孔体积为2.3~3.2nm，应用在电化学电容器上的比容量为79~145F/g。 In the present invention, surfactants, organic titanium sources, inorganic salts, silicon sources and carbon sources are dissolved in a solvent according to a certain ratio, and at a certain temperature, through organic-inorganic synergy, and further carbonized under a high-temperature nitrogen atmosphere to obtain Titanium Nitride/Silicon Dioxide/Carbon Composite, SiO2 removal with alkaline solution. Since the silicon source as a hard template is added in the preparation process, the collapse of the pores during the high-temperature calcination process can be prevented, thereby preparing the titanium nitride/carbon nanometer material with a high specific surface area. The finally obtained titanium nitride/carbon composite nanomaterial has a specific surface area of 383-514m2/g, a pore volume of 2.3-3.2nm, and a specific capacity applied to electrochemical capacitors of 79-145F/g.
本发明和已有技术相比，其技术进步是显著的。本发明解决了现有技术中的制备方法需要较高温度焙烧、操作繁复等缺点，从而抑制了TiN的大规模生产的技术问题。本发明利用有机钛和酚醛树脂分别作为钛源和碳源，其中加入无机盐作为催化剂，利用蒸发诱导自组装的方法在较低温度下得到TiN/C复合纳米材料。本发明具有工艺简单、原料混合均匀、合成时间短、合成温度低，一般的管式炉即可满足焙烧的要求，适用于规模化生产等特点。 Compared with the prior art, the technical progress of the present invention is remarkable. The invention solves the disadvantages of high-temperature roasting and complicated operation in the preparation method in the prior art, thereby suppressing the technical problem of large-scale production of TiN. The invention uses organic titanium and phenolic resin as titanium source and carbon source respectively, adds inorganic salt as catalyst, and obtains TiN/C composite nanometer material at relatively low temperature by the method of evaporation-induced self-assembly. The invention has the characteristics of simple process, uniform mixing of raw materials, short synthesis time, low synthesis temperature, general tube furnace can meet the roasting requirements, and is suitable for large-scale production.
附图说明 Description of drawings
图1是实施例1所得的高结晶度、大比表面积的氮化钛/复合纳米材料的小角XRD图； Fig. 1 is the small angle XRD figure of the titanium nitride/composite nano material of the high crystallinity of embodiment 1 gained, large specific surface area;
图2是实施例1中高结晶度、大比表面积的氮化钛/复合纳米材料大角XRD图谱； Fig. 2 is the large-angle XRD collection of titanium nitride/composite nanomaterials of high crystallinity and large specific surface area in embodiment 1;
图3是实施例1中所得的高结晶度、大比表面积的氮化钛/复合纳米材料的氮气吸附-脱附图； Fig. 3 is the nitrogen adsorption-take off drawing of the titanium nitride/composite nano material of the high crystallinity obtained in embodiment 1, large specific surface area;
图4是实施例1中所得的高结晶度、大比表面积的氮化钛/复合纳米材料的循环伏安图。 4 is a cyclic voltammogram of the titanium nitride/composite nanomaterial with high crystallinity and large specific surface area obtained in Example 1.
具体实施方式 Detailed ways
以下通过具体实施例并结合附图来对本发明进行进一步的描述，但本发明的保护范围不限于此。 The present invention will be further described below through specific embodiments in conjunction with the accompanying drawings, but the protection scope of the present invention is not limited thereto.
所述方法如无特别说明。均为常规方法。所述材料如无特别说明，均能从公开商业途径买得到。 The method is unless otherwise specified. are conventional methods. The materials can be purchased from open commercial channels unless otherwise specified.
本发明各实施例所用的仪器或设备的型号及生产厂家信息如下： The model and manufacturer's information of instrument or equipment used in each embodiment of the present invention are as follows:
电子天平JA203上海海康电子仪器厂 Electronic Balance JA203 Shanghai Haikang Electronic Instrument Factory
马弗炉DC－B8/11北京独创科技有限公司 Muffle Furnace DC－B8/11 Beijing Original Technology Co., Ltd.
电化学工作站CH660D上海辰华仪器公司 Electrochemical workstation CH660D Shanghai Chenhua Instrument Co., Ltd.
