CN113299487B - Composite electrode material and preparation method and application thereof - Google Patents

Composite electrode material and preparation method and application thereof Download PDF

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CN113299487B
CN113299487B CN202110564788.9A CN202110564788A CN113299487B CN 113299487 B CN113299487 B CN 113299487B CN 202110564788 A CN202110564788 A CN 202110564788A CN 113299487 B CN113299487 B CN 113299487B
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electrode material
composite electrode
chitosan
sponge
melamine sponge
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CN113299487A (en
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昌杰
桂君
王守玲
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Chizhou University
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Chizhou University
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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
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • 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
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • 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
    • H01G11/84—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 provides a preparation method and application of a composite electrode material, wherein the composite electrode material is prepared by dipping melamine sponge by chitosan, and performing freeze drying and high-temperature heat treatment under the protection of inert gas, wherein a carbon skeleton is obtained after the melamine sponge is carbonized, and a carbon sheet is obtained after the chitosan is carbonized and embedded into or coated on the carbon skeleton.

Description

Composite electrode material and preparation method and application thereof
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a composite electrode material and a preparation method and application thereof.
Background
With the development of various portable and wearable electronic devices, the development of efficient, safe and green flexible energy storage devices is urgently needed. The super capacitor has the advantages of high charging and discharging speed, high power density, long cycle life and high safety, and has attracted extensive attention. In order to meet the requirements of ultra-thinness, light weight and flexibility, people are dedicated to developing a novel capacitor with excellent electrochemical performance and good mechanical performance. The key influencing the performance of the super capacitor is the electrode material, 10-20% of conductive agent and 5-10% of binder are required to be added when the traditional super capacitor electrode is manufactured, so that the real content of active substances in the whole electrode is less than 80%, and the actual performance of the capacitor is reduced. Therefore, the performance of the electrode can be improved by constructing a self-supporting structure electrode which does not require a binder or a conductive agent.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a composite electrode material, a preparation method and application thereof.
In order to achieve the above objects and other objects, the present invention includes the following technical solutions: the invention firstly provides a preparation method of a composite electrode material, which comprises the following steps: forming a chitosan solution; fully soaking melamine sponge in the chitosan solution, and then carrying out vacuum pumping treatment to obtain chitosan-soaked melamine sponge; freeze-drying the chitosan-impregnated melamine sponge to obtain a precursor of the composite electrode material; and thermally treating the precursor of the composite electrode material under an oxygen-free condition to obtain the composite electrode material.
In one embodiment, the chitosan solution has a mass fraction of 0.5-1.5%.
In one embodiment, the melamine sponge has a thickness of 1-6 cm, a length of 3-15 cm and a width of 2-8 cm.
In one embodiment, the melamine sponge is of a cubic structure with the side length of 3-6 cm.
In one embodiment, the time for the immersion is 1-4 min.
In one embodiment, the vacuum degree of the vacuum pumping treatment is-0.05 to-0.1 MPa.
In one embodiment, the oxygen-free condition is performed under the protection of inert gas, and the inert gas is any one of nitrogen, argon-hydrogen mixed gas and nitrogen-hydrogen mixed gas.
In one embodiment, the heat treatment temperature is 600-1200 ℃, and the heat treatment time is 0.2-6 h.
The invention also provides a composite electrode material prepared by the method.
In one embodiment, the composite electrode material has a capacity of 200F/g at a voltage of-1 to 0V and a current density of 0.2A/g, a capacitance of 118F/g at a current density of 10A/g, and a capacitance retention rate of 59%.
In one embodiment, the content of nitrogen element in the composite electrode material is 3.22-4.99%.
In yet another aspect, the present invention provides an energy storage device comprising a composite electrode material as described above.
In one embodiment, the energy storage device is a super capacitor.
The invention has the beneficial effects that: the prepared composite electrode material has a self-supporting structure and good conductivity, and a conductive agent and a binder are not required to be added during electrode manufacturing, so that the proportion of active materials in the capacitor can be effectively increased, and the real performance of the capacitor is improved. In addition, as the conductive agent and the binder are not required to be added, the whole electrode preparation process is simplified, the electrode manufacturing cost is greatly reduced, the steps of grinding, rolling film forming, drying and the like are omitted during the electrode preparation, and the process cost is reduced.
