CN111261417A - Cobalt oxide-aloe-derived porous carbon composite electrode material and synthesis method and application thereof - Google Patents
Cobalt oxide-aloe-derived porous carbon composite electrode material and synthesis method and application thereof Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 39
- 239000007772 electrode material Substances 0.000 title claims abstract description 37
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 36
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- 238000002360 preparation method Methods 0.000 claims 1
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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Abstract
The invention discloses a cobalt oxide-aloe derived porous layer carbon composite electrode material and a synthesis method and application thereof, belonging to the field of nano electrode materials. The method comprises the steps of taking aloe gel as a carbon source and cobalt nitrate as a cobalt source, and carrying out hydrothermal reaction to grow cobalt oxide particles in situ on the surfaces of aloe gel particles to obtain a compound. Finally, the composite is carbonized and activated, so that the cobalt oxide-aloe derived porous layer carbon composite electrode material is obtained. The synthetic method is simple, the obtained product is uniform in appearance and large in specific surface area, the advantages of the biomass material such as large specific surface area and a layered porous structure are combined, and the heteroatom is introduced to form the pseudo-capacitance, so that the pseudo-capacitance has better electrochemical performance and electrochemical stability when being applied to the manufacture of the electrode of the super capacitor, and is suitable for the fields of energy conversion, storage and the like.
Description
Technical Field
The invention belongs to the field of nano electrode materials, and particularly relates to a cobalt oxide-aloe derived porous layer carbon composite electrode material and a synthesis method and application thereof.
Background
The super capacitor is used as a novel energy storage device combining the advantages of a traditional capacitor and a secondary battery, has higher energy density than the traditional capacitor, has more excellent power density and cycle life than the secondary battery, and is expected to be widely applied to the fields of energy conversion, aerospace systems, communication engineering, microelectronic devices and the like. From the viewpoint of energy storage mechanism, the super capacitor mainly has: an electric double layer capacitor using a carbon-related material as an electrode, which stores energy by means of charge separation at the surface of the electrode/electrolyte; the pseudo capacitor uses polymer and metal oxide as electrodes and stores energy by means of the Faraday reaction of the electrodes in electrolyte. However, supercapacitors have a low energy density (below 5 Wh-kg)-1) This is a challenging problem for the development of the supercapacitor industry. The research of the electrode material is a key way for improving the electrochemical performance of the super capacitor.
Disclosure of Invention
The invention provides a cobalt oxide-aloe derived porous layer carbon composite electrode material and a synthesis method and application thereof.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme.
The invention provides a synthesis method of a cobalt oxide-aloe derived porous layer carbon composite electrode material, which comprises the following steps: taking aloe gel as a carbon source and cobalt nitrate as a cobalt source, and carrying out hydrothermal reaction to grow cobalt oxide on the surface of the aloe gel in situ to obtain a compound; carbonizing the composite to obtain the cobalt oxide-aloe derived porous layer carbon composite electrode material.
Further, the compound is obtained by the following steps:
s1, obtaining aloe gel, adding cobalt nitrate, and uniformly mixing to obtain a mixture;
and S2, adding water into the mixture, placing the mixture into a high-pressure reactor for heating to perform hydrothermal reaction, and after the reaction is finished, cooling, cleaning and drying to obtain the compound.
Further, the carbonizing of the accord comprises:
s3, cleaning the composite, drying and carbonizing in an oxygen-free mode to obtain the cobalt oxide-aloe derived porous layer carbon composite electrode material; wherein the cleaning process is water cleaning, or ethanol and water cleaning.
Further, in step S1: the aloe gel is obtained by removing skin from folium Aloe; the cobalt nitrate is added according to the mass ratio of 1: 1-2: 1 to the dried aloe gel product; wherein the dried product of aloe vera gel is obtained by the following steps: cutting the aloe gel into small pieces, and baking for 6-8 hours at 100-140 ℃ to obtain the aloe gel.
Further: in step S2, the temperature of the hydrothermal reaction is 160-200 ℃ and the time is 10-14 h.
Further: in step S3, the temperature of the oxygen-free carbonization of the compound is 600-800 ℃, and the time is 40-60 min.
The invention also provides a cobalt oxide-aloe derived porous layer carbon composite electrode material which is synthesized according to the synthesis method of the cobalt oxide-aloe derived porous layer carbon composite electrode material, comprises carbonized aloe gel and cobalt oxide attached to the carbonized aloe gel and is applied to preparing electrodes of supercapacitors.
