CN110033950B - Preparation method and application of fusiform cobalt-manganese oxide composite material - Google Patents

Preparation method and application of fusiform cobalt-manganese oxide composite material Download PDF

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CN110033950B
CN110033950B CN201910262895.9A CN201910262895A CN110033950B CN 110033950 B CN110033950 B CN 110033950B CN 201910262895 A CN201910262895 A CN 201910262895A CN 110033950 B CN110033950 B CN 110033950B
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cobalt
composite material
oxide composite
manganese oxide
spindle
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CN110033950A (en
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邹勇进
方淞文
蔡成龙
张锐洁
向翠丽
孙立贤
徐芬
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Guilin University of Electronic Technology
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    • 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
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • 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
    • 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
    • H01G11/32—Carbon-based
    • 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
    • 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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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

Abstract

The invention discloses a fusiform cobalt manganese oxide composite material, which is obtained by complexing cobalt acetate and triammonium citrate and loading Mn, wherein the composite material is wholly in a fusiform structure, and a carbon material exists in the fusiform structure; mn is formed by MnCl2·4H2O and KMnO4The in-situ preparation is carried out directly with cobalt acetate and triammonium citrate complex, and the preparation method comprises the following steps: 1) preparing a complex; 2) compounding manganese element and a complex; 3) and (3) preparing the spindle-shaped cobalt-manganese oxide composite material. As an application of the electrode material of the super capacitor, under a 1M KOH solution, the electrode material can be fully discharged within the range of-0.1-0.5V, and when the discharge current density is 4A/g, the specific capacitance is 410-440F/g. The preparation method is simple, low in cost and suitable for mass production; the waste of cobalt and manganese materials is reduced; spindle-shaped morphology; mn is loaded and Co is protected3O4The structure is reduced, the electrolyte concentration is reduced, and the practical application value is high.

Description

Preparation method and application of fusiform cobalt-manganese oxide composite material
Technical Field
The invention relates to the technical field of supercapacitors, in particular to a fusiform cobalt-manganese oxide composite material and a preparation method and application thereof.
Background
The super capacitor is a high-efficiency and practical energy storage device and has the advantages of short charging time, long service life, good temperature characteristic and the like. With the increasing prominence of the problems of energy shortage and environmental pollution, the super capacitor with environmental protection, no pollution and long cycle service life becomes a hot point for the research of the energy field at present. At present, the key factors influencing the development of the super capacitor mainly comprise an electrode material, electrolyte, a diaphragm and the like, wherein the preparation of the electrode material directly determines the capacity of the capacitor and is one of the most key factors influencing the super capacitor. According to the difference of electrode materials, the super capacitor can be divided into carbon-based super capacitors, metal oxide super capacitors, conductive polymer super capacitors, heteropoly acid super capacitors and the like.
For the super capacitor of transition metal oxide, load Co3O4Has good effect and is widely researched, such as Juan Xu et al (XU J, GAO L, CAO J, et al, 2010. Preparation and electrochemical capacitance of cobalt oxide (Co3O4) nanotubes as supercapacitor material]56: 732-3O4The specific capacitance of the porous material reaches 574F/g under the condition that the electrolyte is 6M KOH and the current density is 0.1A/g, and the specific capacitance is higher. Because of Co3O4Can be kept stable under alkaline conditions to ensure specific capacitance performance, therefore, the main solution of the prior art adopts 6M KOH solution as electrolyte. However, this method has significant technical drawbacks: 1. the strong alkaline electrolyte has strong corrosivity and high requirements on production equipment; 2. the high-concentration electrolyte has higher viscosity, and the charge transmission is influenced; 3. there is a risk of environmental pollution and cost.
The above problems cannot be effectively solved by lowering the electrolyte concentration, and the prior art Jagadale, A.D. et al (JAGADALE A D, KUMBAR V S, LOKHANDE C D2013. Supercapactive activities of porous deposited nanofilakes of cobalt oxides (Co3O4) thin film electrolytes J Colloid Interface Sci [ J3O 4 ]]406: 225-230.) Co prepared using the same materials as described above3O4The material is tested for the capacitance performance under the condition of 1M KOH electrolyte, the obtained specific capacitance is only 365F/g, and the performance is obviously reduced. The reason is that Co cannot be maintained under low alkaline conditions3O4The microstructure of the material proceeds resulting in a degradation of performance.
