WO2018036001A1 - Waxberry-shaped nickel cobalt oxide nanomaterial and preparation method therefor - Google Patents

Waxberry-shaped nickel cobalt oxide nanomaterial and preparation method therefor Download PDF

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WO2018036001A1
WO2018036001A1 PCT/CN2016/106227 CN2016106227W WO2018036001A1 WO 2018036001 A1 WO2018036001 A1 WO 2018036001A1 CN 2016106227 W CN2016106227 W CN 2016106227W WO 2018036001 A1 WO2018036001 A1 WO 2018036001A1
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nickel
preparation
bayberry
nanomaterial
nickel cobaltate
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郑玉婴
郑文庆
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福州大学
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the invention belongs to the field of material synthesis and electrochemistry, and particularly relates to a bayberry-like nickel cobalt nanomaterial and a preparation method thereof.
  • Nickel cobaltate As a promising electrode material, nickel cobaltate has been extensively studied in the application of supercapacitors.
  • Nickel cobaltate is a typical spinel-type mixed valence metal composite oxide. Compared to single nickel oxide and cobalt sesquioxide, nickel cobaltate itself has good electrical conductivity. Among them, nickel ions occupy the octahedral position, and cobalt ions occupy both the octahedral position and the tetrahedral position.
  • the presence of solid redox on Co 2+ /Co 3+ and Ni 2+ /Ni 3+ in the structure provides two active centers for the generation of tantalum capacitors.
  • the addition of binders in conventional electrode preparation methods hinders the rapid transfer of electrons. These factors make the capacitance of the active material far from the theoretical capacitance.
  • the nickel cobaltate material prepared by the prior method has a small specific surface area and is insufficient for use in a supercapacitor.
  • Nickel cobaltate exhibits different electrochemical properties under different nanostructures. It is of great significance to construct a nanomaterial with three-dimensional structure by regulating hydrothermal conditions and heat treatment conditions. Therefore, under certain experimental conditions, the present invention is extremely urgent in preparing a nickel-cobalt-like nano-material having a myrica-like shape to meet the requirements of a supercapacitor.
  • the object of the present invention is to provide a method for preparing a bayberry-like nickel cobaltate nano material and an electrochemical application thereof.
  • Nickel cobaltate nanomaterials can be obtained by simple hydrothermal method and subsequent heat treatment, while hydrothermal temperature and time affect the crystal structure of the precursor, heat treatment temperature and time affect the crystal structure of the secondary recrystallization, thereby affecting its specific surface area.
  • the size which in turn affects its electrochemical performance as an electrode material. Therefore, the present invention constructs a nanostructure having a relatively high specific surface area by adjusting hydrothermal conditions and heat treatment conditions to obtain an electrode material having a large specific capacitance.
  • a preparation method of a bayberry-like nickel cobaltate nano material comprising: the following steps:
  • reaction solution dissolving nickel chloride, cobalt chloride and urea in deionized water and ultrasonically dispersing to form a reaction solution;
  • reaction solution prepared in the step (1) is transferred to an autoclave, and reacted at 90-110 ° C for 9-15 h; after sufficient reaction, it is cooled to room temperature, and the reaction product is obtained. Rinse and vacuum dry to obtain a solid phase precursor;
  • the solid phase precursor is calcined at 300-400 ° C for 3 h in an argon atmosphere, and the heating rate is 2 ° C. /min; Then, it is calcined at 300-400 ° C for 3 h in an air atmosphere at a heating rate of 2 ° C / min, and the obtained product is a bayberry-like nickel cobaltate nanomaterial.
  • the molar ratio of nickel chloride, cobalt chloride and urea in the step (1) is 1:2:6.
  • the vacuum drying described in the step (2) was: vacuum drying at 60 ° C for 24 hours.
  • the carnation-like nickel cobaltate nanomaterial prepared in the step (3) has a nano microsphere structure, and the microspheres have a diameter of 8 ⁇ m to 12 ⁇ m.
