WO2016029841A1 - 钴酸镍介孔微球及其制备方法 - Google Patents

钴酸镍介孔微球及其制备方法 Download PDF

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WO2016029841A1
WO2016029841A1 PCT/CN2015/088029 CN2015088029W WO2016029841A1 WO 2016029841 A1 WO2016029841 A1 WO 2016029841A1 CN 2015088029 W CN2015088029 W CN 2015088029W WO 2016029841 A1 WO2016029841 A1 WO 2016029841A1
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nickel
nickel cobaltate
mesoporous
cobalt
cobaltate
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PCT/CN2015/088029
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French (fr)
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金玉红
王莉
何向明
尚玉明
李建军
高剑
王要武
刘恒伟
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江苏合志锂硫电池技术有限公司
江苏华东锂电技术研究院有限公司
清华大学
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Publication of WO2016029841A1 publication Critical patent/WO2016029841A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel

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  • the invention relates to a nickel cobaltate and a preparation method thereof, in particular to a nickel cobaltate mesoporous microsphere and a preparation method thereof.
  • Nickel cobaltate (NiCo 2 O 4 ) is an AB 2 O 4 type composite oxide having an inverse spinel structure in which nickel ions occupy octahedral voids, and cobalt occupies all tetrahedral voids and half of octahedral voids. Its conductivity and electrochemical activity are much higher than single nickel and cobalt oxides, and there are Co 3+ /Co 2+ and Ni 3+ /Ni 2+ redox couples, and it has the advantages of low cost and environmental friendliness. Supercapacitor electrode materials have great application value.
  • the main synthesis methods of nickel cobalt oxide include high temperature solid phase method, mechanochemical synthesis method, sol-gel method, liquid phase chemical precipitation method and the like.
  • the high-temperature solid-phase chemical reaction method is a traditional synthesis method of nickel cobaltate. Although the process is simple, the reaction time is long, the energy consumption is high, and the product granularity is large; a large amount of strain and defects are introduced in the mechanochemical synthesis process, and the obtained product has poor dispersibility;
  • the particle size obtained by the addition of the surfactant by the gel method is small and uniform, but it is easy to introduce impurities; while the product synthesized by the liquid phase chemical precipitation method is incomplete, and a partially metastable phase is formed.
  • Chinese patent application CN102745752A discloses a hydrothermal synthesis method of nickel cobaltate, which does not need to add a template agent in the preparation process, and the obtained product has high purity and can be used as a supercapacitor electrode material.
  • the product obtained by this method is a solid sphere structure, and its specific surface area still needs to be further improved.
  • a method for preparing a nickel cobaltate mesoporous microsphere comprising: dissolving a cobalt salt and a nickel salt in a ratio of a ratio of a substance of 2:1 in a mixed solvent of isopropyl alcohol and water to form a first solution; Adding urea to the first solution, stirring to form a pink second solution; adding the second solution to the hydrothermal reaction vessel for sufficient reaction and cooling, the obtained pink solid phase product is a precursor; and heat treating the precursor in air .
  • a nickel cobaltate mesoporous microsphere comprising a plurality of nickel cobaltate nanowires, wherein the nickel cobaltate mesoporous microspheres have a hollow structure and have openings.
  • a nickel cobaltate material is prepared by a simple low temperature hydrothermal environment and a subsequent high temperature heat treatment method.
  • a cobalt salt and a nickel salt are used as a raw material in isopropyl alcohol, and a mixed solvent of isopropyl alcohol and water is used as a reaction medium, thereby obtaining a nickel cobaltate mesoporous microsphere having a hollow structure and having an opening. Therefore, the inner surface can be used as an effective surface, which greatly increases the specific surface area of the nickel cobaltate material.
  • 1 is an XRD pattern of a precursor and nickel cobaltate according to an embodiment of the present invention.
  • FESEM field emission scanning electron microscopy
  • Figure 6 is a field emission scanning electron micrograph of the nickel cobaltate product of Comparative Example 1.