Therefore, it is an effort to reduce the concentration of alkali in the electrolyte while maintaining the specific capacitance of the material. The method solves the technical problem, can effectively reduce the cost of production equipment and reduce potential environmental pollution risks, and has high practical application value.
Disclosure of Invention
The invention aims to provide a spindle-shaped cobalt manganese oxide composite material and a preparation method and application thereof.
Performing hydrothermal complexation on cobalt acetate and triammonium citrate, and loading Co ions on the triammonium citrate by utilizing the reaction of an acetate group and an ammonium group to generate a high-activity mixed specific capacitance; then passing through MnCl2·4H2O and KMnO4Reaction: MnCl2+ 2KMnO4= 3MnO2 + O2× + 2KCl, Mn supported on the complex; finally, oxidizing by oxygen in the air to obtain the cobalt manganese oxide.
By adopting the principle, the following effects can be realized:
1. the obtained material has the pseudo-capacitance property generated by the metal oxide and the double-electric-layer capacitance property of the porous carbon at the same time, so that the specific capacitance property of the material is ensured;
2. the introduced carbon material is doped with nitrogen to a certain degree, so that the conductivity of the material is improved, and the specific capacitance is also improved;
3. the preparation conditions are adjusted to realize the control of the microstructure of the material, a spindle-shaped structure is obtained, the stability of the microstructure of the material is improved, and the high surface area of the spindle shape and the morphology which is beneficial to the flow of electrolyte on the surface of the material are utilized to promote the rapid transmission of electrons, reduce the interface impedance of the material and improve the specific capacitance of the material;
4. by introducing Mn, the thermodynamic property of the material is changed, and the stability of the composite material under a low-alkaline condition is realized;
finally, the high specific capacitance performance of the composite material is realized under the condition of 1M KOH electrolyte.
In order to achieve the purpose of the invention, the invention adopts the technical scheme that:
a fusiform cobalt manganese oxide composite material is obtained by complexing cobalt acetate and triammonium citrate and loading Mn, wherein the composite material is wholly fusiform in structure, the average size is 10um and 2.5um respectively in length and width, and a carbon material exists in the fusiform structure;
the MnO2From MnCl2·4H2O and KMnO4Prepared in situ, and directly compounded with cobalt acetate and triammonium citrate complex.
The preparation method of the spindle-shaped cobalt manganese oxide composite material comprises the following steps:
step 1) preparation of a complex, weighing a certain amount of cobalt acetate and triammonium citrate, putting the cobalt acetate and triammonium citrate into distilled water, stirring the mixture to be transparent, putting the mixture into a reaction kettle, and obtaining the cobalt acetate and triammonium citrate complex under a certain condition; the mass ratio of the cobalt acetate to the triammonium citrate is 1: 1; the reaction condition is that the reaction is carried out for 12 to 24 hours in an oven at the temperature of 150 ℃;
step 2) compounding manganese element and complex, and mixing the cobalt acetate and the ammonium citrate triammonium complex obtained in the step 1) with MnCl2·4H2O、KMnO4Mixing with water, stirring for 1h, putting into a reaction kettle, reacting under certain conditions, and drying after the reaction is finished; powder of the cobalt acetate and triammonium citrate complex, MnCl2·4H2O、KMnO4The mass ratio of the water to the water is 1:0.5:0.5: 20; the reaction condition is that the reaction is carried out for 12 to 24 hours in an oven at 120 ℃, and the drying is carried out for 12 to 24 hours at 80 ℃ after the reaction is finished.