  • the carnation-like nickel cobaltate nanomaterial prepared by the invention has a three-dimensional structure, and the surface growth of the nanorods arranged neatly has a large specific surface area, which is favorable for the rapid transmission of electrons and ions at the interface between the electrode and the electrolyte.
  • nickel cobaltate with nano-microsphere structure is constructed.
  • the nano-needle on the surface of the microsphere has a porous structure, which is very favorable for the penetration of electrolyte ions.
  • the porous structure has a large specific surface area.
  • the active sites are increased to exhibit excellent electrochemical performance. Electrochemical tests show that the specific capacitance reaches 2512 F/g at a current density of 1 A/g.
  • Example 1 is an SEM image of a bayberry-like nickel cobaltate nanomaterial prepared in Example 1 of the present invention and an electrochemical charge and discharge graph thereof at 1 A/g;
  • Example 2 is an SEM image of a bayberry-like nickel cobaltate nanomaterial prepared in Example 2 of the present invention and an electrochemical charge and discharge graph thereof at 1 A/g;
  • Example 3 is an SEM image of a bayberry-like nickel cobaltate nanomaterial prepared in Example 3 of the present invention and an electrochemical charge and discharge graph thereof at 1 A/g.
  • a preparation method of a bayberry-like nickel cobaltate nano material comprising the following steps:
  • the substrate prepared in (1) was transferred to 100 mL of polytetrafluoroethylene liner by a substrateless hydrothermal method, and subjected to high temperature and high pressure hydrothermal reaction.
  • the reaction temperature was controlled at 90 ° C, and the reaction time was controlled at 15 h; Cool to room temperature with distilled water
  • the reaction product was washed with ethanol and dried under vacuum at 60 ° C for 24 h to obtain a solid phase precursor;
  • the precursor is subjected to heat treatment by two-step calcination; firstly, calcination in an argon atmosphere for 3 h, the reaction temperature is controlled at 350 ° C; secondly, calcination in an air atmosphere for 3 h, the reaction temperature is controlled at 350 ° C;
  • the obtained product is a bayberry-like nickel cobaltate nanomaterial. It can be seen from the scanning electron micrograph that the obtained nickel cobaltate nanospheres have spherical particles grown on the surface and have a small specific surface area. Electrochemical tests show that the specific capacitance reaches 1912 F/g at a current density of 1 A/g.
  • a preparation method of a bayberry-like nickel cobaltate nano material comprising the following steps:
  • the substrate prepared in (1) was transferred to 100 mL of polytetrafluoroethylene liner by a substrateless hydrothermal method, and subjected to high temperature and high pressure hydrothermal reaction.
  • the reaction temperature was controlled at 100 ° C, and the reaction time was controlled for 12 hours;
  • the reaction product was washed with distilled water and ethanol to room temperature, and dried under vacuum at 60 ° C for 24 h to obtain a solid phase precursor;
  • the precursor is subjected to heat treatment by two-step calcination; firstly, calcination in an argon atmosphere for 3 h, the reaction temperature is controlled at 350 ° C; secondly, calcination in an air atmosphere for 3 h, the reaction temperature is controlled at 300 ° C;
  • the obtained product is a carmine-like nickel cobaltate nanomaterial. It can be seen by scanning electron micrograph that the obtained nickel cobaltate nanospheres have nano-bars with neatly arranged surface, which have a large specific surface area; It has a specific capacitance of 2512 F/g at a current density of 1 A/g.
  • a preparation method of a bayberry-like nickel cobaltate nano material comprising the following steps:
  • the substrate prepared in (1) was transferred to 100 mL of polytetrafluoroethylene liner by a substrateless hydrothermal method, and subjected to high temperature and high pressure hydrothermal reaction.
  • the reaction temperature was controlled at 110 ° C, and the reaction time was controlled for 9 hours;
  • To room temperature, with distilled water and The reaction product was washed with ethanol, and dried under vacuum at 60 ° C for 24 h to obtain a solid phase precursor;
  • the precursor is subjected to heat treatment by two-step calcination; first, calcination in an argon atmosphere for 3 h, the reaction temperature is controlled at 400 ° C; secondly, calcination in an air atmosphere for 3 h, the reaction temperature is controlled at 300 ° C;
  • the obtained product is a bayberry-like nickel cobaltate nanomaterial. It can be seen from the scanning electron micrograph that the obtained nano-cobalt nanospheres have a fluffy surface and a low specific surface area; It has a specific capacitance of 2145 F/g at a current density of 1 A/g.