电热恒温鼓风干燥箱DHG－9070A上海一恒科学仪器 Electric constant temperature blast drying oven DHG－9070A Shanghai Yiheng Scientific Instruments
管式炉，型号SL1700Ⅱ型，生产厂家：上海升利测试仪器有限公司； Tube furnace, model SL1700Ⅱ, manufacturer: Shanghai Shengli Testing Instrument Co., Ltd.;
X-射线衍射仪(XRD)，XPERTPRO荷兰帕纳科公司； X-ray diffractometer (XRD), XPERTPRO Holland PANalytical company;
全自动物理吸附分析仪，ASAP2020美国麦克公司； Fully automatic physical adsorption analyzer, ASAP2020 American Mike Company;
实施例1 Example 1
一种在较低温度下TiN/C复合纳米材料的制备方法，其特征在于包括以下步骤： A kind of preparation method of TiN/C composite nano material at lower temperature, it is characterized in that comprising the following steps:
（1）、在40℃下，将0.3g表面活性剂溶于4g溶剂中混合均匀的溶液中，然后加入0.5ml有机钛源和0.3g无机盐，搅拌混合均匀，之后加入0.4g质量百分比浓度为20%的酚醛树脂乙醇溶液，最后加入0.24g有机硅源，在40℃水浴下充分搅拌形成均相溶液，随后倒入表面皿中，放在40℃鼓风干燥箱24h，然后放到100℃鼓风干燥箱中进行交联。从而得到透明的膜状物。 (1) At 40°C, dissolve 0.3g of surfactant in 4g of solvent and mix uniformly, then add 0.5ml of organic titanium source and 0.3g of inorganic salt, stir and mix evenly, and then add 0.4g of mass percentage concentration It is 20% ethanol solution of phenolic resin, finally add 0.24g organic silicon source, fully stir in 40°C water bath to form a homogeneous solution, then pour it into a watch glass, put it in a blast drying oven at 40°C for 24h, and then put it in 100°C The cross-linking was carried out in a forced air drying oven at ℃. Thus, a transparent film was obtained.
上述所用的表面活性剂、溶剂、有机钛源、无机盐、硅源、质量百分比浓度为20%的酚醛树脂溶液的量，按质量比计算，表面活性剂：溶剂：有机钛源：无机盐：硅源：质量百分比浓度为20%的酚醛树脂溶液为1.0：13：1.7：1：1.3：0.8； The amount of the above-mentioned used surfactant, solvent, organic titanium source, inorganic salt, silicon source, and mass percent concentration of phenolic resin solution is 20%, calculated by mass ratio, surfactant: solvent: organic titanium source: inorganic salt: Silicon source: phenolic resin solution with a mass percent concentration of 20% is 1.0:13:1.7:1:1.3:0.8;
所述的表面活性剂为EO20PO70EO20； Described surfactant is EO 20 PO 70 EO 20 ;
所述溶剂为乙醇和水的混合物； The solvent is a mixture of ethanol and water;
所述有机钛源为柠檬酸钛； The organic titanium source is titanium citrate;
所述无机盐为六水合硝酸镍； The inorganic salt is nickel nitrate hexahydrate;
所述的有机硅源为正硅酸四乙酯； Described organosilicon source is tetraethyl orthosilicate;
（2）、将步骤1中得到的透明膜状物刮下，在管式炉中在氮气保护下先按速率1℃/min从室温升到300℃,焙烧两个小时，再按速率为5℃/min升至700℃进行焙烧2h，然后自然冷却到室温，即得到TiN/SiO2/C的复合物。 (2) Scrape off the transparent membrane obtained in step 1, and raise it from room temperature to 300°C at a rate of 1°C/min in a tube furnace under the protection of nitrogen, bake it for two hours, and then press the rate of Rising to 700°C at 5°C/min for 2h calcination, and then naturally cooling to room temperature to obtain a TiN/SiO 2 /C composite.
（3）、将步骤（2）得到的TiN/SiO2/C复合物加入到0.2mol/L的氢氧化钠溶液中，40℃水浴搅拌10min，然后离心水洗，洗到流出液为中性，然后自然干燥，得到TiN/C复合纳米材料。 (3) Add the TiN/SiO 2 /C composite obtained in step (2) into 0.2mol/L sodium hydroxide solution, stir in a water bath at 40°C for 10 minutes, then wash with centrifugal water until the effluent is neutral, Then dry naturally to obtain TiN/C composite nanomaterials.