Step 3) preparing a fusiform cobalt-manganese oxide composite material, namely putting the powder obtained in the step 2) into a muffle furnace, and calcining under certain conditions to obtain the fusiform cobalt-manganese oxide composite material; the calcination condition is that the temperature is raised to 250-400 ℃ for calcination at the temperature raising rate of 5 ℃/min under the air condition, and then the temperature is kept for 1-5 h.
The application of the spindle-shaped cobalt manganese oxide composite material as the electrode material of the supercapacitor is that the composite material is fully discharged in a range of-0.1-0.5V in a 1M KOH solution, and the specific capacitance is 410-440F/g when the discharge current density is 4A/g.
The spindle-shaped cobalt-manganese oxide composite material disclosed by the invention is detected by experiments, and the result is as follows:
the spindle-shaped cobalt manganese oxide composite material is tested by a scanning electron microscope, and Mn is loaded in the cobalt oxide composite material.
The electrochemical performance test of the spindle-shaped cobalt-manganese oxide composite material detects that the charge and discharge are carried out within the range of-0.1-0.5V, and when the discharge current density is 4A/g, the specific capacitance of the spindle-shaped cobalt-manganese oxide composite material can reach 410 plus 440F/g.
The result of electrochemical performance test by a comparative experiment shows that the specific capacitance of the mixed specific capacitance of the cobalt oxide composite material without loading Mn is 100-300F/g, the discharge time of the spindle-shaped cobalt-manganese oxide composite material is obviously longer than that of the cobalt oxide composite material without loading Mn under the same current density, the discharge time is improved by more than 5 times, the specific capacitance is obviously improved compared with that of the cobalt oxide composite material with single specific capacitance, and the spindle-shaped cobalt-manganese oxide composite material has good super capacitance performance.
The non-spindle cobalt-manganese oxide composite material is also manufactured while the cobalt-manganese composite of the spindle is synthesized. By comparison, under the condition that the current density is 4A/g, the specific capacitance of the spindle cobalt manganese oxide composite material is 414F/g, the specific capacitance of the non-spindle cobalt manganese oxide composite material is 350F/g, and the specific capacitance of the spindle cobalt manganese oxide composite material is 64F/g higher than that of the non-spindle cobalt manganese oxide composite material.
Therefore, compared with the prior art, the spindle-shaped cobalt manganese oxide composite material has the following advantages:
1. the preparation method is simple, the spindle-shaped cobalt-manganese oxide composite material can be obtained by a hydrothermal method and a carbonization method, and the cobalt acetate, the triammonium citrate, the manganese chloride hexahydrate and the potassium permanganate are commercialized, have low price and are suitable for mass production;
2. the nitrogen-doped carbon can effectively improve the adsorption effect on cobalt and manganese ions and reduce the waste of cobalt and manganese materials;
3. the spindle-shaped appearance is beneficial to the reaction of ions and solution liquid, the conductivity is improved, and the specific capacitance of the material is increased;
4. mn is loaded on the cobalt oxide, thereby not only effectively preventing Co3O4The structure is destroyed, electrolyte concentration can be reduced, the service life of the battery is prolonged, and the safety of the battery is guaranteed.
According to the 4 advantages, the cobalt-manganese oxide composite material has high practical application value and wide prospect market.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) of a spindle-shaped cobalt manganese oxide composite material prepared in example 1 of the present invention;
FIG. 2 is an XRD pattern of a fusiform cobalt manganese oxide composite material prepared according to example 1 of the present invention;
FIG. 3 is a graph showing isothermal adsorption curves of a spindle-shaped cobalt manganese oxide composite prepared in example 1 according to the present invention and a cobalt oxide composite not loaded with Mn prepared in comparative example 1 according to the present invention;
FIG. 4 is a graph showing pore size distribution of a spindle-shaped cobalt manganese oxide composite material prepared in example 1 of the present invention and a cobalt oxide composite material not loaded with Mn prepared in comparative example 1 of the present invention;
FIG. 5 is a graph showing constant current charge and discharge curves of a spindle-shaped cobalt manganese oxide composite material prepared in example 1 of the present invention and a cobalt oxide composite material not loaded with Mn prepared in comparative example 1 of the present invention;
FIG. 6 is EIS graphs of a spindle-shaped cobalt manganese oxide composite prepared in example 1 of the present invention and a cobalt oxide composite not loaded with Mn prepared in comparative example 1 of the present invention;
FIG. 7 is a cyclic voltammogram of a cobalt manganese oxide composite prepared in example 2 of the present invention;
fig. 8 is a scanning electron microscope image of a cobalt oxide composite material prepared in comparative example 1 of the present invention without supporting Mn.