  • Figure 7 is a scanning electron micrograph of a field emission of a nickel cobaltate product of Comparative Example 2.
  • Figure 8 is a scanning electron micrograph of a field emission of a nickel cobaltate product of Comparative Example 3.
  • Figure 9 is a scanning electron micrograph of a field emission of a nickel cobaltate product of Comparative Example 4.
  • Figure 10 is a scanning electron micrograph of a field emission of a nickel cobaltate product of Comparative Example 5.
  • the embodiment of the invention provides a preparation method of nickel cobaltate mesoporous microspheres, comprising the following steps:
  • the second solution is added to the hydrothermal reaction vessel to be fully reacted and then cooled, and the obtained pink solid phase product is a precursor;
  • the precursor is heat treated in air.
  • the volume ratio of the isopropyl alcohol to water may be from 10:1 to 1:10, preferably from 1:5 to 5:1. Both the cobalt salt and the nickel salt are completely soluble in the mixed solvent of isopropyl alcohol and water.
  • the cobalt salt is cobalt nitrate (Co(NO 2 ) 2 ) or cobalt chloride (CoCl 2 ).
  • the nickel salt is nickel nitrate (Ni(NO 2 ) 2 ); when the cobalt salt is cobalt chloride, the nickel salt is nickel chloride (NiCl 2 ).
  • the concentration of the cobalt salt in the mixed solvent may be 0.001 mol/L to 0.02 mol/L, and the concentration of the nickel salt in the mixed solvent may be 0.0005 mol/L to 0.01 mol/L.
  • the urea is slowly added to the first solution.
  • the urea is preferably added in an amount sufficient to sufficiently precipitate the cobalt salt and the nickel salt.
  • the concentration of the urea in the mixed solvent may be from 1 mol/L to 5 mol/L.
  • the reaction temperature of the second solution in the hydrothermal reaction vessel may be 80 ° C to 180 ° C, and the reaction time may be 2 hours to 20 hours.
  • the furnace is cooled to room temperature, and the solid phase product is separated. Specifically, it may be vacuum filtered, washed three times with deionized water, then vacuum filtered again, and finally washed three times with ethanol at 60 ° C to 100 ° C. Drying in vacuum for 12 hours to 24 hours gives a purer precursor pink solid powder.
  • the pink solid powder already has the morphology of mesoporous microspheres, and the mesoporous microspheres have a hollow structure and are secondary hollow spheres formed by a large number of precursor nanowires.
  • the temperature of the heat treatment may be 200 ° C to 300 ° C, and the time may be 2 hours to 5 hours.
  • the temperature increase rate of the heat treatment may be from 1 ° C / min to 2 ° C / min.
  • the product was obtained as black nickel cobaltate mesoporous microspheres.
  • the heat treatment is only a process of transforming the material, and the morphology of the precursor and the product before and after the heat treatment is substantially the same.
  • the pink solid precursor formed in the preparation process and the black solid product obtained after the heat treatment were characterized by XRD, and it was confirmed that the pink solid precursor was a basic cobalt cobalt carbonate containing water of crystallization, and a black solid was obtained after heat treatment.
  • the product is nickel cobaltate.
  • the nickel cobaltate mesoporous microspheres obtained by the above method include a plurality of nickel cobaltate nanowires. Specifically, it is a secondary hollow mesoporous microsphere composed of a large amount of nickel cobaltate nanowires and having a hollow structure.
  • the hollow structure of the nickel cobaltate mesoporous microspheres has a diameter of about 2 micrometers to 10 micrometers and a wall thickness of less than 1 micrometer, preferably 0.3 to 0.6 micrometers.
  • the secondary hollow mesopores are microscopic and have openings. The size of the opening is large, so that the nickel cobaltate mesoporous microspheres are bowl-shaped hemispheres or spherical defects.