Abstract

A method for preparing a waxberry-shaped nickel cobalt oxide nanomaterial, comprising: dissolving nickel chloride, cobalt chloride, and urea in deionized water at a molar ratio of 1:2:6, stirring to form a pink solution, then transferring the solution to a high pressure reactor for completely reacting, cooling the solution to room temperature, and drying same to obtain a solid-phase precursor; and performing thermal treatment on the solid-phase precursor by a two-step calcination method to obtain the waxberry-shaped nickel cobalt oxide nanomaterial. The material has a nano-microsphere structure. Nanorods are arranged in a tidy array on the surface of microspheres so that the material has a higher specific surface area of 81m2·g-1, and can be used as an electrode material of a supercapacitor.

Description

一种杨梅状钴酸镍纳米材料及其制备方法Arbutus-like nickel cobaltate nano material and preparation method thereof 技术领域Technical field
本发明属于材料合成和电化学领域，具体涉及一种杨梅状钴酸镍纳米材料及其制备方法。The invention belongs to the field of material synthesis and electrochemistry, and particularly relates to a bayberry-like nickel cobalt nanomaterial and a preparation method thereof.
背景技术Background technique
钴酸镍作为一种有前景的电极材料，在超级电容器的应用中得到了广泛的研究。钴酸镍是一种典型的尖晶石型混合价态金属复合氧化物，相比于单一的氧化镍和四氧化三钴，钴酸镍本身具有较好的导电性。其中，镍离子占据八面***置，钴离子既占有八面***置又占据四面***置。固态氧化还原对Co2+/Co3+和Ni2+/Ni3+在结构中的出现为赝电容的产生提供了两个活性中心。尽管这些材料已经得到了广泛的研究，但是在传统电极制备方法中粘结剂的添加，阻碍了电子的快速传递，这些因素使得活性材料的电容与理论电容值相去甚远。并且现有方法制得的钴酸镍材料比表面积较小，不足以用于超级电容器。As a promising electrode material, nickel cobaltate has been extensively studied in the application of supercapacitors. Nickel cobaltate is a typical spinel-type mixed valence metal composite oxide. Compared to single nickel oxide and cobalt sesquioxide, nickel cobaltate itself has good electrical conductivity. Among them, nickel ions occupy the octahedral position, and cobalt ions occupy both the octahedral position and the tetrahedral position. The presence of solid redox on Co 2+ /Co 3+ and Ni 2+ /Ni 3+ in the structure provides two active centers for the generation of tantalum capacitors. Although these materials have been extensively studied, the addition of binders in conventional electrode preparation methods hinders the rapid transfer of electrons. These factors make the capacitance of the active material far from the theoretical capacitance. Moreover, the nickel cobaltate material prepared by the prior method has a small specific surface area and is insufficient for use in a supercapacitor.
钴酸镍在其不同纳米结构下表现的电化学性能不同，通过调控水热条件和热处理条件，构建一种具有三维结构的纳米材料具有重要意义。因此本发明在一定的实验条件下，制备出具有杨梅状的钴酸镍纳米材料以满足人们对超级电容器的要求就显得极为迫切。Nickel cobaltate exhibits different electrochemical properties under different nanostructures. It is of great significance to construct a nanomaterial with three-dimensional structure by regulating hydrothermal conditions and heat treatment conditions. Therefore, under certain experimental conditions, the present invention is extremely urgent in preparing a nickel-cobalt-like nano-material having a myrica-like shape to meet the requirements of a supercapacitor.