FIG. 9 is a scanning electron micrograph of a non-spun cobalt manganese oxide composite prepared according to comparative example 2 of the present invention;
fig. 10 is a graph of potentiostatic charge and discharge curves of the composite material of the spindle-shaped cobalt manganese oxide prepared in example 1 of the present invention and the composite material of the non-spindle-shaped cobalt manganese oxide prepared in comparative example 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings, which are given by way of examples, but are not intended to limit the present invention.
Example 1
A preparation method of a fusiform cobalt manganese oxide composite material comprises the following steps:
step 1) preparation of a complex, 1g of cobalt acetate and 1g of triammonium citrate are weighed and put into 40mL of distilled water, and stirred until the mixture is transparent. The solution was then poured into a reaction kettle, and the program was set: the reaction temperature is 120 ℃, the reaction time is 15 hours, and after the reaction is finished, filtering and drying are carried out;
step 2) compounding manganese element and complex, and mixing the cobalt acetate and the ammonium citrate triammonium complex obtained in the step 1) with MnCl2·4H2O、KMnO4Mixing with water, wherein the powder of cobalt acetate and triammonium citrate complex, MnCl2·4H2O、KMnO4And the mass ratio of water is 1:0.5:0.5: stirring for 1h at 20; then placing the mixture into a reaction kettle, reacting at the reaction temperature of 150 ℃ for 14h, filtering and drying after the reaction is finished;
and 3) preparing the spindle-shaped cobalt-manganese oxide composite material, namely putting the powder obtained in the step 2) into a muffle furnace, heating to 250 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 1 h.
SEM tests were performed in order to obtain the microstructure of the spindle-shaped cobalt manganese oxide composite. As a result, as shown in fig. 1, the microstructure of the spindle-shaped cobalt manganese oxide composite material prepared in example 1 of the present invention was spindle-shaped.
In order to obtain the composition of the spindle-shaped cobalt manganese oxide composite material prepared in example 1 of the present invention, the structural composition thereof was mainly composed of Co as shown in FIG. 2 by XRD analysis3O4、MnO2And (CoMn)2O4And (4) forming.
In order to obtain the isothermal adsorption curve of the spindle-shaped cobalt manganese oxide composite material prepared in example 1 of the present invention, the test results are shown in FIG. 3, and the specific surface area is425m2/g。
In order to obtain the pore size distribution of the spindle-shaped cobalt manganese oxide composite material prepared in example 1 of the present invention, the test result is shown in fig. 4, and the ratio is the highest when the pore size distribution is 4 nm.
In order to obtain the specific capacitance of the spindle-shaped cobalt-manganese oxide composite material prepared in example 1 of the present invention, an electrode sheet was prepared using the spindle-shaped cobalt-manganese oxide composite material as an active material, and an electrochemical test was performed.
The preparation method of the pole piece comprises the following steps: weighing 0.08 g of cobalt manganese oxide composite material, 0.01 g of acetylene black and 0.01 g of polytetrafluoroethylene micro powder, placing the materials in a small agate grinding bowl, and adding 0.5 mL of ethanol for grinding; and pressing the ground sample with a foamed nickel current collector with the thickness of 1 mm under the pressure of 10 kPa, drying in air at room temperature, cutting into 2 cm multiplied by 2 cm to prepare the electrode of the super capacitor, and testing the specific capacitance of the electrode.
The electrode plate test result of the spindle-shaped cobalt manganese oxide composite material prepared in the embodiment 1 of the invention is shown in fig. 5, and the specific capacitance reaches 414F/g under the condition of 4A/g.