  • a nickel cobaltate material is prepared by a simple low temperature hydrothermal environment and a subsequent high temperature heat treatment method.
  • cobalt nitrate or cobalt chloride is used as a raw material with nickel nitrate or nickel chloride, and a mixed solvent of isopropyl alcohol and water is used as a reaction medium, thereby obtaining a nickel cobaltate mesoporous microstructure having a hollow structure. ball.
  • the nickel cobalt oxide secondary hollow sphere synthesized by the method may have an opening to form a hemispherical or spherically shaped hollow sphere structure, so that the inner surface can serve as an effective surface, and the specific surface area of the nickel cobaltate material is greatly improved.
  • the pink solution is transferred to a steel-lined polytetrafluoroethylene hydrothermal reactor, heated at 80-180 ° C for 2-20 hours, then cooled to room temperature with the furnace, taken out, subjected to vacuum filtration - three times of water washing - vacuum suction filtration -
  • the prepared sample was post-treated by three times of ethanol washing, and vacuum-dried at 60 ° C for 12 hours to obtain a pink precursor powder.
  • the prepared precursor powder was placed in a muffle furnace, and raised to 300 ° C at a heating rate of 1 ° C per minute under an air atmosphere for 2 hours, and then cooled to room temperature with a furnace to obtain a black solid powder, namely, cobalt acid.
  • Nickel mesoporous microspheres were placed in a muffle furnace, and raised to 300 ° C at a heating rate of 1 ° C per minute under an air atmosphere for 2 hours, and then cooled to room temperature with a furnace to obtain a black solid powder, namely, cobalt
  • the reaction conditions were the same as in the above Example 1, except that Co(NO 2 ) 2 6H 2 O and Ni(NO 2 ) 2 6H 2 O were replaced with CoCl 2 6H 2 O and NiCl 2 6H 2 O, and the obtained product was Nickel cobaltate mesoporous microspheres.
  • the reaction conditions were the same as in the above Example 1, except that the mixed solvent was replaced with pure water.
  • Fig. 6 it can be seen from the FESEM photograph of the product that only pure nickel cobaltate can be synthesized when using pure water as a solvent, and only the outer surface of the solid sphere can be used as an effective surface for calculating the specific surface area, so that Small specific surface area.
  • reaction conditions were the same as in the above Example 1, except that the mixed solvent was replaced with a mixed solvent of methanol and water (by volume ratio of 3:1).
  • Figure 7 it can be seen from the FESEM photograph of the product that the product synthesized as a solvent mixed with methanol and water is still a solid nickel cobaltate ball.
  • reaction conditions were the same as in the above Example 1, except that the mixed solvent was replaced with a mixed solvent of ethylene glycol and water (by volume ratio of 3:1).
  • the mixed solvent was replaced with a mixed solvent of ethylene glycol and water (by volume ratio of 3:1).
  • reaction conditions were the same as in the above Example 1, except that the mixed solvent was replaced with a mixed solvent of glycerin and water (by volume ratio of 3:1).
  • a mixed solvent of glycerin and water by volume ratio of 3:1.
  • reaction conditions were the same as in the above Example 1, except that the mixed solvent was replaced with a mixed solvent of N,N-dimethylformamide (DMF) and water (by volume ratio of 3:1).
  • DMF N,N-dimethylformamide
  • water by volume ratio of 3:1.