发明内容Summary of the invention
本发明的目的在于提供一种杨梅状钴酸镍纳米材料的制备方法及其电化学应用。钴酸镍纳米材料可以通过简单的水热法和后续热处理获得，而水热温度和时间影响前驱体的晶体结构，热处理温度和时间影响二次重结晶的晶型结构，从而影响其比表面积的大小，进而影响其作为电极材料的电化学性能。因此本发明通过调控水热条件和热处理条件，构建一种具有较高比表面积的纳米结构，以得到一种具有较大比电容的电极材料。The object of the present invention is to provide a method for preparing a bayberry-like nickel cobaltate nano material and an electrochemical application thereof. Nickel cobaltate nanomaterials can be obtained by simple hydrothermal method and subsequent heat treatment, while hydrothermal temperature and time affect the crystal structure of the precursor, heat treatment temperature and time affect the crystal structure of the secondary recrystallization, thereby affecting its specific surface area. The size, which in turn affects its electrochemical performance as an electrode material. Therefore, the present invention constructs a nanostructure having a relatively high specific surface area by adjusting hydrothermal conditions and heat treatment conditions to obtain an electrode material having a large specific capacitance.
为实现本发明的目的，采用如下技术方案：To achieve the object of the present invention, the following technical solutions are adopted:
一种杨梅状钴酸镍纳米材料的制备方法，其特征在于：包括以下步骤：A preparation method of a bayberry-like nickel cobaltate nano material, comprising: the following steps:
(1)反应溶液的制备：将氯化镍、氯化钴和尿素溶解在去离子水中，超声分散形成反应溶液；(1) Preparation of a reaction solution: dissolving nickel chloride, cobalt chloride and urea in deionized water and ultrasonically dispersing to form a reaction solution;
(2)固相前驱体的制备：将步骤(1)中所制得的反应溶液转移至高压反应釜中，在90-110℃下反应9-15h；充分反应后冷却至室温，对反应产物进行冲洗，真空干燥得到固相前驱体；(2) Preparation of solid phase precursor: The reaction solution prepared in the step (1) is transferred to an autoclave, and reacted at 90-110 ° C for 9-15 h; after sufficient reaction, it is cooled to room temperature, and the reaction product is obtained. Rinse and vacuum dry to obtain a solid phase precursor;
(3)后续热处理：将固相前驱体在氩气保护气氛中300-400℃煅烧3h，升温速率为2℃ /min；然后，在空气气氛中300-400℃煅烧3h，升温速率为2℃/min，所得产物即为杨梅状钴酸镍纳米材料。(3) Subsequent heat treatment: the solid phase precursor is calcined at 300-400 ° C for 3 h in an argon atmosphere, and the heating rate is 2 ° C. /min; Then, it is calcined at 300-400 ° C for 3 h in an air atmosphere at a heating rate of 2 ° C / min, and the obtained product is a bayberry-like nickel cobaltate nanomaterial.
步骤(1)中氯化镍、氯化钴和尿素的摩尔量之比为：1:2:6。The molar ratio of nickel chloride, cobalt chloride and urea in the step (1) is 1:2:6.
步骤(2)中所述的真空干燥为：在60℃下真空干燥24h。The vacuum drying described in the step (2) was: vacuum drying at 60 ° C for 24 hours.
步骤(3)所制得的杨梅状钴酸镍纳米材料具有纳米微球结构，微球尺寸为直径8μm-12μm。The carnation-like nickel cobaltate nanomaterial prepared in the step (3) has a nano microsphere structure, and the microspheres have a diameter of 8 μm to 12 μm.
本发明所制得的杨梅状钴酸镍纳米材料具有三维结构，表面生长整齐排列的纳米棒，使其具有较大比表面积，有利于电子和离子在电极与电解液的界面上快速传输。The carnation-like nickel cobaltate nanomaterial prepared by the invention has a three-dimensional structure, and the surface growth of the nanorods arranged neatly has a large specific surface area, which is favorable for the rapid transmission of electrons and ions at the interface between the electrode and the electrolyte.
