CN109671574B - MnCo2O4Nano-spherical particles, preparation method thereof and application thereof in super capacitor - Google Patents

MnCo2O4Nano-spherical particles, preparation method thereof and application thereof in super capacitor Download PDF

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CN109671574B
CN109671574B CN201910088454.1A CN201910088454A CN109671574B CN 109671574 B CN109671574 B CN 109671574B CN 201910088454 A CN201910088454 A CN 201910088454A CN 109671574 B CN109671574 B CN 109671574B
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mnco
acetate tetrahydrate
particles
manganese acetate
super capacitor
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CN109671574A (en
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黄田富
胡志彪
丘则海
郎小玲
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Longyan University
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Longyan University
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their materials
    • H01G11/46Metal oxides, e.g. ruthenium oxide
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

Abstract

The invention discloses MnCo2O4Nanoparticle of manganese acetate tetrahydrate, acetic acid tetrahydrateCobalt, a complexing agent and a surfactant; mixing manganese acetate tetrahydrate and cobalt acetate tetrahydrate, and adding water to form a uniform solution; adding polyacrylic acid and peregal O-20 to form a uniform mixed solution; then transferring the mixture to a reaction kettle for reaction, filtering, washing, drying and calcining the product to obtain MnCo2O4Nanoparticle, MnCo prepared therefrom2O4The preparation method is simple and easy to operate, the raw material sources are rich, the cost is low, the method is green and environment-friendly, and the obtained MnCo is2O4The nanosphere particles have small particle size, good size uniformity and small agglomeration degree, are prepared into the cathode material of the super capacitor, have high specific capacitance and can meet the requirement of preparing high-performance super capacitor devices.