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Abstract

本发明涉及一种钴酸镍介孔微球的制备方法，包括：将钴盐与镍盐按照物质的量比为2:1的比例溶解在异丙醇与水的混合溶剂中形成第一溶液；向该第一溶液中加入尿素，搅拌形成粉色的第二溶液；将该第二溶液加入水热反应釜中充分反应后冷却，得到的粉色固相产物为前驱体；以及将该前驱体在空气中热处理。本发明还涉及一种钴酸镍介孔微球，包括多个钴酸镍纳米线，其中，该钴酸镍介孔微球为空心结构，且具有开口。

Description

钴酸镍介孔微球及其制备方法 技术领域
本发明涉及一种钴酸镍及其制备方法，尤其涉及一种钴酸镍介孔微球及其制备方法。
背景技术
钴酸镍(NiCo2O4)为反尖晶石型结构的AB2O4型复合氧化物，其中镍离子占据八面体空隙，钴占据全部的四面体空隙及半数的八面体空隙。其导电性及电化学活性远高于单一镍、钴氧化物，存在Co3+/Co2+及Ni3+/Ni2+氧化还原电对，同时具有成本低廉，环境友好等优点，可作为超级电容器电极材料，具有巨大的应用价值。
钴酸镍的主要合成方法有：高温固相法、机械化学合成法、溶胶-凝胶法、液相化学沉淀法等。其中高温固相化学反应法为钴酸镍传统合成方法，虽然工艺简单，但反应时间长、能耗高、产品粒度大；机械化学合成过程中引入大量应变和缺陷，所得产物分散性差；溶胶凝胶法通过加入表面活性剂得到的产物颗粒粒径较小且分布均匀，但易引入杂质；而液相化学沉淀法合成的产物结构不完整，会生成部分亚稳相。
中国专利申请CN102745752A公开了一种钴酸镍的水热合成方法，在制备过程中不需添加模板剂，所得产物纯度高，可以用做超级电容器电极材料。然而，该方法得到的产物为实心球体结构，其比表面积仍然需要进一步提高。
发明内容
有鉴于此，确有必要提供一种具有较高比表面积的钴酸镍介孔微球的制备方法。
一种钴酸镍介孔微球的制备方法，包括：将钴盐与镍盐按照物质的量比为2:1的比例溶解在异丙醇与水的混合溶剂中形成第一溶液；向该第一溶液中加入尿素，搅拌形成粉色的第二溶液；将该第二溶液加入水热反应釜中充分反应后冷却，得到的粉色固相产物为前驱体；以及将该前驱体在空气中热处理。
一种钴酸镍介孔微球，包括多个钴酸镍纳米线，其中，该钴酸镍介孔微球为空心结构，且具有开口。
本发明实施例通过简单的低温水热环境和后续高温热处理法制备钴酸镍材料。在制备过程中，将钴盐与镍盐在异丙醇做为原料，并采用异丙醇与水的混合溶剂作为反应介质，从而可以得到具有空心结构的钴酸镍介孔微球且具有开口，从而使内部的表面可以作为有效表面，大大提高了钴酸镍材料的比表面积。
 附图说明
图1为本发明实施例的前驱体和钴酸镍的XRD图。
图2至图5为本发明实施例的钴酸镍介孔微球不同放大倍数下的场发射扫描电镜(FESEM)照片。
图6为对比例1的钴酸镍产品的场发射扫描电镜照片。
图7为对比例2的钴酸镍产品的场发射扫描电镜照片。
图8为对比例3的钴酸镍产品的场发射扫描电镜照片。
图9为对比例4的钴酸镍产品的场发射扫描电镜照片。
图10为对比例5的钴酸镍产品的场发射扫描电镜照片。
如下具体实施方式将结合上述附图进一步说明本发明。
具体实施方式
下面将结合附图及具体实施例对本发明提供的钴酸镍介孔微球的制备方法作进一步的详细说明。
本发明实施例提供一种钴酸镍介孔微球的制备方法，包括以下步骤：
S1，将钴盐与镍盐按照物质的量比为2:1的比例溶解在异丙醇与水的混合溶剂中形成第一溶液；