本发明的优点在于：The advantages of the invention are:
通过调控水热条件和热处理条件，构建具有纳米微球结构的钴酸镍，微球表面的纳米针具有多孔结构，十分有利于电解质离子的渗透，同时，多孔结构使其具有较大的比表面积，活性位点增多，使其展现出优秀的电化学性能。通过电化学测试表明，其在1A/g的电流密度下比电容达到2512F/g。By adjusting hydrothermal conditions and heat treatment conditions, nickel cobaltate with nano-microsphere structure is constructed. The nano-needle on the surface of the microsphere has a porous structure, which is very favorable for the penetration of electrolyte ions. At the same time, the porous structure has a large specific surface area. The active sites are increased to exhibit excellent electrochemical performance. Electrochemical tests show that the specific capacitance reaches 2512 F/g at a current density of 1 A/g.
附图说明DRAWINGS
图1为本发明的实施例1制备的杨梅状钴酸镍纳米材料的SEM图和其在1A/g下的电化学充放电曲线图；1 is an SEM image of a bayberry-like nickel cobaltate nanomaterial prepared in Example 1 of the present invention and an electrochemical charge and discharge graph thereof at 1 A/g;
图2为本发明的实施例2制备的杨梅状钴酸镍纳米材料的SEM图和其在1A/g下的电化学充放电曲线图；2 is an SEM image of a bayberry-like nickel cobaltate nanomaterial prepared in Example 2 of the present invention and an electrochemical charge and discharge graph thereof at 1 A/g;
图3为本发明的实施例3制备的杨梅状钴酸镍纳米材料的SEM图和其在1A/g下的电化学充放电曲线图。3 is an SEM image of a bayberry-like nickel cobaltate nanomaterial prepared in Example 3 of the present invention and an electrochemical charge and discharge graph thereof at 1 A/g.
具体实施方式detailed description
为进一步公开而不是限制本发明，以下结合实例对本发明作进一步的详细说明。In order to further disclose, not limit the invention, the invention will be further described in detail in the following examples.
实施例1Example 1
一种杨梅状钴酸镍纳米材料的制备方法，包括以下步骤：A preparation method of a bayberry-like nickel cobaltate nano material, comprising the following steps:
(1)反应溶液的制备(1) Preparation of reaction solution
将1mmol氯化镍、2mmol氯化钴与6mmol尿素溶解在70mL的去离子水中，搅拌并超声30min后形成粉色混合溶液；1 mmol of nickel chloride, 2 mmol of cobalt chloride and 6 mmol of urea were dissolved in 70 mL of deionized water, stirred and sonicated for 30 min to form a pink mixed solution;
(2)固相前驱体的制备(2) Preparation of solid phase precursor
采用无基板水热法，将(1)中所制得溶液转移至100mL聚四氟乙烯内胆中，进行高温高压水热反应，反应温度控制在90℃，反应时间控制在15h；充分反应后冷却至室温，用蒸馏水 和乙醇对反应产物进行冲洗，在60℃下真空干燥24h后得到固相前驱体；The substrate prepared in (1) was transferred to 100 mL of polytetrafluoroethylene liner by a substrateless hydrothermal method, and subjected to high temperature and high pressure hydrothermal reaction. The reaction temperature was controlled at 90 ° C, and the reaction time was controlled at 15 h; Cool to room temperature with distilled water The reaction product was washed with ethanol and dried under vacuum at 60 ° C for 24 h to obtain a solid phase precursor;
(3)后续热处理(3) Subsequent heat treatment
采用两步煅烧对前驱体进行热处理；首先，在氩气保护气氛中煅烧3h，反应温度控制在350℃；其次，在空气气氛中煅烧3h，反应温度控制在350℃；The precursor is subjected to heat treatment by two-step calcination; firstly, calcination in an argon atmosphere for 3 h, the reaction temperature is controlled at 350 ° C; secondly, calcination in an air atmosphere for 3 h, the reaction temperature is controlled at 350 ° C;
所得产物即为杨梅状钴酸镍纳米材料。通过扫描电镜图可以看出，获得的钴酸镍纳米微球，表面生长球状微粒，比表面积较小。电化学测试表明，其在1A/g的电流密度下比电容达到1912F/g。The obtained product is a bayberry-like nickel cobaltate nanomaterial. It can be seen from the scanning electron micrograph that the obtained nickel cobaltate nanospheres have spherical particles grown on the surface and have a small specific surface area. Electrochemical tests show that the specific capacitance reaches 1912 F/g at a current density of 1 A/g.
