CN108832137B - Preparation method of N-doped carbon nanospheres supported NiCoMnO4 nanoparticles - Google Patents
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Abstract
本发明公开了一种N掺杂纳米碳球负载NiCoMnO4纳米颗粒复合材料（NiCoMnO4/NCS）的制备方法，在室温下原位聚合吡咯制得分散均匀的聚吡咯分散液，将Ni(CH3CO2)2·4H2O、Co(CH3CO2)2·4H2O和Mn(CH3CO2)2·4H2O的水溶液分别加入到上述聚吡咯的分散液中，剧烈搅拌，将混合物转移到水热高压釜反应器中持续反应一段时间，离心，洗涤并干燥制得NiCoMnO4/NCS复合材料。该复合材料为可用于氧反应的能量存储/转换装置（如金属‑氧气电池或燃料电池）提供了低成本且高效的电催化剂，本发明制备方法简单、成本较低，展示了良好的应用前景。
The invention discloses a preparation method of N-doped nano-carbon ball-supported NiCoMnO 4 nano-particle composite material (NiCoMnO 4 /NCS). The in-situ polymerization of pyrrole at room temperature obtains a uniformly dispersed polypyrrole dispersion, and Ni(CH The aqueous solutions of 3 CO 2 ) 2 .4H 2 O, Co(CH 3 CO 2 ) 2 .4H 2 O and Mn(CH 3 CO 2 ) 2 .4H 2 O were respectively added to the above polypyrrole dispersion and stirred vigorously. , the mixture was transferred to a hydrothermal autoclave reactor for a period of time, centrifuged, washed and dried to obtain NiCoMnO 4 /NCS composites. The composite material provides a low-cost and high-efficiency electrocatalyst for energy storage/conversion devices (such as metal-oxygen batteries or fuel cells) that can be used for oxygen reactions. The preparation method of the invention is simple and low in cost, and shows good application prospects. .
Description
技术领域technical field
本发明属于材料领域，具体为一种氮掺杂碳纳米球负载NiCoMnO4纳米颗粒的制备方法。The invention belongs to the field of materials, in particular to a preparation method of NiCoMnO 4 nanoparticles supported by nitrogen-doped carbon nano-spheres.
背景技术Background technique
具有尖晶石结构的混合价态过渡金属氧化物在锂离子电池，超级电容器及电催化剂等应用方面都获得了广泛的应用。由于与这些尖晶石结构相结合的阳离子多价态的存在赋予了它们比简单的金属氧化物更优异的性能。这种多价性质通过提供可逆吸附的供体-受体化学吸附位点，使得其在电化学反应中具有更强的电催化活性。特别地，尖晶石钴酸盐由于其优异的电催化活性，易制备性，高稳定性和低成本而引起了人们的极大关注。NiCoMnO4由于Co含量低，稳定性高，电化学活性好，用作电池和超级电容器中的电极材料有着重要的意义。Mixed-valence transition metal oxides with spinel structures have been widely used in lithium-ion batteries, supercapacitors, and electrocatalysts. The presence of cationic polyvalent states associated with these spinel structures endows them with superior properties over simple metal oxides. This multivalent nature enables stronger electrocatalytic activity in electrochemical reactions by providing reversibly adsorbed donor-acceptor chemisorption sites. In particular, spinel cobaltates have attracted great attention due to their excellent electrocatalytic activity, facile preparation, high stability, and low cost. NiCoMnO 4 is of great significance as an electrode material in batteries and supercapacitors due to its low Co content, high stability, and good electrochemical activity.
最近，科学家报道合成了NiCoMnO4/N-MWCNT及NiCoMnO4/N-RGO纳米复合材料并测试了其在氧还原和吸氧反应方面的电催化活性，证明了NiCoMnO4/N-MWCN及NiCoMnO4/N-RGO纳米复合材料作为电催化剂的巨大潜力。与商业催化剂相比，NiCoMnO4/N-MWCNT及NiCoMnO4/N-RGO均显示了良好的电催化活性。这些结果表明NiCoMnO4与碳载体相结合显示了较强的电催化活性，然而NCS载体用来负载NiCoMnO4的催化剂还未得到报道。Recently, scientists reported the synthesis of NiCoMnO 4 /N-MWCNT and NiCoMnO 4 /N-RGO nanocomposites and tested their electrocatalytic activities in oxygen reduction and oxygen absorption reactions, proving that NiCoMnO 4 /N-MWCN and NiCoMnO 4 /N-RGO nanocomposites have great potential as electrocatalysts. Compared with commercial catalysts, both NiCoMnO 4 /N-MWCNT and NiCoMnO 4 /N-RGO showed good electrocatalytic activity. These results indicate that NiCoMnO 4 combined with carbon supports shows strong electrocatalytic activity, however, the use of NCS supports to support NiCoMnO 4 as a catalyst has not been reported yet.