The invention adopts a method of combining solution dipping with freeze drying to prepare a melamine sponge precursor wrapped by chitosan, and the melamine sponge precursor is calcined in inert gas to obtain the carbon/carbon composite electrode material. By utilizing the large specific surface area of the chitosan carbon sheet, the energy storage active sites are effectively improved, the specific capacity of the electrode is improved, and the characteristics of good conductivity, high porosity and good mechanical stability of the carbon foam framework can ensure the contact of the active material and the electrolyte, the rapid transmission of ions and electrons and the structural stability in the charging and discharging processes, thereby improving the electrochemical performance of the active material.
The above-described and other features, aspects, and advantages of the present application will become more apparent with reference to the following detailed description.
Drawings
Fig. 1 is a Raman spectrum of the composite electrode materials obtained in examples 1, 2 and 3 and the carbon foam electrode material obtained in comparative example 1.
FIG. 2 is a scanning electron micrograph of the composite electrode material obtained in example 1.
FIG. 3 is a scanning electron micrograph of the composite electrode material obtained in example 1.
FIG. 4 is a plot of specific capacitance versus current density for composite electrode materials made in examples 1, 2, and 3, and for carbon foam electrode material made in comparative example 1.
FIG. 5 is a plot of specific capacitance versus cycle number for composite electrode materials prepared in examples 1, 2, and 3, and for carbon foam electrode materials prepared in comparative example 1.
FIG. 6 is a SEM photograph of a composite electrode material obtained in example 2.
FIG. 7 is a SEM photograph of a composite electrode material obtained in example 2.
FIG. 8 is a SEM photograph of a composite electrode material obtained in example 3.
FIG. 9 is a SEM photograph of a composite electrode material obtained in example 3.
Fig. 10 is a scanning electron micrograph of the carbon foam electrode material prepared in comparative example 1.
Fig. 11 is an external scanning electron micrograph of the composite electrode material prepared in comparative example 2.
Fig. 12 is an internal scanning electron micrograph of the composite electrode material prepared in comparative example 2.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Please refer to fig. 1 to 12. The invention firstly provides a preparation method of a composite electrode material, which comprises the following steps of S1-S4:
-S1: forming a chitosan solution;
-S2: fully soaking melamine sponge in the chitosan solution, and then carrying out vacuum pumping treatment to obtain chitosan-soaked melamine sponge;
-S3: freeze-drying the chitosan-impregnated melamine sponge to obtain a precursor of the composite electrode material;
-S4: and thermally treating the precursor of the composite electrode material under an oxygen-free condition to obtain the composite electrode material.
In step S1, the chitosan solution may be prepared by dissolving chitosan in acetic acid, the dissolving may be performed under stirring, the chitosan may be 80-95% deacetylated chitosan, in some embodiments, the chitosan may be chitosan manufactured by Adamas reagent company, the volume concentration of the acetic acid may be 0.2-1%, and the dissolving temperature of the chitosan in the acetic acid may be 10-50 ℃. In some embodiments, the chitosan solution may have a mass fraction of 0.5 to 1.5%, and further may have a mass fraction of 0.5 to 1.0%, such as 0.6%, 0.7%, 0.8%, and the like.