实施例2Example 2
一种杨梅状钴酸镍纳米材料的制备方法，包括以下步骤：A preparation method of a bayberry-like nickel cobaltate nano material, comprising the following steps:
(1)反应溶液的制备(1) Preparation of reaction solution
将1mmol氯化镍、2mmol氯化钴与6mmol尿素溶解在70mL的去离子水中，搅拌并超声30min后形成粉色混合溶液；1 mmol of nickel chloride, 2 mmol of cobalt chloride and 6 mmol of urea were dissolved in 70 mL of deionized water, stirred and sonicated for 30 min to form a pink mixed solution;
(2)固相前驱体的制备(2) Preparation of solid phase precursor
采用无基板水热法，将(1)中所制得溶液转移至100mL聚四氟乙烯内胆中，进行高温高压水热反应，反应温度控制在100℃，反应时间控制12h；充分反应后冷却至室温，用蒸馏水和乙醇对反应产物进行冲洗，在60℃下真空干燥24h后得到固相前驱体；The substrate prepared in (1) was transferred to 100 mL of polytetrafluoroethylene liner by a substrateless hydrothermal method, and subjected to high temperature and high pressure hydrothermal reaction. The reaction temperature was controlled at 100 ° C, and the reaction time was controlled for 12 hours; The reaction product was washed with distilled water and ethanol to room temperature, and dried under vacuum at 60 ° C for 24 h to obtain a solid phase precursor;
(3)后续热处理(3) Subsequent heat treatment
采用两步煅烧对前驱体进行热处理；首先，在氩气保护气氛中煅烧3h，反应温度控制在350℃；其次，在空气气氛中煅烧3h，反应温度控制在300℃；The precursor is subjected to heat treatment by two-step calcination; firstly, calcination in an argon atmosphere for 3 h, the reaction temperature is controlled at 350 ° C; secondly, calcination in an air atmosphere for 3 h, the reaction temperature is controlled at 300 ° C;
所得产物即为杨梅状钴酸镍纳米材料，通过扫描电镜图可以看出，获得的钴酸镍纳米微球，表面生长整齐排列的纳米棒，使其具有较大比表面积；通过电化学测试表明，其在1A/g的电流密度下比电容达到2512F/g。The obtained product is a carmine-like nickel cobaltate nanomaterial. It can be seen by scanning electron micrograph that the obtained nickel cobaltate nanospheres have nano-bars with neatly arranged surface, which have a large specific surface area; It has a specific capacitance of 2512 F/g at a current density of 1 A/g.
实施例3Example 3
一种杨梅状钴酸镍纳米材料的制备方法，包括以下步骤：A preparation method of a bayberry-like nickel cobaltate nano material, comprising the following steps:
(1)反应溶液的制备(1) Preparation of reaction solution
将1mmol氯化镍、2mmol氯化钴与6mmol尿素溶解在70mL的去离子水中，搅拌并超声30min后形成粉色混合溶液；1 mmol of nickel chloride, 2 mmol of cobalt chloride and 6 mmol of urea were dissolved in 70 mL of deionized water, stirred and sonicated for 30 min to form a pink mixed solution;
(2)固相前驱体的制备(2) Preparation of solid phase precursor
采用无基板水热法，将(1)中所制得溶液转移至100mL聚四氟乙烯内胆中，进行高温高压水热反应，反应温度控制在110℃，反应时间控制9h；充分反应后冷却至室温，用蒸馏水和 乙醇对反应产物进行冲洗，在60℃下真空干燥24h后得到固相前驱体；The substrate prepared in (1) was transferred to 100 mL of polytetrafluoroethylene liner by a substrateless hydrothermal method, and subjected to high temperature and high pressure hydrothermal reaction. The reaction temperature was controlled at 110 ° C, and the reaction time was controlled for 9 hours; To room temperature, with distilled water and The reaction product was washed with ethanol, and dried under vacuum at 60 ° C for 24 h to obtain a solid phase precursor;
(3)后续热处理(3) Subsequent heat treatment
采用两步煅烧对前驱体进行热处理；首先，在氩气保护气氛中煅烧3h，反应温度控制在400℃；其次，在空气气氛中煅烧3h，反应温度控制在300℃；The precursor is subjected to heat treatment by two-step calcination; first, calcination in an argon atmosphere for 3 h, the reaction temperature is controlled at 400 ° C; secondly, calcination in an air atmosphere for 3 h, the reaction temperature is controlled at 300 ° C;
所得产物即为杨梅状钴酸镍纳米材料，通过扫描电镜图可以看出，获得的钴酸镍纳米微球，表面生长的纳米棒呈绒毛状，使其比表面积较低；通过电化学测试表明，其在1A/g的电流密度下比电容达到2145F/g。The obtained product is a bayberry-like nickel cobaltate nanomaterial. It can be seen from the scanning electron micrograph that the obtained nano-cobalt nanospheres have a fluffy surface and a low specific surface area; It has a specific capacitance of 2145 F/g at a current density of 1 A/g.