发明内容SUMMARY OF THE INVENTION
本发明目的是提出将NiCoMnO4颗粒锚定在低成本的氮掺杂纳米碳球上的研究策略，具体以N掺杂碳纳米球为载体实现NCS负载NiCoMnO4纳米颗粒复合材料的制备，为高效的双功能电催化剂的合成提供了更廉价更简单的方法。The purpose of the present invention is to propose a research strategy for anchoring NiCoMnO 4 particles on low-cost nitrogen-doped carbon nanospheres . The synthesis of bifunctional electrocatalysts provides a cheaper and simpler method.
本发明是采用如下技术方案实现的：The present invention adopts the following technical scheme to realize:
一种氮掺杂碳纳米球负载NiCoMnO4纳米颗粒的制备方法，包括以下步骤，A method for preparing NiCoMnO nanoparticles supported by nitrogen-doped carbon nanospheres, comprising the following steps:
（1）、首先制备N掺杂碳纳米球载体的前驱体即球形聚吡咯；(1) First, prepare the precursor of N-doped carbon nanosphere carrier, namely spherical polypyrrole;
（2）、将一定浓度球形聚吡咯的分散液与一定体积的Ni(CH3CO2)2·4H2O, Co(CH3CO2)2·4H2O和Mn(CH3CO2)2·4H2O的水溶液混合搅拌均匀；(2), mix a certain concentration of spherical polypyrrole dispersion with a certain volume of Ni(CH 3 CO 2 ) 2 ·4H 2 O, Co(CH 3 CO 2 ) 2 ·4H 2 O and Mn(CH 3 CO 2 ) 2. The aqueous solution of 4H 2 O is mixed and stirred evenly;
（3）、将上述混合溶液进一步转移到水热高压釜反应器中并在一定的温度下持续反应一定的时间；(3), further transfer the above-mentioned mixed solution to the hydrothermal autoclave reactor and continue to react for a certain time at a certain temperature;
（4、）最后离心、洗涤并干燥而成。(4,) Finally, it is centrifuged, washed and dried.
步骤（1）中，球形聚吡咯的制备过程如下：5mL的吡咯加入500mL水中，加入0.5gFeCl2及25mL H2O2进行氧化聚合反应12小时，多次离心、洗涤及干燥得到聚吡咯微球，将制得的聚吡咯微球分散到水中超声即得到聚吡咯分散液。In step (1), the preparation process of spherical polypyrrole is as follows: 5 mL of pyrrole is added to 500 mL of water, 0.5 g of FeCl 2 and 25 mL of H 2 O 2 are added to carry out oxidative polymerization for 12 hours, and polypyrrole microspheres are obtained by centrifuging, washing and drying multiple times. , disperse the prepared polypyrrole microspheres in water and ultrasonically obtain a polypyrrole dispersion.
步骤（2）中，聚吡咯分散液的浓度为1.0-5.0mg/mL，体积为20-50mL。In step (2), the concentration of the polypyrrole dispersion is 1.0-5.0 mg/mL, and the volume is 20-50 mL.
步骤（2）中，Ni(CH3CO2)2·4H2O、Co(CH3CO2)2·4H2O和Mn(CH3CO2)2·4H2O的体积均为1.0-5.0mL。In step (2), the volumes of Ni(CH 3 CO 2 ) 2 ·4H 2 O, Co(CH 3 CO 2 ) 2 ·4H 2 O and Mn(CH 3 CO 2 ) 2 ·4H 2 O are all 1.0- 5.0 mL.
步骤（2）中，剧烈搅拌的时间为1-5小时。In step (2), the vigorous stirring time is 1-5 hours.
步骤（3）中，搅拌反应后的样品置于体积为50的水热高压釜反应器中进行水热反应；反应的温度为100-250℃，反应时间为1-5小时。In step (3), the sample after stirring and reacting is placed in a hydrothermal autoclave reactor with a volume of 50 for hydrothermal reaction; the reaction temperature is 100-250°C, and the reaction time is 1-5 hours.
步骤（3）中，离心的转速为4000-8000转，离心时间为10-20分钟，洗涤所用的溶剂为乙醇及去离子水，干燥的温度为50-150℃。In step (3), the rotation speed of centrifugation is 4000-8000 rpm, the centrifugation time is 10-20 minutes, the solvent used for washing is ethanol and deionized water, and the drying temperature is 50-150°C.