According to the invention, the dipping amount of chitosan on the melamine sponge can be better controlled by controlling the mass fraction of chitosan, so that the content of carbon sheet materials formed after the chitosan is carbonized in the composite electrode material is further controlled, in some embodiments, the weight gain ratio of the melamine sponge can be 60-180%, the weight gain ratio of the melamine sponge can be the ratio of the difference between the weight of a precursor of the composite electrode material and the weight of the melamine sponge before the chitosan solution is dipped to the weight of the melamine sponge before the chitosan solution is dipped, and further, the mass fraction of chitosan can influence the content of nitrogen elements in the composite electrode material to a certain extent. The molecular formula of the melamine sponge is C3H6N6And the molecular formula of the chitosan is (C)6H11NO4) N, the content of nitrogen element in the melamine sponge is obviously higher than that of chitosan according to the molecular formula, so that the content of nitrogen element in a carbon skeleton formed by the carbonized melamine sponge is higher than that of nitrogen element in a carbon sheet formed by the chitosan, and the larger the chitosan impregnation amount is, the lower the content of nitrogen element in the final composite electrode material is. Furthermore, the higher the mass fraction of chitosan, the lower the mass fraction of nitrogen in the finally obtained composite electrode material, so that the chitosan solution with a smaller mass fraction needs to be selected for soaking to a certain extent so as to obtain the composite electrode material with relatively higher nitrogen content, and further, the mass fraction of nitrogen in the composite electrode material can be 3.22-4.99％。
In step S2, the melamine sponge may be a sound-insulating flame-retardant sponge, and the melamine sponge of the present invention may be carbonized at a high temperature to become a nitrogen-doped carbon foam with good conductivity, while still maintaining an open pore structure and high mechanical strength. In addition, the melamine sponge has high nitrogen content, a large amount of nitrogen remains after carbonization, the obtained nitrogen-doped carbon foam has better conductivity and hydrophilicity due to the characteristic of electron donating, and meanwhile, the doping of nitrogen on a carbon skeleton can bring more defects and vacancies, so that the electrochemical activity of the material is higher. The melamine sponge can be a cuboid or a cubic structure, and further can be a cubic structure, the thickness of the melamine sponge can be 1-6 cm, the length can be 3-15 cm, the width can be 2-8 cm, in some embodiments, the size of the melamine sponge can be a cubic structure of 5 × 5 × 5cm, in some embodiments, the melamine sponge can be a sponge of a super-quality model, the dipping can be realized by completely immersing the melamine sponge in the chitosan solution, and the amount of the chitosan solution can be significantly excessive, so that the melamine sponge is completely immersed in the chitosan solution. The dipping time can be 1-4 min, such as 2min, 3min, 4min and the like, and the sufficient dipping can be realized by flattening the melamine sponge, dipping the melamine sponge into a chitosan solution, and then repeating the pressing for 3-4 times after the melamine sponge is freely unfolded to the volume before the pressing.
In step S2, the vacuum pumping process may be performed by turning on a vacuum pump in a vacuum drying oven, the vacuum degree in the vacuum drying oven may be-0.05 to-0.1 MPa, the vacuum pumping process time in the vacuum drying oven may be 6 to 60min, for example, 10min, 15min, 20min, etc., and the vacuum pumping process may completely strip air in the melamine sponge, so that the chitosan solution may sufficiently impregnate the sponge, thereby improving the impregnation rate and the impregnation uniformity of the chitosan.
In step S3, the freeze-drying step may be to freeze the melamine sponge fully soaked with chitosan in a freezing chamber, where the temperature of the freezing chamber may be-40 to-65 ℃, the freezing time may be 6 to 72 hours, and after the freezing step, the frozen melamine sponge may be transferred to a freeze-drying oven for freeze-drying.
In step S4, the oxygen-free condition may be performed under the protection of an inert gas, which may be an inert gas such as nitrogen, argon-hydrogen mixture, and nitrogen-hydrogen mixture. The temperature of the heat treatment can be 600-1200 ℃, such as 800 ℃, 1000 ℃ and the like, the time of the heat treatment can be 0.2-6 h, such as 1, 2, 4, 5h and the like, and the heat treatment can be carried out in a tube furnace, such as a quartz tube furnace. The temperature rise rate of the tube furnace can be 5-10 ℃/min.
The invention also provides a composite electrode material prepared by the method, the composite electrode material consists of a foam carbon skeleton and a carbon sheet, the carbon sheet can be embedded into or coated on the carbon foam skeleton, the foam carbon skeleton of the composite electrode material has good conductivity, and the carbon sheet embedded into or coated on the foam carbon also has certain conductivity, so that the composite electrode material does not need to be additionally added with a conductive agent during use, and the amount of the chitosan carbon sheet embedded into or coated on the carbon skeleton is controlled within a certain range, so that the carbon sheet and the foam carbon skeleton have good bonding performance, and the electrode material does not need a binder during use. The composite electrode material has the capacity of up to 200F/g at the highest under the voltage range of-1-0V and the current density of 0.2A/g, can still reach 118F/g under the current density of 10A/g, and has the specific capacitance retention rate of 59%.
In yet another aspect, the present invention provides an energy storage device, which may have a composite electrode material as described above, and in some embodiments, the energy storage device may be a super capacitor, such as a flexible or solid-state capacitor, etc., although the energy storage device of the present invention is not limited thereto, and may also be various electrochemical energy storage devices including lithium batteries, etc.
