CN110571439A - Preparation method and application of carbon nanotube-coated cobalt simple substance composite material - Google Patents

Preparation method and application of carbon nanotube-coated cobalt simple substance composite material Download PDF

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Publication number
CN110571439A
CN110571439A CN201910758555.5A CN201910758555A CN110571439A CN 110571439 A CN110571439 A CN 110571439A CN 201910758555 A CN201910758555 A CN 201910758555A CN 110571439 A CN110571439 A CN 110571439A
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cobalt
composite material
coated
mixed solution
simple substance
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梁萍
孟顶顶
梁一
谢卓鸿
张弛
张忠华
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Wuyi University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

the invention relates to the technical field of nano composite materials, in particular to a preparation method and application of a carbon nano tube coated cobalt simple substance composite material. The preparation method comprises the following steps: (1) adding water into soluble cobalt salt and surfactant to prepare mixed solution A; (2) adding water into cobalt cyanide to prepare a mixed solution B; (3) uniformly mixing the mixed solution A and the mixed solution B, standing for layering, removing supernatant, washing the lower-layer solution with water and alcohol for several times, and collecting solids; (4) drying the solid to obtain cobalt-based Prussian blue powder; (5) and carbonizing the cobalt-based Prussian blue powder to obtain the composite material of the carbon nano tube coated with the cobalt simple substance. The method has the advantages of cheap raw materials, simple preparation method and easy operation, and the obtained material ORR has excellent electrocatalytic performance which is close to the electrocatalytic effect of Pt-C.