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。 The above are only the preferred embodiments of the present invention, and all changes and modifications made to the scope of the present invention should fall within the scope of the present invention.

Claims (4)

  1. 一种杨梅状钴酸镍纳米材料的制备方法，其特征在于：包括以下步骤：A preparation method of a bayberry-like nickel cobaltate nano material, comprising: the following steps:
    (1)反应溶液的制备：将氯化镍、氯化钴和尿素溶解在去离子水中，超声分散形成反应溶液；(1) Preparation of a reaction solution: dissolving nickel chloride, cobalt chloride and urea in deionized water and ultrasonically dispersing to form a reaction solution;
    (2)固相前驱体的制备：将步骤(1)中所制得的反应溶液转移至高压反应釜中，在90-110℃下反应9-15h；充分反应后冷却至室温，对反应产物进行冲洗，真空干燥得到固相前驱体；(2) Preparation of solid phase precursor: The reaction solution prepared in the step (1) is transferred to an autoclave, and reacted at 90-110 ° C for 9-15 h; after sufficient reaction, it is cooled to room temperature, and the reaction product is obtained. Rinse and vacuum dry to obtain a solid phase precursor;
    (3)后续热处理：将固相前驱体在氩气保护气氛中300-400℃煅烧3h，升温速率为2℃/min；然后，在空气气氛中300-400℃煅烧3h，升温速率为2℃/min，所得产物即为杨梅状钴酸镍纳米材料。(3) Subsequent heat treatment: the solid phase precursor is calcined at 300-400 ° C for 3 h in an argon atmosphere, and the heating rate is 2 ° C / min; then, calcined at 300-400 ° C for 3 h in an air atmosphere, the heating rate is 2 ° C /min, the obtained product is a bayberry-like nickel cobaltate nanomaterial.
  2. 根据权利要求1所述的杨梅状钴酸镍纳米材料的制备方法，其特征在于：步骤(1)中氯化镍、氯化钴和尿素的摩尔量之比为：1:2:6。The method for preparing a bayberry-like nickel cobaltate nanomaterial according to claim 1, wherein the ratio of the molar amount of nickel chloride, cobalt chloride and urea in the step (1) is 1:2:6.
  3. 根据权利要求1所述的杨梅状钴酸镍纳米材料的制备方法，其特征在于：步骤(2)中所述的真空干燥为：在60℃下真空干燥24h。The method for preparing a bayberry-like nickel cobaltate nanomaterial according to claim 1, wherein the vacuum drying in the step (2) is: vacuum drying at 60 ° C for 24 hours.
  4. 根据权利要求1所述的杨梅状钴酸镍纳米材料的制备方法，其特征在于：步骤(3)所制得的杨梅状钴酸镍纳米材料具有纳米微球结构，微球尺寸为直径8μm-12μm。 The method for preparing a bayberry-like nickel cobaltate nanomaterial according to claim 1, wherein the carnation-like nickel cobalt nanomaterial prepared in the step (3) has a nanosphere structure, and the microsphere size is 8 μm in diameter- 12μm.
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