Note that "%" and "part(s)" shown herein mean "% by mass" and "part(s) by mass", respectively, unless otherwise specified.
Hereinafter, the present invention will be more specifically explained by referring to examples, which should not be construed as limiting. Appropriate modifications may be made within the scope consistent with the gist of the present invention, and all of them fall within the technical scope of the present invention.
The electrochemical performance test in the invention is to clamp the prepared electrode material into foamed nickel or into a platinum sheet electrode clamp as a working electrode after cutting the electrode material into small pieces, and the electrochemical performance of the electrode material is researched by utilizing a three-electrode system. The specific operation is as follows:
(1) the prepared carbon foam is cut into small pieces and directly used as an electrode material.
(2) Weighing the small pieces of the electrode material obtained in (1), and sandwiching the small pieces of the electrode material between two pieces having an area of about 1cm2And a nickel sheet is introduced between the two pieces of foamed nickel to be used as a lead. And then tabletting by using a hydraulic press to obtain the working electrode for testing.
(3) And (3) taking the electrode obtained in the step (2) as a working electrode, taking an Hg/HgO (1M NaOH) electrode as a reference electrode, taking a platinum sheet electrode as a counter electrode, and taking 6M KOH solution as electrolyte to form a three-electrode system. The electrochemical performance of the material is characterized by adopting Cyclic Voltammetry (CV) and constant current charging and discharging as means.
Examples of the invention
Example 1
3mL of glacial acetic acid is transferred into 297mL of deionized water, the mixture is heated to 40 ℃, 1.5g of chitosan is added in a small amount for a plurality of times under magnetic stirring, and the mixture is stirred until the chitosan is completely dissolved, so that a chitosan solution with the mass fraction of about 0.5% is obtained. Cutting the melamine sponge into sponge blocks with uniform size (length, width and height are about 5cm), immersing the sponge blocks into a beaker filled with 0.5% chitosan solution by mass, then transferring the beaker into a vacuum drying oven, starting a vacuum pump, and continuously exhausting air for 30min under-0.1 MPa to ensure that the solution fully impregnates the sponge. And taking out the soaked sponge, putting the sponge into a freezing chamber for freezing, and transferring the sponge into a freeze drying box for freeze drying.
And (3) putting the freeze-dried sponge into a quartz tube furnace, heating to 800 ℃ at a heating rate of 10 ℃/min under the protection of nitrogen, preserving the heat for 2h, and cooling to room temperature to obtain the composite electrode material.
In fig. 1, a curve b is a Raman spectrum of the composite electrode material prepared in this example, and the spectrum shows a distinct D peak and a distinct G peak of carbon.
Fig. 2 and 3 are scanning electron micrographs of the composite electrode material prepared in this example, and clearly show the carbon skeleton obtained from the melamine sponge and the embedded or coated carbon sheet obtained from the carbonized chitosan.
In fig. 4, a curve b is a relation curve between the specific capacitance and the current density obtained in the constant current charge and discharge test of the composite electrode material prepared in this embodiment, and it can be seen that the specific capacitance of the material can reach 169F/g at a current density of 0.2A/g, the specific capacitance of 10A/g still maintains 120F/g, and good rapid charge and discharge characteristics are shown.
In fig. 5, a curve b is a relation curve between the specific capacitance and the number of charge and discharge cycles of the composite electrode material prepared in this example at a current density of 4A/g for 3000 cycles, and it can be seen that after 3000 cycles, the capacity retention rate is 100%, and excellent cycle stability is shown.
Example 2
3mL of glacial acetic acid is transferred and added into 297mL of deionized water, the mixture is heated to 40 ℃, 3g of chitosan is added for a plurality of times in small amount under magnetic stirring, and the mixture is stirred until the chitosan is completely dissolved, so that a chitosan solution with the mass fraction of about 1% is obtained. Cutting the melamine sponge into sponge blocks with uniform size (length, width and height are about 5cm), immersing the sponge blocks into a beaker filled with a chitosan solution with the mass fraction of 1%, then transferring the beaker into a vacuum drying oven, and starting a vacuum pump to continuously exhaust air at-0.1 MPa for 30min to ensure that the solution fully impregnates the sponge. And taking out the soaked sponge, putting the sponge into a freezing chamber for freezing, and transferring the sponge into a freeze drying box for freeze drying.