Description

preparation method and application of carbon nanotube-coated cobalt simple substance composite material
Technical Field
The invention relates to the technical field of nano composite materials, in particular to a preparation method and application of a carbon nano tube coated cobalt simple substance composite material.
Background
With the development of society, the demand of human beings for energy is increasing day by day. The current main sources of energy acquisition are still petroleum, coal and other resources, and besides non-renewable properties, the use of these traditional mineral resources also causes a series of environmental pollution problems. Therefore, the development of energy conversion and storage devices, such as fuel cells and metal-air batteries, is of great interest. However, the Oxygen Reduction Reaction (ORR) occurring at the fuel cell and the cathode of the metal-air battery is a four-electron reaction, and the reaction speed is slow, greatly limiting the performance of the battery. The current commercial electrocatalyst is a platinum-carbon (Pt-C) catalyst, which accelerates the ORR reaction process. However, platinum is expensive and has poor stability, so that large-scale use of such batteries cannot be realized. The material with low cost and high electrocatalytic activity is explored to be used as a substitute of the platinum-carbon catalyst, and has important significance.
Currently, the electrocatalysts still in the experimental stage mainly include carbon-based catalysts, transition metal-based catalysts, carbon-transition metal composite electrocatalysts and the like. Among them, the carbon-cobalt-based composite electrocatalyst can simultaneously have the stability of carbon and the high activity of a cobalt-based material, and is widely studied. For example, Su et al (Nanoscale,2014,6,15080-15089) synthesize spherical carbon-coated elemental cobalt by a hydrothermal carbonization strategy, show an ORR electrocatalytic effect superior to that of Pt-C, however, the synthesized material is synthesized by hydrothermal or carbonization, generally has no good porous structure and channel, and the morphology and components of the material are not easily regulated, thereby affecting the electrocatalytic performance of the material in ORR. Wang et al (Nature energy,2016,1,15006) obtained nitrogen-doped carbon nanotube frameworks by carbonizing ZIF-67, used as ORR electrocatalysts, and achieved better catalytic effects than Pt-C. Aijaz et al (Angew. chem., int. Ed. Engl.) use ZIF-67 as a precursor in the reaction of H2the product obtained by medium carbonization and oxidation in air has Co @ Co3O4The encapsulated carbon nanotube-nitrogen doped carbon polyhedron has good catalytic effect in ORR and electrocatalytic oxygen production reaction (OER), and can be used as bifunctional catalyst, while ZIF-67 is selectedas a precursor, the synthesized carbon-cobalt composite material does not usually have a bamboo-shaped carbon nanotube structure, which is not beneficial to ion transmission and active site exposure.
Disclosure of Invention
Aiming at the defects of the prior art, the cobalt-based Prussian blue is adopted as a precursor, and the composite material (CNT @ Co) with the carbon nano tube coated with the cobalt simple substance can be obtained through one-step carbonization and is used as an electrocatalyst of the ORR. The method has cheap raw materials, the preparation method is simple and easy to operate, and the obtained material ORR has excellent electrocatalytic performance which is close to the electrocatalytic effect of Pt-C.
the invention adopts the following technical scheme.
a preparation method of a carbon nanotube coated cobalt simple substance composite material comprises the following steps:
(1) Adding water into soluble cobalt salt and surfactant to prepare mixed solution A;
(2) Adding water into cobalt cyanide to prepare a mixed solution B;
(3) Uniformly mixing the mixed solution A and the mixed solution B, standing for layering, removing supernatant, washing the lower-layer solution with water and alcohol for several times, and collecting solids;
(4) drying the solid to obtain cobalt-based Prussian blue powder;
(5) And carbonizing the cobalt-based Prussian blue powder to obtain the composite material of the carbon nano tube coated with the cobalt simple substance.
preferably, the ratio of the soluble cobalt salt to the surfactant is 1-3 mmol: 1-9 g.
Preferably, the soluble cobalt salt is cobalt nitrate hexahydrate or cobalt acetate tetrahydrate; the surfactant is polyvinylpyrrolidone.
In the invention, the amount of the added polyvinylpyrrolidone has an important influence on the particle size of the cobalt-based Prussian blue precursor powder particles, too much addition can cause the particle size to be too small, and too little addition can cause the particle size to be too large. If the particle size is too small, the particles can agglomerate to reduce the electrocatalytic performance, and if the particle size is too large, the formation of the carbon nano tube can be influenced.
preferably, the concentration of the cobalt cyanide in the mixed liquid B is 0.00125-0.02 mol/L.
preferably, the cobalt cyanide is potassium cobalt cyanide.
Preferably, the mixture is left standing for 12 to 24 hours.
preferably, the drying temperature is 60-80 ℃ and the drying time is 10-24 hours.
preferably, the carbonization is carried out in protective atmosphere, the reaction is carried out for 1 to 1.5 hours at the temperature of 450 to 600 ℃, and then the reaction is carried out for 2 to 4 hours at the temperature of 550 to 1000 ℃, and the temperature rising speed is 1 to 10 ℃/min; the protective atmosphere is one of nitrogen, argon or hydrogen. In the two-step carbonization process, the simple substance cobalt can migrate in the material in the carbonization process under the protective atmosphere, and finally the bamboo-shaped carbon nano tube is formed.
The carbon nano tube coated cobalt simple substance composite material prepared by the method. The carbon nanotubes in the composite material of the carbon nanotube-coated cobalt simple substance are bamboo-like, have the advantages of one-dimensional materials and hollow structures, have strong conductivity and are beneficial to material transmission in the electrocatalysis process; the specific surface area is high, and active sites are increased; the cobalt simple substance is coated by the carbon nano tube, so that the structure is more stable; the cobalt simple substance and the carbon material have synergistic effect, and are beneficial to improving the electrocatalysis performance.
The carbon nanotube-coated cobalt simple substance composite material is applied to batteries.
preferably, the application of the composite material with the carbon nano tube coating the cobalt simple substance as an electrocatalyst in a battery specifically comprises the following steps:
(1) mixing the obtained composite material with carbon black, isopropanol and Nafion to obtain a mixture;
(2) And (3) carrying out ultrasonic treatment on the mixture, dripping 5-15 mu L of the ultrasonic suspension on a glassy carbon electrode, and drying for 5-24h for later use.
Preferably, the ratio of the composite material of the carbon nano tube coated cobalt simple substance to the carbon black, the isopropanol and the Nafion is 5-10 mg: 5-10 mg: 10-500. mu.L: 10-50 μ L, wherein the concentration of Nafion is 1-10 wt%.
Further preferably, the ratio of the composite material with the carbon nanotube coated with the cobalt simple substance to the carbon black, the isopropanol and the Nafion is 5 mg: 5 mg: 150 μ L of: 50 μ L, wherein the concentration of Nafion is 5 wt%.
The invention has the beneficial effects that: the cobalt-based Prussian blue is used as a precursor to synthesize the bamboo-like carbon nanotube-coated cobalt simple substance composite material, the material cost is low, the synthesis process is simple, complex equipment is not needed, and the morphology and structure are easy to regulate and control. The obtained bamboo-like carbon nanotube-coated cobalt simple substance composite material has good electrocatalysis performance in ORR, and is close to the catalytic effect of commercial Pt-C.
Drawings
FIG. 1 is a TEM image of a composite material prepared in example 2 of the present invention, in which a cobalt simple substance is coated with carbon nanotubes;
Fig. 2 is an XRD chart of the composite material of elemental cobalt coated with carbon nanotubes prepared in example 2 of the present invention;
Fig. 3 is a linear sweep voltammetry curve of the composite material prepared in example 2 of the present invention, in which the carbon nanotubes coat the cobalt element.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments.
Example 1
A preparation method of a carbon nanotube coated cobalt simple substance composite material comprises the following steps:
(1) 0.2910g (1mmol) of cobalt nitrate hexahydrate and 1g of polyvinylpyrrolidone are added into 100mL of water to prepare a mixed solution A;
(2) 0.1662g (0.5mmol) of potassium cobalt cyanide is added into 100mL of water to prepare a mixed solution B;
(3) uniformly mixing the mixed solution A and the mixed solution B, standing for 24 hours for layering, removing supernatant, washing the lower-layer solution with water and ethanol for 3 times, and centrifuging to collect solids;
(4) Drying the solid at 80 ℃ for 10 hours to obtain cobalt-based Prussian blue powder;
(5) Carbonizing the cobalt-based Prussian blue powder in a nitrogen atmosphere, heating to 550 ℃ at the speed of 5 ℃/min, reacting for 1 hour, heating to 900 ℃ at the speed of 5 ℃/min, and reacting for 2 hours to obtain the carbon nanotube-coated cobalt simple substance composite material.
example 2
A preparation method of a carbon nanotube coated cobalt simple substance composite material comprises the following steps:
(1) 0.5821g (2mmol) of cobalt nitrate hexahydrate and 5g of polyvinylpyrrolidone are added into 200mL of water to prepare a mixed solution A;
(2) 0.3324(1mmol) potassium cobalt cyanide is added into 200mL water to prepare a mixed solution B;
(3) uniformly mixing the mixed solution A and the mixed solution B, standing for 24 hours for layering, removing supernatant, washing the lower-layer solution with water and ethanol for 3 times, and centrifuging to collect solids;
(4) drying the solid at 80 ℃ for 18 hours to obtain cobalt-based Prussian blue powder;
(5) Carbonizing the cobalt-based Prussian blue powder in a nitrogen atmosphere, heating to 550 ℃ at the speed of 2 ℃/min, reacting for 1 hour, heating to 1000 ℃ at the speed of 2 ℃/min, and reacting for 2 hours to obtain the carbon nanotube-coated cobalt simple substance composite material.
Example 3
A preparation method of a carbon nanotube coated cobalt simple substance composite material comprises the following steps:
(1) 0.7472g (3mmol) of cobalt acetate tetrahydrate and 9g of polyvinylpyrrolidone are added into 400mL of water to prepare a mixed solution A;
(2) 0.6647g (2mmol) of potassium cobalt cyanide is added into 400mL of water to prepare a mixed solution B;
(3) Uniformly mixing the mixed solution A and the mixed solution B, standing for 12 hours for layering, removing supernatant, washing the lower-layer solution with water and ethanol for 3 times, and centrifuging to collect solids;
(4) Drying the solid at 60 ℃ for 15 hours to obtain cobalt-based Prussian blue powder;
(5) Carbonizing the cobalt-based Prussian blue powder in a nitrogen atmosphere, heating to 500 ℃ at the speed of 3 ℃/min, reacting for 1 hour, heating to 900 ℃ at the speed of 3 ℃/min, and reacting for 2 hours to obtain the carbon nanotube-coated cobalt simple substance composite material.
Experimental example 1
The obtained composite material of the carbon nano tube coated with the cobalt simple substance is characterized. The morphology of the composite material of the carbon nanotube coated cobalt simple substance was observed in a Transmission Electron Microscope (TEM), and the result is shown in fig. 1. The TEM image shows bamboo-like hollow carbon nanotubes with black cobalt particles distributed therein.
the material was subjected to X-ray diffraction, the results of which are shown in fig. 2. The results show that cobalt is present in the material in elemental form.
Experimental example 2
The composite material of the carbon nano tube coated with the cobalt simple substance is used as an electrocatalyst in a battery, and specifically, 5mg of the composite material of the carbon nano tube coated with the cobalt simple substance, 5mg of carbon black, 150 muL of isopropanol and 50 muL of Nafion are mixed to obtain a mixture, wherein the concentration of the Nafion is 5 wt%, and the mixture is subjected to ultrasonic treatment for 30 min.
10uL of the suspension after the ultrasonic treatment was dropped onto the glassy carbon electrode, and then the glass carbon electrode was dried in a vacuum vessel for 8 hours. Taking 0.1M potassium hydroxide solution, and performing ORR test by adopting linear sweep voltammetry under oxygen saturation environment, wherein the reference electrode is silver/silver chloride (saturated potassium chloride solution), and the counter electrode is a platinum wire. The voltage scanning interval is 0 to-0.8V, and the rotating speed of the rotating disc electrode is 1600 revolutions per minute.
the linear sweep voltammetry curve of the prepared composite material with the carbon nanotube coated with the cobalt simple substance is shown in fig. 3.
The results show that the current density is-3 mA/cm2The corresponding potential (half-wave potential) vs. Ag/AgCl is about 0.2V and is close to a commercial Pt/C catalyst, and the composite material has good ORR electro-catalytic performance.