Description

MnCo2O4Nano-spherical particles, preparation method thereof and application thereof in super capacitor
Technical Field
The invention relates to MnCo2O4A nano-sphere particle, a preparation method thereof and application thereof in a super capacitor belong to the field of electrode material preparation.
Background
With the great use of coal, petroleum and natural gas, serious global environmental pollution is caused, and a green and efficient energy storage system device is urgently needed to be invented. A supercapacitor is an energy storage element which stores electric charges by using the surface electrochemical process of positive and negative electrodes of electrode materials and electrolyte, and is also called as an electrochemical capacitor. There are two main types of supercapacitors, one being double layer capacitors and the other being faraday pseudocapacitors, depending on the mechanism of energy storage. Electric double layer capacitors store charge by reversible electrostatic adsorption of electrolyte ions on the surface of an active material, mainly carbon materials; the Faraday pseudocapacitor stores energy through a rapid and reversible redox reaction on the surface of an active electrode material, and mainly comprises a conductive polymer material and a transition metal composite material. The performance of the supercapacitor device depends on electrode materials, the preparation technology of the electrode, electrolyte matched with the electrode materials and the like, wherein the electrode materials are key factors determining the performance of the device.
In recent years, the development of new electrode materials is a breakthrough direction for improving the energy density of supercapacitors. Transition metal elements generally have multiple oxidation states relative to carbon materials, and more energy can be stored by redox reactions in electrochemical energy storage. The Mn and Co metal bimetal oxide serving as the positive electrode material of the Faraday pseudocapacitor has the characteristics of high specific capacity, wide working voltage range and good cycling stability, is low in cost and environment-friendly, and is expected to become one of the next generation of most potential high-performance supercapacitor electrode materials.
MnCo2O4Is a bimetallic oxide with a spinel structure, and MnCo with different shapes2O4Such as nanowire arrays, nanosheets, rods and the like, have been prepared, such as by performing a coprecipitation reaction at room temperature and subsequent heat treatment to grow porous MnCo on three-dimensional Ni foam2O4Nano-rod array or nano-MnCo prepared by microwave heating synthesis technology2O4And can be used for super capacitor anode material, but the nano MnCo prepared at present2O4Large grain diameter, small specific surface area, complex preparation method and mild reaction conditions.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide MnCo with the grain diameter of 7.5nm and excellent diameter uniformity2O4The preparation method of the nanosphere particles adopts a simple and easy-to-operate hydrothermal method, the raw material source is rich, the cost is low, the method is green and environment-friendly, and the obtained MnCo2O4The nanosphere particles have small particle size, good size uniformity and small agglomeration degree, are prepared into the cathode material of the super capacitor, have high specific capacitance and can meet the requirement of preparing high-performance super capacitor devices.
In order to achieve the purpose, the invention adopts the following technical scheme:
MnCo2O4The nano-sphere particles are prepared from the following raw materials: manganese acetate tetrahydrate (Mn (CH)3COO)2·4H2O), cobalt acetate tetrahydrate (Co (CH)3COO)2·4H2O), a complexing agent and a surfactant, wherein the molar ratio of manganese acetate tetrahydrate, cobalt acetate tetrahydrate, the complexing agent and the surfactant is as follows: 1-4: 2-8: 3-15: 0.5-4. Preferably, the molar ratio of manganese acetate tetrahydrate, cobalt acetate tetrahydrate, complexing agent and surfactant is 2:4:6: 1.
MnCo prepared by the invention2O4The nano-sphere particles have small particle size of about 7.5nm, good size uniformity and small agglomeration degree, are used for preparing the anode material of the super capacitor, and have high specific capacitance and good circulation stability.
Further, the complexing agent is polyacrylic acid (PAA) with the molecular weight of 2000-; the surfactant is peregal O-20.
Polyacrylic acid is taken as a complexing agent, peregal O-20 is taken as a surfactant, so that the normal reaction of the raw materials can be effectively ensured, and the MnCo with high performance and good quality can be prepared2O4A nanoparticle.
The invention also provides MnCo2O4The preparation method of the nano-sphere particles comprises the following steps:
1) weighing the raw materials according to the molar ratio;
2) adding water into manganese acetate tetrahydrate and cobalt acetate tetrahydrate, ultrasonically stirring and dispersing for 20-25min to obtain a uniform solution for later use;
3) adding a complexing agent and a surfactant into the uniform solution obtained in the step 2), and continuing to perform ultrasonic stirring and dispersing for 25-35min to form a mixed solution for later use;
4) transferring the mixed solution into a reaction kettle for reaction, naturally cooling after the reaction is finished, taking out an inner container of the reaction kettle, removing supernatant, transferring the reaction kettle into a centrifugal tube for centrifugal separation to obtain solid particles, repeatedly washing the solid particles respectively by deionized water and absolute ethyl alcohol for 3-5 times, then placing the solid particles into a 75-85 ℃ blast drying oven, and drying for 6 hours;
5) putting the dried solid particles into a quartz boat, heating to 400-450 ℃ at the heating rate of 3-5 ℃/min in the air atmosphere, calcining for 3-5h, preferably for 4h at 425 ℃, naturally cooling to 20-30 ℃, and naturally cooling to obtain MnCo2O4A nanoparticle.
The raw materials required in the preparation process are rich, convenient and easily available, do not generate toxic and harmful gases, and are green and environment-friendly; simple operation, mild reaction condition, suitability for large-scale production and good application prospect.
Further, the adding amount of water in the step 2) is 15-60mL of water added into every 1mmol of manganese acetate tetrahydrate; the reaction kettle in the step 4) is a stainless steel reaction kettle with a polytetrafluoroethylene inner container, the reaction time in the reaction kettle is 10-18h, preferably 14h, the reaction temperature is 100-140 ℃, preferably 125 ℃, and the cooling is carried out to 20-30 ℃.