采用X射线粉末衍射仪（PANalyticalX′Pertdiffractometer）对上述步骤（3）最终所得的高结晶度、大比表面积的氮化钛/碳纳米复合材料进行测定，所得的小角XRD图谱如图1所示，从图1中可以看出，所得的高结晶度、大比表面积的氧化铁/碳纳米复合材料在2斯塔1°左右有一个明显的衍射峰，由此表明了氧化铁/碳纳米复合材料具有良好的有序性。 Using X-ray powder diffractometer (PANalyticalX'Pertdiffractometer) to measure the titanium nitride/carbon nanocomposite material with high crystallinity and large specific surface area finally obtained in the above step (3), the obtained small-angle XRD pattern is shown in Figure 1. It can be seen from Figure 1 that the obtained iron oxide/carbon nanocomposites with high crystallinity and large specific surface area have an obvious diffraction peak at about 2 Sta 1°, which indicates that the iron oxide/carbon nanocomposites Has good orderliness.
采用X射线粉末衍射仪（PANalyticalX′Pertdiffractometer）对上述步骤（3）最终所得的高结晶度、大比表面积的氮化钛/碳纳米复合材料进行测定，所得的大角XRD图谱如图2所示，从图2可以看出代表TiN的衍射峰非常尖锐，证明了形成的TiN具有高的洁净度，而且镍是以单质的形式存在，并没有参加反应形成化合物，只是起来了催化剂的作用。 The titanium nitride/carbon nanocomposite material with high crystallinity and large specific surface area finally obtained in the above step (3) was measured by an X-ray powder diffractometer (PANalyticalX'Pertdiffractometer), and the obtained large-angle XRD pattern is shown in Figure 2. It can be seen from Figure 2 that the diffraction peak representing TiN is very sharp, which proves that the formed TiN has a high degree of cleanliness, and nickel exists in the form of simple substance, and does not participate in the reaction to form compounds, but only acts as a catalyst.
采用比表面积及孔隙度分析仪器，按照氮气吸脱附方法对上述步骤（3）所得的氮化钛/碳纳米复合材料进行测定，所得的氮气吸附-脱附结果如图3所示，从图3中可以看出曲线具有非常明显的回滞环，由此表明了制备得到的二氧化铁/碳纳米复合材料是介孔材料，且具有大的比表面积其比表面积为456m2/g，孔容为0.339cm3/g，孔径为2.9nm。 Using the specific surface area and porosity analysis instrument, the titanium nitride/carbon nanocomposite material obtained in the above step (3) is measured according to the nitrogen adsorption and desorption method, and the obtained nitrogen adsorption-desorption results are shown in Figure 3, from Figure 3 3, it can be seen that the curve has a very obvious hysteresis loop, which indicates that the prepared iron dioxide/carbon nanocomposite is a mesoporous material with a large specific surface area of 456m 2 /g, and the pores The volume is 0.339cm 3 /g, and the pore diameter is 2.9nm.
将上述所得的介孔氮化钛/碳复合纳米材料研磨成粉末，与导电剂乙炔黑、聚四氟乙烯按质量比为8:1:1的比例混合，均匀的涂在准确称量的泡沫镍上，在真空干燥箱中控制温度在120℃下处理12h，在10MPa压力下压片，制作成工作电极，以参比电极Ag/AgCl，对电极铂电极，和1mol/L的KOH水溶液为电解液构成三电极体系，用来测试电化学性能。 Grind the mesoporous titanium nitride/carbon composite nanomaterial obtained above into powder, mix it with the conductive agent acetylene black and polytetrafluoroethylene in a mass ratio of 8:1:1, and evenly coat it on an accurately weighed foam On nickel, control the temperature in a vacuum drying oven at 120°C for 12 hours, press the tablet under a pressure of 10MPa, and make it into a working electrode. The reference electrode Ag/AgCl, the counter electrode platinum electrode, and 1mol/L KOH aqueous solution are used as the The electrolyte constitutes a three-electrode system for testing electrochemical performance.