To obtain the resistance of the spindle-shaped cobalt manganese oxide composite material prepared in example 1 of the present invention, the spindle-shaped cobalt manganese oxide composite material was subjected to the EIS test, and the resistance was about 0.8 Ω as shown in fig. 6.
In order to obtain the influence of different temperatures on the spindle-shaped cobalt manganese oxide composite material, the cobalt manganese oxide composite material is prepared at different calcination temperatures.
Example 2
The preparation method of the spindle-shaped cobalt manganese oxide composite material at different calcination temperatures, which is the same as the preparation method of example 1 except that the steps not specifically described in the specific steps are as follows: step 3) the calcination temperature was 200 ℃.
In order to compare the influence of different calcination temperatures on the electrode material, the cobalt-manganese oxide composite material prepared in example 2 was prepared into an electrode sheet, and the preparation method of the electrode sheet was the same as that of the electrode sheet prepared in example 1.
The test results are shown in FIG. 7, and the specific capacitance is 0.702F/cm2。
Example 3
The preparation method of the spindle-shaped cobalt manganese oxide composite material at different calcination temperatures, which is the same as the preparation method of example 1 except that the steps not specifically described in the specific steps are as follows: step 3) the calcination temperature was 300 ℃.
In order to compare the influence of different calcination temperatures on the electrode material, the cobalt-manganese oxide composite material prepared in example 3 was prepared into an electrode sheet, and the preparation method of the electrode sheet was the same as that of the electrode sheet prepared in example 1.
The test results are shown in FIG. 7, and the specific capacitance is 0.683F/cm2。
By comparison of FIG. 7, the specific capacitance of the fusiform cobalt manganese oxide composite prepared by example 1 was 0.725F/cm2And is larger than the specific capacitance of the cobalt manganese oxide composite prepared in the example 2 and the cobalt manganese oxide composite prepared in the example 3. It shows that the specific capacitance is highest under the condition that the calcining temperature is 250 ℃.
In order to compare the effect of Mn having an increased specific capacitance in cobalt oxide, a cobalt oxide composite material containing no manganese was prepared.
Comparative example 1
The preparation method of the cobalt oxide composite material not supporting Mn, which is the same as the preparation method of example 1 except that the steps not specifically described in the specific steps are: after step 1, step 3 is performed directly, i.e., step 2 is not included.
The scanning electrogram of the cobalt oxide composite material prepared in comparative example 1 without supporting Mn was measured and shown in fig. 8, and was in a granular morphology.
In order to obtain the isothermal adsorption curve of the cobalt oxide composite material not loaded with Mn prepared in comparative example 1, BET test was performed, and the test result is shown in fig. 3, in which the isothermal adsorption curve is lower in height than the isothermal adsorption curve of the spindle-shaped cobalt manganese oxide composite material, indicating that the specific surface area is smaller than that of the spindle-shaped cobalt manganese oxide composite material.
In order to obtain a pore size distribution diagram of the cobalt oxide composite material not loaded with Mn prepared in comparative example 1, a pore size distribution test was performed thereon, as shown in fig. 4, it can be known that the spindle-shaped cobalt manganese oxide composite material contains a large amount of mesoporous structures, while the cobalt oxide composite material not loaded with Mn has a small content of mesopores.
In order to obtain comparative example 1 in order to compare the effect of Mn on increasing specific capacitance in cobalt oxide, the cobalt oxide composite material prepared in comparative example 1, which does not contain Mn, was prepared into an electrode sheet in the same manner as the electrode sheet of example 1.
The test results are shown in FIG. 5, which shows that the specific capacitance is 287F/g, which is smaller than that of the spindle-shaped cobalt manganese oxide composite material, and the specific capacitance is increased after loading Mn.
In order to obtain the resistance of the cobalt oxide composite material not loaded with Mn according to comparative example 1 of the present invention, the cobalt oxide composite material not loaded with Mn was subjected to the EIS test, and the resistance was 1.9 Ω as shown in fig. 6. It can be seen from the figure that the composite material of spindle-shaped cobalt manganese oxide of example 1 of the present invention has a small resistance value, which is advantageous for electron transport.