The invention determines the hydrothermal reaction condition and the calcination temperature by selecting manganese acetate, cobalt acetate, complexing agent and surfactant and accurately selecting the volume of the added deionized water so as to ensure that the prepared MnCo2O4The particle diameter of the nanosphere is small and the diameter is uniform.
The invention also provides a super capacitor, and the anode material of the super capacitor is made of the MnCo2O4And (4) preparing nanosphere particles.
MnCo of the invention2O4The nano-sphere particles are prepared into the positive electrode material of the super capacitor, the specific capacitance is high and reaches 765.68F/g under the current density of 1A/g through electrochemical performance comprehensive test, 87.26% can be maintained after 4000 times of charge-discharge cycle, and the cycle stability is good.
Drawings
FIG. 1 shows MnCo in example 1 of the present invention2O4X-ray diffraction patterns of nanosphere particles;
FIG. 2 shows MnCo in example 1 of the present invention2O4Scanning electron micrographs of the nanosphere particles;
FIG. 3 shows MnCo in example 1 of the present invention2O4A constant current charge-discharge curve diagram of the super capacitor anode material prepared from the nano-sphere particles under the current density of 1A/g;
FIG. 4 shows MnCo in example 1 of the present invention2O4A curve diagram for testing the electrochemical cycling stability of the super capacitor anode material prepared from the nano-spherical particles is shown.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Accurately weighing 0.3721g (2mmol) of manganese acetate tetrahydrate and 0.9963g (4mmol) of cobalt acetate tetrahydrate, putting into 60mL of deionized water, and ultrasonically stirring and dispersing for 25min to form a uniform solution; then 1.6845g (6mmol) of polyacrylic acid and 1.1995g (1mmol) of surfactant peregal O-20 are added, and ultrasonic stirring and dispersion are continued for 30min to form a uniform mixed solution; then transferring the uniformly mixed solution to a stainless steel reaction kettle with a polytetrafluoroethylene inner container, reacting for 14 hours at 125 ℃, and naturally cooling to 20 ℃. Filtering, washing, drying, and calcining at 425 ℃ for 4h to obtain MnCo2O4A nanoparticle.
For the prepared MnCo2O4The X-ray diffraction pattern (XRD) and Scanning Electron Microscope (SEM) photographs of the nano-spherical particles are respectively shown in figure 1 and figure 2, and as can be seen from figure 1, the positions of peaks of the pattern are consistent with JCPDS 23-1237, and the prepared product is MnCo2O4And no hetero-peak, indicating a pure phase and no impurity, as can be seen from FIG. 2, MnCo2O4Shape ofThe appearance is spherical, the grain diameter is small and reaches 7.5nm, the size uniformity is good, and the agglomeration degree is small.
Example 2
Accurately weighing 0.3721g of manganese acetate tetrahydrate and 0.9963g of cobalt acetate tetrahydrate, putting into 60mL of deionized water, and ultrasonically stirring and dispersing for 25min to form a uniform solution; adding 1.6845g of polyacrylic acid and 1.1995g of surfactant peregal O-20, and continuing to ultrasonically stir and disperse for 30min to form a uniform mixed solution; then transferring the uniformly mixed solution to a stainless steel reaction kettle with a polytetrafluoroethylene inner container, reacting for 10 hours at 110 ℃, and naturally cooling to 20 ℃. Filtering, washing, drying, and calcining at 400 ℃ for 3h to obtain MnCo2O4A nanoparticle.
Example 3
Accurately weighing 0.3721g of manganese acetate tetrahydrate and 0.9963g of cobalt acetate tetrahydrate, putting into 60mL of deionized water, and ultrasonically stirring and dispersing for 25min to form a uniform solution; adding 1.6845g of polyacrylic acid and 1.1995g of surfactant peregal O-20, and continuing to ultrasonically stir and disperse for 30min to form a uniform mixed solution; then transferring the uniformly mixed solution to a stainless steel reaction kettle with a polytetrafluoroethylene inner container, reacting for 18h at 140 ℃, and naturally cooling to 30 ℃. Filtering, washing, drying, and calcining at 450 deg.C for 5h to obtain MnCo2O4A nanoparticle.
Example 4
Accurately weighing 0.3721g of manganese acetate tetrahydrate and 0.9963g of cobalt acetate tetrahydrate, putting into 60mL of deionized water, and ultrasonically stirring and dispersing for 25min to form a uniform solution; adding 1.6845g of polyacrylic acid and 1.1995g of surfactant peregal O-20, and continuing to ultrasonically stir and disperse for 30min to form a uniform mixed solution; then transferring the uniformly mixed solution to a stainless steel reaction kettle with a polytetrafluoroethylene inner container, reacting for 10 hours at 125 ℃, and naturally cooling to 25 ℃. Filtering, washing, drying, and calcining at 425 ℃ for 5h to obtain MnCo2O4A nanoparticle.
Example 5
0.3721g of manganese acetate tetrahydrate and 0.9963g of cobalt acetate tetrahydrate are accurately weighed and placed in 60mL of deionized water, and ultrasonic agitation is carried outStirring and dispersing for 25min to form a uniform solution; adding 1.6845g of polyacrylic acid and 1.1995g of surfactant peregal O-20, and continuing to ultrasonically stir and disperse for 30min to form a uniform mixed solution; then transferring the uniformly mixed solution to a stainless steel reaction kettle with a polytetrafluoroethylene inner container, reacting for 14 hours at 110 ℃, and naturally cooling to 28 ℃. Filtering, washing, drying, and calcining at 450 deg.C for 3h to obtain MnCo2O4A nanoparticle.
Performance testing
MnCo prepared in example 12O4Mixing the nano-spherical particles, the acetylene black and the polytetrafluoroethylene according to the mass ratio of 85:10:5, uniformly mixing, then coating on foamed nickel, tabletting under 12MPa, and drying in vacuum at 80 ℃ to prepare the positive electrode of the super capacitor.
Adopts a three-electrode system, a platinum electrode is used as a counter electrode, a Hg/HgO electrode is used as a reference electrode, and MnCo2O4And (3) taking an electrode made of the nano-spherical particles as a working electrode, carrying out comprehensive electrochemical performance test within a voltage range of 0-0.6V, and recording the result.
The constant current charge-discharge curve under the current density is shown in figure 3, and the electrochemical cycle stability test curve is shown in figure 4; as is clear from FIG. 3, the specific capacitance was high at a current density of 1A/g, and reached 765.68F/g, and as is clear from FIG. 4, after 4000 cycles of charge and discharge, it was kept at 87.26%, and the cycle stability was good.