上述所得的超级电容器所用的电极材料通过上海辰华CHI660C电化学工作站采用循环伏安法进行测定，结果如图4所示，结果得到电极的电容量在10mV/s、20mV/s、50mV/s、100mV/s、200mV/s扫描速率下的电容量分别为97F/g、87F/g、81F/g、75F/g、68F/g。 The electrode materials used in the above-mentioned supercapacitors were measured by Shanghai Chenhua CHI660C electrochemical workstation using cyclic voltammetry. The results are shown in Figure 4. As a result, the capacitance of the electrodes is 10mV/s, 20mV/s, 50mV/s , 100mV/s, and 200mV/s scan rates are 97F/g, 87F/g, 81F/g, 75F/g, 68F/g respectively.
实施例2 Example 2
一种在较低温度下TiN/C复合纳米材料的制备方法，其特征在于包括以下步骤： A kind of preparation method of TiN/C composite nano material at lower temperature, it is characterized in that comprising the following steps:
（1）、在40℃下，将0.6g表面活性剂溶于12g溶剂中混合均匀的溶液中，然后加入1.8ml有机钛源和1.5g无机盐，搅拌混合均匀，之后加入1.2g质量百分比浓度为20%的酚醛树脂乙醇溶液，最后加入0.6g有机硅源，在40℃水浴下充分搅拌形成均相溶液，随后倒入表面皿中，放在40℃鼓风干燥箱24h，然后放到100℃鼓风干燥箱中进行交联。从而得到透明的膜状物。 (1) At 40°C, dissolve 0.6g of surfactant in 12g of solvent and mix uniformly, then add 1.8ml of organic titanium source and 1.5g of inorganic salt, stir and mix evenly, and then add 1.2g of mass percentage concentration It is a 20% ethanol solution of phenolic resin, and finally add 0.6g of organic silicon source, fully stir in a water bath at 40°C to form a homogeneous solution, then pour it into a watch glass, put it in a blast drying oven at 40°C for 24h, and then put it in 100°C The cross-linking was carried out in a forced air drying oven at ℃. Thus, a transparent film was obtained.
上述所用的表面活性剂、溶剂、有机钛源、无机盐、硅源、质量百分比浓度为20%的酚醛树脂溶液的量，按质量比计算，表面活性剂：溶剂：有机钛源：无机盐：硅源：质量百分比浓度为20%的酚醛树脂溶液为1.0：20：3：2.5：2：1； The amount of the above-mentioned used surfactant, solvent, organic titanium source, inorganic salt, silicon source, and mass percent concentration of phenolic resin solution is 20%, calculated by mass ratio, surfactant: solvent: organic titanium source: inorganic salt: Silicon source: phenolic resin solution with a mass percent concentration of 20% is 1.0:20:3:2.5:2:1;
所述的表面活性剂为EO132PO60EO132； Described surfactant is EO 132 PO 60 EO 132 ;
所述溶剂为甲醇和水的混合物； The solvent is a mixture of methanol and water;
所述有机钛源为柠檬酸钛； The organic titanium source is titanium citrate;
所述无机盐为九水合硝酸铁； Described inorganic salt is ferric nitrate nonahydrate;
所述的有机硅源为正硅酸四甲酯； Described organosilicon source is tetramethyl orthosilicate;
（2）、将步骤1中得到的透明膜状物刮下，在管式炉中在氮气保护下先按速率1℃/min从室温升到300℃,焙烧两个小时，再按速率为5℃/min升至800℃进行焙烧2h，然后自然冷却到室温，即得到TiN/SiO2/C的复合物。 (2) Scrape off the transparent membrane obtained in step 1, and raise it from room temperature to 300°C at a rate of 1°C/min in a tube furnace under the protection of nitrogen, bake it for two hours, and then press the rate of 5°C/min was raised to 800°C for 2h, and then naturally cooled to room temperature to obtain a TiN/SiO 2 /C composite.
（3）、将步骤（2）得到的TiN/SiO2/C复合物加入到0.5mol/L的氢氧化钠溶液中，40℃水浴搅拌30min，然后离心水洗，洗到流出液为中性，然后自然干燥，得到TiN/C复合纳米材料。 (3) Add the TiN/SiO 2 /C composite obtained in step (2) into 0.5mol/L sodium hydroxide solution, stir in a water bath at 40°C for 30 minutes, then wash with centrifugal water until the effluent is neutral, Then dry naturally to obtain TiN/C composite nanomaterials.