S2，向该第一溶液中加入尿素，搅拌形成粉色的第二溶液；
S3，将该第二溶液加入水热反应釜中充分反应后冷却，得到的粉色固相产物为前驱体；以及
S4，将该前驱体在空气中热处理。
在该步骤S1中，该异丙醇与水的体积比可以为10:1~1:10，优选为1:5~5:1。钴盐与镍盐均在该异丙醇与水的混合溶剂中能够完全溶解。该钴盐为硝酸钴(Co(NO2)2)或氯化钴(CoCl2)。当钴盐为硝酸钴时，镍盐为硝酸镍(Ni(NO2)2)；当钴盐为氯化钴时，镍盐为氯化镍(NiCl2)。
钴盐在该混合溶剂中的浓度可以为0.001 mol/L ~0.02 mol/L，镍盐在该混合溶剂中的浓度可以为0.0005 mol/L ~0.01 mol/L。
在该步骤S2中，该尿素为缓慢加入该第一溶液中。该尿素加入的量优选为能够将钴盐与镍盐充分沉淀。该尿素在该混合溶剂中的浓度可以为1 mol/L ~5 mol/L。
在该步骤S3中，该第二溶液在水热反应釜中的反应温度可以为80℃~180℃，反应时间可以为2小时~20小时。水热反应完毕后随炉冷却至室温，分离出固相产物，具体可以是先真空抽滤，再三次去离子水洗涤，之后再次真空抽滤，最后三次乙醇洗涤，并在60℃~100℃真空干燥12小时~24小时，得到较为纯净的前驱体粉色固体粉末。该粉色固体粉末已经具有介孔微球的形貌，且该介孔微球具有空心结构，是由大量前驱体纳米线形成的二次空心球。
在该步骤S4中，该热处理的温度可以为200℃~300℃，时间可以为2小时~5小时。热处理的升温速度可以为1℃/分钟~2℃/分钟。热处理后得到产物为黑色的钴酸镍介孔微球。该热处理只是使材料转变的过程，热处理前后的前驱体与产物的形貌基本相同。
请参阅图1，将制备过程中生成的粉色固体前驱体与热处理后得到的黑色固体产物进行XRD表征，证明该粉色固体前驱体是含结晶水的碱式碳酸钴镍，经过热处理后得到黑色固体产物是钴酸镍。
请参阅图2~图5，通过上述方法得到的钴酸镍介孔微球包括多个钴酸镍纳米线。具体是由大量钴酸镍纳米线组成且具有空心结构的二次空心介孔微球。该空心结构的钴酸镍介孔微球直径约为2微米~10微米，壁厚小于1微米，优选为0.3~0.6微米。并且，该二次空心介孔微且具有开口。该开口的尺寸较大，从而使该钴酸镍介孔微球为碗状的半球或球缺。
本发明实施例通过简单的低温水热环境和后续高温热处理法制备钴酸镍材料。在制备过程中，将硝酸钴或氯化钴与硝酸镍或氯化镍做为原料，并采用异丙醇与水的混合溶剂作为反应介质，从而可以得到具有空心结构的钴酸镍介孔微球。该方法合成的钴酸镍二次空心球可以具有开口，形成的是半球状或球缺状的空心球结构，从而使内部的表面可以作为有效表面，大大提高了钴酸镍材料的比表面积。
实施例1
将1mol Co(NO2)26H2O和0.5mol Ni(NO2)26H2O在搅拌条件下溶解在异丙醇与水的混合溶剂（按体积比3:1）中，反应液总体积是120ml，形成均一溶液后缓慢加入25.2克尿素，搅拌20分钟形成粉色溶液。将该粉色溶液转移至钢衬聚四氟乙烯水热反应釜中，在80-180℃加热2-20小时，然后随炉冷却至室温，取出，经过真空抽滤-三次水洗-真空抽滤-三次乙醇洗对所制备的样品进行后处理，在60℃下真空干燥12小时，可得到粉色前驱体粉末。将制备的前驱体粉末置于马弗炉中，在空气气氛下，以每分钟1℃升温速率升到300℃，保持2小时，然后随炉冷却至室温，可得到黑色固体粉末，即钴酸镍介孔微球。
实施例2