Claims (10)

1. a preparation method of a carbon nanotube coated cobalt simple substance composite material is characterized by comprising the following steps:
(1) Adding water into soluble cobalt salt and surfactant to prepare mixed solution A;
(2) Adding water into cobalt cyanide to prepare a mixed solution B;
(3) Uniformly mixing the mixed solution A and the mixed solution B, standing for layering, removing supernatant, washing the lower-layer solution with water and alcohol for several times, and collecting solids;
(4) Drying the solid to obtain cobalt-based Prussian blue powder;
(5) And carbonizing the cobalt-based Prussian blue powder to obtain the composite material of the carbon nano tube coated with the cobalt simple substance.
2. The method for preparing the composite material of the carbon nano tube coated cobalt simple substance according to claim 1, wherein the ratio of the soluble cobalt salt to the surfactant is 1-3 mmol: 1-9 g.
3. The method for preparing the carbon nanotube-coated cobalt elemental composite material as claimed in claim 1, wherein the soluble cobalt salt is cobalt nitrate hexahydrate or cobalt acetate tetrahydrate; the surfactant is polyvinylpyrrolidone.
4. the method of claim 1, wherein the concentration of cobalt cyanide in the mixed solution B is 0.00125-0.02 mol/L.
5. The method of claim 1, wherein the cobalt cyanide is potassium cobalt cyanide.
6. the method for preparing the carbon nanotube-coated cobalt elemental composite material as claimed in claim 1, wherein the drying temperature is 60-80 ℃ and the drying time is 10-24 hours.
7. the method for preparing the composite material of the carbon nano tube coated cobalt simple substance as claimed in claim 1, wherein the carbonization is carried out in a protective atmosphere, the reaction is carried out for 1-1.5 hours at 450-600 ℃, and then the reaction is carried out for 2-4 hours at 550-1000 ℃, and the temperature rising speed is 1-10 ℃/min; the protective atmosphere is one of nitrogen, argon or hydrogen.
8. The carbon nanotube-coated cobalt composite material prepared by the method of any one of claims 1 to 7.
9. the use of the carbon nanotube elemental cobalt coated composite material of claim 8 in a battery.
10. the use of the carbon nanotube elemental cobalt coated composite material of claim 9 as an electrocatalyst in a battery.
CN201910758555.5A 2019-08-16 2019-08-16 Preparation method and application of carbon nanotube-coated cobalt simple substance composite material Pending CN110571439A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111570786A (en) * 2020-05-12 2020-08-25 中国科学技术大学 Magnetic porous cobalt nanocube and preparation method and application thereof
CN113200556A (en) * 2021-05-20 2021-08-03 黑龙江大学 Preparation method and application of high-stability micron-sized cubic cobalt-based Prussian blue analogue
CN113675387A (en) * 2021-07-15 2021-11-19 南京信息工程大学 Sulfur-carbon composite material, preparation method and application thereof
CN113782728A (en) * 2021-09-15 2021-12-10 浙江王点科技有限公司 Preparation method and application of cobalt Prussian blue analogue/carbon nano tube composite material

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CN108878803A (en) * 2018-05-23 2018-11-23 广东工业大学 A kind of Prussian blue similar object electrode material of hollow core-shell structure and its preparation method and application
CN108855159A (en) * 2018-06-27 2018-11-23 广东工业大学 A kind of phosphatization cobalt and its preparation method and application with the synthesis of Prussian blue derivative

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CN108878803A (en) * 2018-05-23 2018-11-23 广东工业大学 A kind of Prussian blue similar object electrode material of hollow core-shell structure and its preparation method and application
CN108855159A (en) * 2018-06-27 2018-11-23 广东工业大学 A kind of phosphatization cobalt and its preparation method and application with the synthesis of Prussian blue derivative

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111570786A (en) * 2020-05-12 2020-08-25 中国科学技术大学 Magnetic porous cobalt nanocube and preparation method and application thereof
CN111570786B (en) * 2020-05-12 2021-12-14 中国科学技术大学 Magnetic porous cobalt nanocube and preparation method and application thereof
CN113200556A (en) * 2021-05-20 2021-08-03 黑龙江大学 Preparation method and application of high-stability micron-sized cubic cobalt-based Prussian blue analogue
CN113675387A (en) * 2021-07-15 2021-11-19 南京信息工程大学 Sulfur-carbon composite material, preparation method and application thereof
CN113782728A (en) * 2021-09-15 2021-12-10 浙江王点科技有限公司 Preparation method and application of cobalt Prussian blue analogue/carbon nano tube composite material

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