And (3) putting the freeze-dried sponge into a quartz tube furnace, heating to 800 ℃ at a heating rate of 10 ℃/min under the protection of nitrogen, preserving the heat for 2h, and cooling to room temperature to obtain the composite electrode material.
Fig. 1, curve c is a Raman spectrum of the composite electrode material prepared in this example, which shows distinct peaks D and G of carbon.
Fig. 6 and 7 are scanning electron micrographs of the composite electrode material prepared in this example, and clearly show the carbon skeleton obtained from melamine sponge and the embedded or coated carbon sheet obtained from chitosan.
In fig. 4, a curve c is a relation curve between the specific capacitance and the current density obtained in the constant current charge and discharge test of the composite electrode material prepared in this embodiment, and it can be seen that the specific capacitance of the material can reach 171F/g at a current density of 0.2A/g, the specific capacitance of 10A/g still maintains 113F/g, and a good rapid charge and discharge characteristic is shown.
Fig. 5, curve c is a relation curve between the specific capacitance and the number of charge and discharge cycles of the composite electrode material prepared in this example at a current density of 4A/g for 3000 cycles, and it can be seen that after 3000 cycles, the capacity retention rate is 100%, and excellent cycle stability is shown.
Example 3
3mL of glacial acetic acid is transferred and added into 297mL of deionized water, the mixture is heated to 40 ℃, 4.5g of chitosan is added in a small amount for a plurality of times under magnetic stirring, and the mixture is stirred until the chitosan is completely dissolved, so that a chitosan solution with the mass fraction of about 1.5% is obtained. Cutting the melamine sponge into sponge blocks with uniform size (length, width and height are about 5cm), immersing the sponge blocks into a beaker filled with a chitosan solution with the mass fraction of 1.5%, then transferring the beaker into a vacuum drying oven, and starting a vacuum pump to continuously exhaust air at-0.1 MPa for 30min to ensure that the solution fully impregnates the sponge. And taking out the soaked sponge, putting the sponge into a freezing chamber for freezing, and transferring the sponge into a freeze drying box for freeze drying.
And (3) putting the freeze-dried sponge into a quartz tube furnace, heating to 800 ℃ at a heating rate of 10 ℃/min under the protection of nitrogen, preserving the heat for 2h, and cooling to room temperature to obtain the composite electrode material.
Fig. 1 is a graph D showing a Raman spectrum of the composite electrode material prepared in this example, in which a D peak and a G peak of carbon are clearly shown.
Fig. 2 is a scanning electron micrograph of the composite electrode material prepared in this example, in which the carbon skeleton derived from melamine sponge and the embedded or coated carbon sheets derived from chitosan are clearly visible.
Fig. 4 is a curve d of a relationship between a specific capacitance and a current density obtained in a constant current charge and discharge test of the composite electrode material prepared in this embodiment, and it can be seen that the specific capacitance of the material can reach 200F/g at a current density of 0.2A/g, the specific capacitance of 10A/g still maintains 118F/g, and a good rapid charge and discharge characteristic is shown.
Fig. 5 is a curve d of the relationship between the specific capacitance and the number of charge and discharge cycles of the composite electrode material prepared in this example at a current density of 4A/g for 3000 cycles, and it can be seen that after 3000 cycles, the capacity retention rate is 88.5%, and good cycle stability is shown.
Comparing example 3 with example 1-2, it can be seen that when the chitosan mass fraction content reaches 1.5%, the rate charge and discharge performance and the cycle stability are inferior to those of example 1-2 due to the increased content of carbon sheets generated from chitosan in the composite electrode material.
Comparative example 1
The melamine sponge is cut into sponge blocks (the length, the width and the height are about 5cm) with uniform sizes, and the sponge blocks are cleaned by deionized water and then placed into a vacuum drying oven for drying. And (3) putting the dried sponge into a quartz tube furnace, heating to 800 ℃ at a heating rate of 10 ℃/min under the protection of nitrogen, preserving the heat for 2h, and cooling to room temperature to obtain the electrode material only containing carbon foam.