Claims (2)

1. MnCo2O4The nano-sphere particles are characterized by being prepared from the following raw materials in molar ratio: manganese acetate tetrahydrate: cobalt acetate tetrahydrate: polyacrylic acid having a molecular weight of 2000-: peregal O-20 is 1-4: 2-8: 3-15: 0.5 to 4;
the MnCo2O4The preparation method of the nano-sphere particles comprises the following steps:
1) weighing the raw materials according to the molar ratio;
2) adding water into manganese acetate tetrahydrate and cobalt acetate tetrahydrate, ultrasonically stirring and dispersing for 25min to obtain a uniform solution for later use, wherein the addition amount is 15-60mL of water added into every 1mmol of manganese acetate tetrahydrate;
3) adding polyacrylic acid with molecular weight of 2000-;
4) transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene inner container, reacting at the temperature of 100 ℃ and 140 ℃ for 10-18h, naturally cooling to 20-30 ℃ after the reaction is finished, taking out the inner container of the reaction kettle, removing supernatant, transferring into a centrifugal tube, carrying out centrifugal separation to obtain solid particles, washing the solid particles, and drying;
5) putting the dried solid particles into a quartz boat, heating to 400-450 ℃ at the heating rate of 5 ℃/min in the air atmosphere, calcining for 3-5h, and naturally cooling to 20-30 ℃ to obtain the MnCo2O4A nanoparticle.
2. A supercapacitor, characterized in that the positive electrode material of the supercapacitor is composed of MnCo as claimed in claim 12O4And (4) preparing nanosphere particles.
CN201910088454.1A 2018-08-27 2019-01-30 MnCo2O4Nano-spherical particles, preparation method thereof and application thereof in super capacitor Active CN109671574B (en)

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