反应条件与上述实施例1相同，区别仅在将Co(NO2)26H2O和Ni(NO2)26H2O替换为CoCl26H2O和NiCl26H2O，得到的产物为钴酸镍介孔微球。
对比例1
反应条件与上述实施例1相同，区别仅在将混合溶剂替换为纯水。请参阅图6，从产物的FESEM照片中可以看到，当以纯水作为溶剂时仅能合成出钴酸镍实心球，该实心球只有外表面可以作为计算比表面积的有效表面，因此具有较小的比表面积。
对比例2
反应条件与上述实施例1相同，区别仅在将混合溶剂替换为甲醇与水的混合溶剂（按体积比3:1）。请参阅图7，从产物的FESEM照片中可以看到，当以甲醇与水混合作为溶剂合成产物仍然是钴酸镍实心球。
对比例3
反应条件与上述实施例1相同，区别仅在将混合溶剂替换为乙二醇与水的混合溶剂（按体积比3:1）。请参阅图8，从产物的FESEM照片中可以看到，当以乙二醇与水混合作为溶剂合成产物为钴酸镍实心球和一些不成形的团聚产物。
对比例4
反应条件与上述实施例1相同，区别仅在将混合溶剂替换为丙三醇与水的混合溶剂（按体积比3:1）。请参阅图9，从产物的FESEM照片中可以看到，当以丙三醇与水混合作为溶剂合成产物无特定形状。
对比例5
反应条件与上述实施例1相同，区别仅在将混合溶剂替换为N,N-二甲基甲酰胺(DMF)与水的混合溶剂（按体积比3:1）。请参阅图10，从产物的FESEM照片中可以看到，当以DMF与水混合作为溶剂合成产物无特定形状。
另外，本领域技术人员还可在本发明精神内做其他变化，当然，这些依据本发明精神所做的变化，都应包含在本发明所要求保护的范围之内。

Claims (10)

  1. 一种钴酸镍介孔微球的制备方法，包括：
    将钴盐与镍盐按照物质的量比为2:1的比例溶解在异丙醇与水的混合溶剂中形成第一溶液；
    向该第一溶液中加入尿素，搅拌形成粉色的第二溶液；
    将该第二溶液加入水热反应釜中充分反应后冷却，得到的粉色固相产物为前驱体；以及
    将该前驱体在空气中热处理。
  2. 如权利要求1所述的钴酸镍介孔微球的制备方法，其特征在于，该异丙醇与水的体积比为1:10~10:1。
  3. 如权利要求1所述的钴酸镍介孔微球的制备方法，其特征在于，该钴盐在该混合溶剂中的浓度为0.001 mol/L ~0.02 mol/L，该硝盐在该混合溶剂中的浓度为0.0005 mol/L ~0.01 mol/L，该尿素在该混合溶剂中的浓度为1 mol/L ~5 mol/L。
  4. 如权利要求1所述的钴酸镍介孔微球的制备方法，其特征在于，该钴盐为硝酸钴或氯化钴，当钴盐为硝酸钴时，镍盐为硝酸镍；当钴盐为氯化钴时，镍盐为氯化镍。
  5. 如权利要求1所述的钴酸镍介孔微球的制备方法，其特征在于，该第二溶液在水热反应釜中的反应温度为80℃~180℃。
  6. 如权利要求1所述的钴酸镍介孔微球的制备方法，其特征在于，该热处理的温度为200℃~300℃。
  7. 如权利要求1所述的钴酸镍介孔微球的制备方法，其特征在于，该前驱体为碱式碳酸钴镍。
  8. 一种钴酸镍介孔微球，包括多个钴酸镍纳米线，其特征在于，该钴酸镍介孔微球为空心结构，且具有开口。
  9. 如权利要求8所述的钴酸镍介孔微球，其特征在于，该空心结构的钴酸镍介孔微球的壁厚小于1微米。
  10. 如权利要求8所述的钴酸镍介孔微球，其特征在于，该钴酸镍介孔微球为半球状或球缺状的空心球体结构。
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