与现有技术相比，本发明的有益效果为：Compared with the prior art, the beneficial effects of the present invention are:
1、本发明提供了一种成本低、合成步骤简单的NCS负载NiCoMnO4纳米颗粒复合材料的制备方法。1. The present invention provides a preparation method of NCS-supported NiCoMnO 4 nanoparticle composite material with low cost and simple synthesis steps.
2、本发明利用碳纳米球表面的N原子与Co、Ni及Mn之间的络合作用，有效的提高了NiCoMnO4纳米颗粒的分散性和稳定性。2. The present invention effectively improves the dispersibility and stability of NiCoMnO 4 nanoparticles by utilizing the complexation between N atoms on the surface of carbon nanospheres and Co, Ni and Mn.
3、新型的N掺杂纳米碳球负载NiCoMnO4纳米颗粒催化剂的制备为电催化反应提供了新的催化剂。3. The preparation of a novel N-doped carbon nanosphere-supported NiCoMnO4 nanoparticle catalyst provides a new catalyst for electrocatalytic reactions.
4、该方法步骤简单、成本较低，适合大规模制备。4. The method has simple steps and low cost, and is suitable for large-scale preparation.
本发明设计合理，为混合价态过渡金属氧化物NiCoMnO4的制备提供了一种新的碳载体，通过将N掺杂碳纳米球载体的前驱体即球形聚吡咯的分散液与一定体积Ni(CH3CO2)2·4H2O、Co(CH3CO2)2·4H2O和Mn(CH3CO2)2·4H2O的水溶液均匀混合，剧烈搅拌一定时间后，将混合物转移到水热高压釜反应器中并在一定温度下持续反应一定时间，最后离心、洗涤并干燥而制得，提供了一种成本低、合成步骤简单的NCS负载NiCoMnO4纳米颗粒复合材料的制备方法。The present invention has a reasonable design, and provides a new carbon carrier for the preparation of mixed valence transition metal oxide NiCoMnO 4 . The aqueous solutions of CH 3 CO 2 ) 2 ·4H 2 O, Co(CH 3 CO 2 ) 2 ·4H 2 O and Mn(CH 3 CO 2 ) 2 ·4H 2 O were uniformly mixed, and after vigorous stirring for a certain period of time, the mixture was transferred into a hydrothermal autoclave reactor and continue to react at a certain temperature for a certain period of time, and finally centrifuged, washed and dried to obtain a preparation method of NCS-supported NiCoMnO 4 nanoparticle composite material with low cost and simple synthesis steps. .
附图说明Description of drawings
图1表示本发明实施例制备的掺杂碳纳米球负载NiCoMnO4纳米颗粒的SEM图。FIG. 1 shows the SEM image of the doped carbon nanosphere-supported NiCoMnO 4 nanoparticles prepared in the embodiment of the present invention.
具体实施方式Detailed ways
下面对本发明的具体实施例进行详细说明。Specific embodiments of the present invention will be described in detail below.
本发明所述的N掺杂纳米碳球负载NiCoMnO4纳米颗粒复合材料（NiCoMnO4/NCS）的制备方法，在室温下原位聚合吡咯制得分散均匀的聚吡咯分散液，将Ni(CH3CO2)2·4H2O、Co(CH3CO2)2·4H2O和Mn(CH3CO2)2·4H2O的水溶液分别加入到上述聚吡咯的分散液中，剧烈搅拌后，将混合物转移到水热高压釜反应器中持续反应一段时间，离心，洗涤并干燥制得NiCoMnO4/NCS复合材料。According to the preparation method of the N-doped nano-carbon ball-supported NiCoMnO 4 nanoparticle composite material (NiCoMnO 4 /NCS) according to the present invention, a uniformly dispersed polypyrrole dispersion is obtained by in-situ polymerization of pyrrole at room temperature, and Ni(CH 3 The aqueous solutions of CO 2 ) 2 ·4H 2 O, Co(CH 3 CO 2 ) 2 ·4H 2 O and Mn(CH 3 CO 2 ) 2 ·4H 2 O were respectively added to the above polypyrrole dispersion, and after vigorous stirring , the mixture was transferred to a hydrothermal autoclave reactor for a period of time, centrifuged, washed and dried to obtain NiCoMnO 4 /NCS composites.