采用比表面积及孔隙度分析仪器，按照氮气吸脱附方法对上述步骤（3）所得的介孔氮化钛/碳纳米复合材料进行测定，所得的氮气吸附-脱附结果测的材料的比表面积为385m2/g，孔容为0.278cm3/g，孔径为2.3nm。 The specific surface area and porosity analysis instrument is used to measure the mesoporous titanium nitride/carbon nanocomposite material obtained in the above step (3) according to the nitrogen adsorption and desorption method, and the specific surface area of the material measured by the obtained nitrogen adsorption-desorption results It is 385m 2 /g, the pore volume is 0.278cm 3 /g, and the pore diameter is 2.3nm.
将上述所得的介孔氮化钛/碳复合纳米材料研磨成粉末，与导电剂乙炔黑、聚四氟乙烯按质量比为8:1:1的比例混合，均匀的涂在准确称量的泡沫镍上，在真空干燥箱中控制温度在120℃下处理12h，在10MPa压力下压片，制作成工作电极，以参比电极Ag/AgCl，对电极铂电极，和1mol/L的KOH水溶液为电解液构成三电极体系，用来测试电化学性能。 Grind the mesoporous titanium nitride/carbon composite nanomaterial obtained above into powder, mix it with the conductive agent acetylene black and polytetrafluoroethylene in a mass ratio of 8:1:1, and evenly coat it on an accurately weighed foam On nickel, control the temperature in a vacuum drying oven at 120°C for 12 hours, press the tablet under a pressure of 10MPa, and make it into a working electrode. The reference electrode Ag/AgCl, the counter electrode platinum electrode, and 1mol/L KOH aqueous solution are used as the The electrolyte constitutes a three-electrode system for testing electrochemical performance.
上述所得的超级电容器所用的电极材料通过上海辰华CHI660C电化学工作站采用循环伏安法进行测定，结果如图4所示，结果得到电极的电容量在10mV/s扫描速率下的电流密度下为82F/g。 The electrode material used in the supercapacitor of the above-mentioned gained is measured by Shanghai Chenhua CHI660C electrochemical workstation using cyclic voltammetry, and the results are shown in Figure 4. As a result, the capacitance of the electrode obtained at the current density at a scan rate of 10mV/s is 82F/g.
实施例3 Example 3
一种在较低温度下TiN/C复合纳米材料的制备方法，其特征在于包括以下步骤： A kind of preparation method of TiN/C composite nano material at lower temperature, it is characterized in that comprising the following steps:
（1）、在40℃下，将1g表面活性剂溶于30g溶剂中混合均匀的溶液中，然后加入5ml有机钛源和4g无机盐，搅拌混合均匀，之后加入4g质量百分比浓度为20%的酚醛树脂乙醇溶液，最后加入3g有机硅源，在40℃水浴下充分搅拌形成均相溶液，随后倒入表面皿中，放在40℃鼓风干燥箱24h，然后放到100℃鼓风干燥箱中进行交联。从而得到透明的膜状物。 (1) At 40°C, dissolve 1g of surfactant in 30g of solvent and mix uniformly, then add 5ml of organic titanium source and 4g of inorganic salt, stir and mix evenly, and then add 4g of 20% by mass concentration Phenolic resin ethanol solution, finally add 3g of organic silicon source, fully stir in a 40°C water bath to form a homogeneous solution, then pour it into a watch glass, put it in a blast drying oven at 40°C for 24 hours, and then put it in a blast drying oven at 100°C in cross-linking. Thus, a transparent film was obtained.