To demonstrate the effect of the spindle-like structure on the electrochemical performance, non-spindle-like cobalt manganese oxide composites were prepared.
Comparative example 2
The steps not specifically described in the specific steps of the non-spindle cobalt manganese oxide composite material are the same as the preparation method of example 1, except that: powder of cobalt acetate and triammonium citrate complex in step 2), MnCl2·4H2O、KMnO4And the mass ratio of water is 1: 1: 1: 20.
in order to obtain the micro-morphology of the non-spun cobalt manganese oxide composite prepared in comparative example 2, SEM tests were performed. The result is shown in fig. 9, the microstructure of the non-spindle cobalt manganese oxide composite material of comparative example 2 of the present invention is a non-spindle structure, which indicates that the spindle microstructure can be obtained only by controlling the raw material ratio.
In order to obtain the influence of the spindle-shaped structure on the electrochemical performance, the non-spindle-shaped cobalt manganese oxide composite material prepared in the comparative example 2 is prepared into an electrode slice, and the preparation method of the electrode slice is the same as that of the electrode slice in the example 1.
The test result is shown in fig. 10, the specific capacitance of which is 350F/g and is smaller than that of the spindle-shaped cobalt manganese oxide composite material, and the spindle-shaped morphology can increase the specific capacitance of the composite material.

Claims (8)

1. A fusiform cobalt manganese oxide composite material is characterized in that: the cobalt manganese oxide composite material is obtained by complexing cobalt acetate and triammonium citrate and loading Mn, wherein the composite material is integrally in a spindle-shaped structure, the average size is 10um and 2.5um respectively in length and width, and the carbon material exists in the spindle-shaped structure.
2. The fusiform cobalt manganese oxide composite material according to claim 1, wherein: the Mn is formed by MnCl2·4H2O and KMnO4Prepared in situ, and directly loaded with cobalt acetate and triammonium citrate complex.
3. The method for preparing a fusiform cobalt manganese oxide composite material according to claim 1, comprising the steps of:
step 1) preparation of a complex, weighing a certain amount of cobalt acetate and triammonium citrate, putting the cobalt acetate and triammonium citrate into distilled water, stirring the mixture to be transparent, putting the mixture into a reaction kettle, and obtaining the cobalt acetate and triammonium citrate complex under a certain condition;
step 2) compounding manganese element and complex, and mixing the cobalt acetate and the ammonium citrate triammonium complex obtained in the step 1) with MnCl2·4H2O、KMnO4Mixing with water, stirring for 1h, putting into a reaction kettle, reacting under certain conditions, and drying after the reaction is finished;
and 3) preparing the fusiform cobalt-manganese oxide composite material, namely putting the powder obtained in the step 2) into a muffle furnace, and calcining under certain conditions to obtain the fusiform cobalt-manganese oxide composite material.
4. The production method according to claim 3, characterized in that: the mass ratio of the cobalt acetate to the triammonium citrate in the step 1) is 1: 1; the reaction condition of the step 1) is that the reaction is carried out for 12 to 24 hours in an oven at the temperature of 150 ℃.
5. The production method according to claim 3, characterized in that: the step 2) powder of cobalt acetate and triammonium citrate complex, MnCl2·4H2O、KMnO4The mass ratio of the water to the water is 1:0.5:0.5: 20.
6. The production method according to claim 3, characterized in that: the reaction condition of the step 2) is that the reaction is carried out for 12 to 24 hours in an oven at the temperature of 120 ℃.
7. The production method according to claim 3, characterized in that: the calcination condition of the step 3) is to heat up to 200-400 ℃ at a heating rate of 5 ℃/min for calcination under the air condition, and then to preserve heat for 1-5 h.
8. The use of the fusiform cobalt manganese oxide composite material as an electrode material of a supercapacitor according to claim 1, wherein: under 1M KOH solution, the discharge is carried out in the range of-0.1-0.5V, and the specific capacitance is 410-440F/g when the discharge current density is 4A/g.
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