Curve a in FIG. 1 is a Raman spectrum of the carbon foam obtained in the comparative example, showing a distinct D peak and a distinct G peak of the carbon.
FIG. 10 is a scanning electron micrograph of the carbon foam obtained in this comparative example, from which the carbon foam skeleton obtained from the melamine sponge can be clearly seen.
In fig. 4, curve a is a relation curve of the specific capacitance and the current density obtained in the constant current charge and discharge test of the carbon foam prepared in this example, and it can be seen that the specific capacitance of the material can reach 123F/g at the current density of 0.2A/g, the specific capacitance of 10A/g is still 77F/g, and although good rapid charge and discharge characteristics are shown, the specific capacitance of the carbon foam at each current density is significantly lower than that of the carbon foam sponge (examples 1, 2 and 3) compounded by the carbon sheets.
In fig. 5, curve a is the relationship curve between the specific capacitance and the number of charge and discharge cycles of 3000 cycles of the carbon foam prepared in this example at a current density of 4A/g, and it can be seen that the capacity retention rate is 100% after 3000 cycles, showing excellent cycle stability.
Comparative example 2
3mL of glacial acetic acid is transferred and added into 297mL of deionized water, the mixture is heated to 40 ℃, 1.5g of chitosan is added in a small amount for a plurality of times under magnetic stirring, and the mixture is stirred until the chitosan is completely dissolved, so that a chitosan solution with the mass fraction of about 0.5% is obtained. The melamine sponge was cut into sponge pieces of uniform size (about 5cm in length, width and height) and immersed in a beaker containing 0.5% by mass of chitosan solution to impregnate the sponge with the solution. And taking out the soaked sponge, putting the sponge into a freezing chamber for freezing, and transferring the sponge into a freeze drying box for freeze drying. After freeze-drying, the outer surface of the sponge is hard, the inner part is soft, and the inner part and the outer part are not uniform.
And (3) putting the freeze-dried sponge into a quartz tube furnace, heating to 800 ℃ at a heating rate of 10 ℃/min under the protection of nitrogen, preserving heat for 2 hours, and cooling to room temperature to obtain the composite electrode material.
Fig. 11 is a scanning electron micrograph of the outer layer of the composite electrode material prepared in this comparative example, and it is clearly seen that the chitosan carbon sheet is thick.
Fig. 12 is a scanning electron micrograph of the composite electrode material prepared in this comparative example, in which almost no carbon sheet is embedded or coated inside, and only the carbon foam skeleton is seen, illustrating that the composite electrode material prepared in this comparative example is non-uniform inside and outside.
It is necessary to point out here: the above examples are only for further illustration of the present invention and should not be construed as limiting the scope of the present invention, and the non-essential modifications and adaptations of the present invention by those skilled in the art based on the foregoing descriptions are within the scope of the present invention.

Claims (8)

1. A preparation method of the composite electrode material is characterized by comprising the following steps: the method comprises the following steps:
forming a chitosan solution;
fully soaking melamine sponge in the chitosan solution, and then carrying out vacuum pumping treatment to obtain chitosan-soaked melamine sponge;
freeze-drying the chitosan-impregnated melamine sponge to obtain a precursor of the composite electrode material;
thermally treating a precursor of the composite electrode material under an oxygen-free condition to obtain the composite electrode material; the mass fraction of the chitosan solution is 0.5-1.5%; the temperature of the heat treatment is 600-1200 DEG CoAnd C, the heat treatment time is 0.2-6 h.
2. The method of claim 1, wherein: the melamine sponge is 1-6 cm in thickness, 3-15 cm in length and 2-8 cm in width.
3. The method of claim 1, wherein: the dipping time is 1-4 min.
4. The method of claim 1, wherein: the vacuum degree of the vacuum pumping treatment is-0.05 to-0.1 MPa.
5. The method of claim 1, wherein: the oxygen-free condition is carried out under the protection of gas, and the gas is any one of nitrogen, argon-hydrogen mixed gas and nitrogen-hydrogen mixed gas.
6. A composite electrode material prepared according to any one of claims 1 to 5.
7. An energy storage device, characterized by: the energy storage device comprises the composite electrode material of claim 6.
8. The energy storage device of claim 7, wherein: the energy storage device is a super capacitor.
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