实施例1Example 1
5mL吡咯加入500mL水中，加入0.5gFeCl2及25mLH2O2进行氧化聚合反应12小时，多次离心、洗涤及干燥得到聚吡咯微球。5 mL of pyrrole was added to 500 mL of water, 0.5 g of FeCl 2 and 25 mL of H 2 O 2 were added to carry out oxidative polymerization for 12 hours, and polypyrrole microspheres were obtained by centrifugation, washing and drying several times.
将一定质量的制得的PPy微球分散到水中即得到浓度为1.0mg/mL的聚吡咯分散液，体积为50mL。Disperse a certain mass of the prepared PPy microspheres into water to obtain a polypyrrole dispersion with a concentration of 1.0 mg/mL, and the volume is 50 mL.
将50mL浓度为1.0mg/mL的聚吡咯分散液与体积均为3mL的Ni(CH3CO2)2·4H2O，Co(CH3CO2)2·4H2O和Mn(CH3CO2)2·4H2O均匀混合，并剧烈搅拌3-5小时。50 mL of polypyrrole dispersion with a concentration of 1.0 mg/mL was mixed with Ni(CH 3 CO 2 ) 2 ·4H 2 O, Co(CH 3 CO 2 ) 2 ·4H 2 O and Mn(CH 3 CO 2 ) with a volume of 3 mL. 2 ) 2.4H2O is mixed evenly and vigorously stirred for 3-5 hours.
将搅拌反应后的样品进一步转移到50mL水热高压釜反应器中并在150℃持续反应2小时，以6000rpm离心15分钟，用乙醇和去离子水分别洗涤数次，在烘箱中70℃干燥，即可制得N掺杂碳纳米球负载NiCoMnO4纳米颗粒复合材料。The stirred reaction samples were further transferred to a 50 mL hydrothermal autoclave reactor and continued to react at 150 °C for 2 hours, centrifuged at 6000 rpm for 15 minutes, washed several times with ethanol and deionized water, and dried at 70 °C in an oven. The N-doped carbon nanosphere-supported NiCoMnO 4 nanoparticle composite material can be prepared.
实施例2Example 2
5mL吡咯加入500mL水中，加入0.5g FeCl2及25mL H2O2进行氧化聚合反应12小时，多次离心、洗涤及干燥得到聚吡咯微球。5 mL of pyrrole was added to 500 mL of water, 0.5 g of FeCl 2 and 25 mL of H 2 O 2 were added to carry out oxidative polymerization for 12 hours, and polypyrrole microspheres were obtained by centrifugation, washing and drying several times.
将一定质量的制得的PPy微球分散到水中即得到浓度为3.0mg/mL的聚吡咯分散液，体积30mL。Disperse a certain mass of the prepared PPy microspheres into water to obtain a polypyrrole dispersion with a concentration of 3.0 mg/mL, with a volume of 30 mL.
将30mL浓度为3.0mg/mL的聚吡咯分散液与体积均为1mL的Ni(CH3CO2)2·4H2O，Co(CH3CO2)2·4H2O和Mn(CH3CO2)2·4H2O均匀混合，并剧烈搅拌1-3小时。30 mL of polypyrrole dispersion with a concentration of 3.0 mg/mL was mixed with Ni(CH 3 CO 2 ) 2 ·4H 2 O, Co(CH 3 CO 2 ) 2 ·4H 2 O and Mn(CH 3 CO 2 ) with a volume of 1 mL. 2 ) 2.4H2O is mixed evenly and vigorously stirred for 1-3 hours.
将搅拌反应后的样品进一步转移到50mL水热高压釜反应器中并在100℃持续反应3小时，以4000rpm离心10分钟，用乙醇和去离子水分别洗涤数次，在烘箱中50℃干燥，即可制得N掺杂碳纳米球负载NiCoMnO4纳米颗粒复合材料。The stirred reaction samples were further transferred to a 50 mL hydrothermal autoclave reactor and continued to react at 100 °C for 3 hours, centrifuged at 4000 rpm for 10 minutes, washed several times with ethanol and deionized water, and dried in an oven at 50 °C. The N-doped carbon nanosphere-supported NiCoMnO 4 nanoparticle composite material can be prepared.
实施例3Example 3
5mL吡咯加入500mL水中，加入0.5g FeCl2及25mL H2O2进行氧化聚合反应12小时，多次离心、洗涤及干燥得到聚吡咯微球。5 mL of pyrrole was added to 500 mL of water, 0.5 g of FeCl 2 and 25 mL of H 2 O 2 were added to carry out oxidative polymerization for 12 hours, and polypyrrole microspheres were obtained by centrifugation, washing and drying several times.