上述所用的表面活性剂、溶剂、有机钛源、无机盐、硅源、质量百分比浓度为20%的酚醛树脂溶液的量，按质量比计算，表面活性剂：溶剂：有机钛源：无机盐：硅源：质量百分比浓度为20%的酚醛树脂溶液为1.0：30：5：4：4：3； The amount of the above-mentioned used surfactant, solvent, organic titanium source, inorganic salt, silicon source, and mass percent concentration of phenolic resin solution is 20%, calculated by mass ratio, surfactant: solvent: organic titanium source: inorganic salt: Silicon source: phenolic resin solution with a mass percent concentration of 20% is 1.0:30:5:4:4:3;
所述的表面活性剂为EO106PO70EO106； Described surfactant is EO 106 PO 70 EO 106 ;
所述溶剂为乙二醇和水的混合物； Described solvent is the mixture of ethylene glycol and water;
所述有机钛源为柠檬酸钛； The organic titanium source is titanium citrate;
所述无机盐为六水合硝酸钴； The inorganic salt is cobalt nitrate hexahydrate;
所述的有机硅源为正硅酸四丙酯； Described organosilicon source is tetrapropyl orthosilicate;
（2）、将步骤1中得到的透明膜状物刮下，在管式炉中在氮气保护下先按速率1℃/min从室温升到300℃,焙烧两个小时，再按速率为5℃/min升至900℃进行焙烧2h，然后自然冷却到室温，即得到TiN/SiO2/C的复合物。 (2) Scrape off the transparent membrane obtained in step 1, and raise it from room temperature to 300°C at a rate of 1°C/min in a tube furnace under the protection of nitrogen, bake it for two hours, and then press the rate of 5°C/min was raised to 900°C for 2h calcination, and then naturally cooled to room temperature to obtain a TiN/SiO 2 /C composite.
（3）、将步骤（2）得到的TiN/SiO2/C复合物加入到2mol/L的氢氧化钠溶液中，40℃水浴搅拌30min，然后离心水洗，洗到流出液为中性，然后自然干燥，得到TiN/C复合纳米材料。 (3) Add the TiN/SiO 2 /C complex obtained in step (2) into 2mol/L sodium hydroxide solution, stir in a water bath at 40°C for 30 minutes, then wash with centrifugal water until the effluent is neutral, then Dry naturally to obtain a TiN/C composite nanomaterial.
采用比表面积及孔隙度分析仪器，按照氮气吸脱附方法对上述步骤（3）所得的介孔氮化钛/碳纳米复合材料进行测定，所得的氮气吸附-脱附结果测的材料的比表面积为512m2/g，孔容为0.423cm3/g，孔径为3.1nm。 The specific surface area and porosity analysis instrument is used to measure the mesoporous titanium nitride/carbon nanocomposite material obtained in the above step (3) according to the nitrogen adsorption and desorption method, and the specific surface area of the material measured by the obtained nitrogen adsorption-desorption results It is 512m 2 /g, the pore volume is 0.423cm 3 /g, and the pore diameter is 3.1nm.
将上述所得的介孔氮化钛/碳复合纳米材料研磨成粉末，与导电剂乙炔黑、聚四氟乙烯按质量比为8:1:1的比例混合，均匀的涂在准确称量的泡沫镍上，在真空干燥箱中控制温度在120℃下处理12h，在10MPa压力下压片，制作成工作电极，以参比电极Ag/AgCl，对电极铂电极，和1mol/L的KOH水溶液为电解液构成三电极体系，用来测试电化学性能。 Grind the mesoporous titanium nitride/carbon composite nanomaterial obtained above into powder, mix it with the conductive agent acetylene black and polytetrafluoroethylene in a mass ratio of 8:1:1, and evenly coat it on an accurately weighed foam On nickel, control the temperature in a vacuum drying oven at 120°C for 12 hours, press the tablet under a pressure of 10MPa, and make it into a working electrode. The reference electrode Ag/AgCl, the counter electrode platinum electrode, and 1mol/L KOH aqueous solution are used as the The electrolyte constitutes a three-electrode system for testing electrochemical performance.
上述所得的超级电容器所用的电极材料通过上海辰华CHI660C电化学工作站采用循环伏安法进行测定，结果如图4所示，结果得到电极的电容量在10mV/s扫描速率下的电流密度下为145F/g。 The electrode material used in the supercapacitor of the above-mentioned gained is measured by Shanghai Chenhua CHI660C electrochemical workstation using cyclic voltammetry, and the results are shown in Figure 4. As a result, the capacitance of the electrode obtained at the current density at a scan rate of 10mV/s is 145F/g.
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