将一定质量的制得的PPy微球分散到水中即得到浓度为5.0mg/mL的聚吡咯分散液，体积20mL。Disperse a certain mass of the prepared PPy microspheres into water to obtain a polypyrrole dispersion with a concentration of 5.0 mg/mL, with a volume of 20 mL.
将20mL浓度为5.0mg/mL的聚吡咯分散液与体积均为5mL的Ni(CH3CO2)2·4H2O，Co(CH3CO2)2·4H2O和Mn(CH3CO2)2·4H2O均匀混合，并剧烈搅拌1-3小时。20 mL of polypyrrole dispersion with a concentration of 5.0 mg/mL was mixed with Ni(CH 3 CO 2 ) 2 ·4H 2 O, Co(CH 3 CO 2 ) 2 · 4H 2 O and Mn(CH 3 CO 2 ) with a volume of 5 mL. 2 ) 2.4H2O is mixed evenly and vigorously stirred for 1-3 hours.
将搅拌反应后的样品进一步转移到50mL水热高压釜反应器中并在250℃持续反应2小时，以8000rpm离心20分钟，用乙醇和去离子水分别洗涤数次，在烘箱中150℃干燥，即可制得N掺杂碳纳米球负载NiCoMnO4纳米颗粒复合材料。The stirred reaction samples were further transferred to a 50 mL hydrothermal autoclave reactor and continued to react at 250°C for 2 hours, centrifuged at 8000 rpm for 20 minutes, washed several times with ethanol and deionized water, and dried at 150°C in an oven. The N-doped carbon nanosphere-supported NiCoMnO 4 nanoparticle composite material can be prepared.
本发明制备的复合材料为可用于氧反应的能量存储/转换装置（如金属-氧气电池或燃料电池）提供了低成本且高效的电催化剂，本发明的创新点在于首次提出了N掺杂碳纳米球负载NiCoMnO4纳米颗粒的实验方案，制备方法简单且成本较低，展示了良好的应用前景。The composite material prepared by the present invention provides a low-cost and high-efficiency electrocatalyst for energy storage/conversion devices (such as metal-oxygen batteries or fuel cells) that can be used for oxygen reactions. The innovation of the present invention is that N-doped carbon is proposed for the first time. The experimental scheme of nanosphere-loaded NiCoMnO4 nanoparticles, the preparation method is simple and the cost is low, and it shows a good application prospect.
应当指出，对于本技术领域的一般技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和应用，这些改进和应用也视为本发明的保护范围。It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, several improvements and applications can also be made, and these improvements and applications are also regarded as the protection scope of the present invention.
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|---|---|---|---|---|
| CN103272591A (en) * | 2013-05-27 | 2013-09-04 | 浙江大学 | Preparation method of anode catalyst for sodium borohydride fuel battery |
| CN105304895A (en) * | 2015-10-23 | 2016-02-03 | 南京邮电大学 | Lithium-containing metal oxide lithium electricity nanoelectrode materials and preparation method thereof |
| CN107556475A (en) * | 2017-09-12 | 2018-01-09 | 太原理工大学 | The synthetic method of the controllable spherical polypyrrole of size |
| CN107768622A (en) * | 2017-09-28 | 2018-03-06 | 东华大学 | A kind of nitrogen-doped carbon nano-fiber/molybdenum disulfide composite and its preparation method and application |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103272591A (en) * | 2013-05-27 | 2013-09-04 | 浙江大学 | Preparation method of anode catalyst for sodium borohydride fuel battery |
| CN105304895A (en) * | 2015-10-23 | 2016-02-03 | 南京邮电大学 | Lithium-containing metal oxide lithium electricity nanoelectrode materials and preparation method thereof |
| CN107556475A (en) * | 2017-09-12 | 2018-01-09 | 太原理工大学 | The synthetic method of the controllable spherical polypyrrole of size |
| CN107768622A (en) * | 2017-09-28 | 2018-03-06 | 东华大学 | A kind of nitrogen-doped carbon nano-fiber/molybdenum disulfide composite and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| NiCoMnO4nanoparticles on N-doped graphene: Highly efficient bifunctional electrocatalyst for oxygen reduction/evolution reactions;Afshin Pendashteh，et al.;《Applied Catalysis B: Environmental》;20160817;第241-252页 * |
| Three-dimensional hybrid aerogels built from graphene and polypyrrole-derived nitrogen-doped carbon nanotubes as a high-efficiency Pt-based catalyst support;Li-Mei Zhang，et al.;《Carbon》;20170609;第518-526页 * |
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