The invention has the beneficial effects that:
1. the synthesis method is simple, biomass is used as an electrode substrate, and the electrode substrate is rich in raw materials, environment-friendly and low in price. Cobalt is doped into the biomass material by using an in-situ growth mode, and the obtained product has uniform appearance and large specific surface area.
2. The advantages of large specific surface area and layered porous structure of the biomass material are combined, and heteroatom is introduced to form pseudo capacitance, so that the surface structure of carbon atoms can be effectively improved, and the specific capacitance is remarkably improved. When the composite material is manufactured into the electrode of the super capacitor, the super capacitor has larger capacitance, longer service life and good conductivity and rate capability.
Drawings
FIG. 1 is an SEM image of sample ALC-700 provided in example 1.
FIG. 2 is an elemental distribution diagram of the sample ALC-700 provided in example 1.
FIG. 3(a) shows the ALC-700 sample provided in example 1 and Co provided in comparative example 13O4XRD pattern of (a).
FIG. 3(b) is a sample of ALC-700 provided in example 1 and Co provided in comparative example 13O4The raman spectrum of (a).
FIG. 4(a) shows the ALC-700 sample provided in example 1 and Co provided in comparative example 13O4At 10mV · s-1
The lower CV curve;
FIG. 4(b) is a CV curve of the ALC-700 samples provided in example 1 at different scan rates;
FIG. 4(c) is a sample of ALC-700 provided in example 1 and Co provided in comparative example 13O4At 1 A.g-1Lower constant current discharge curve;
FIG. 4(d) is a charge-discharge curve of the ALC-700 sample provided in example 1 at different current densities; FIG. 4(e) shows the ALC-700 sample provided in example 1 and Co provided in comparative example 13O4At 10-2–105Electrochemical impedance spectroscopy in the frequency range of Hz;
FIG. 4(f) is the cycle life and coulombic efficiency (inset is TEM morphology of the ALC-700 sample after 10000 cycles) of the symmetric supercapacitor devices made from the ALC-700 samples provided in example 1.
FIG. 5 is a schematic diagram of a symmetrical supercapacitor device assembled from ALC-700 and activated carbon provided in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The cobalt oxide-aloe derived porous carbon composite electrode material, the synthesis method and the application thereof according to the embodiment of the present invention will be specifically described below.
The invention provides a synthesis method of a cobalt oxide-aloe derived porous layer carbon composite electrode material, which comprises the following steps: taking aloe gel as a carbon source and cobalt nitrate as a cobalt source, and carrying out hydrothermal reaction to grow cobalt oxide on the surface of the aloe gel in situ to obtain a compound; carbonizing the composite to obtain the cobalt oxide-aloe derived porous layer carbon composite electrode material. The carbonization step can activate the aloe carbon material, enrich the porous structure of the aloe carbon material and improve the conductivity and capacitance of the aloe carbon material.
Wherein the compound is obtained by the following steps: s1, obtaining aloe gel, adding cobalt nitrate, and uniformly mixing to obtain a mixture; and S2, adding water into the mixture, placing the mixture into a high-pressure reactor for heating to perform hydrothermal reaction, and after the reaction is finished, cooling, cleaning and drying to obtain the compound.
Further, in step S1: the aloe gel is obtained by removing skin from folium Aloe; the cobalt nitrate is added according to the mass ratio of 1: 1-2: 1 to the dried aloe gel product; wherein the dried product of aloe vera gel is obtained by the following steps: cutting the aloe gel into small pieces, and baking for 6-8 hours at 100-140 ℃ to obtain the aloe gel.
Further: in step S2, the temperature of the hydrothermal reaction is 160-200 ℃ and the time is 10-14 h. Sufficient reaction time is beneficial to uniformly grow cobalt oxide particles on the surface of the aloe gel.
Wherein the step of carbonizing the composite comprises: s3, cleaning the composite, drying and carbonizing in an oxygen-free mode to obtain the cobalt oxide-aloe derived porous layer carbon composite electrode material; wherein the cleaning process is water cleaning, or ethanol and water cleaning.
Further, in step S3, the temperature of the oxygen-free carbonization of the composite is 600-800 ℃ and the time is 40-60 min. The aloe carbon material further forms a porous structure after anaerobic carbonization: the micropores can improve the specific surface area of the material and enhance the electric double layer capacitance; the mesoporous channel provides a passage for ion transmission; the formation of large pores is beneficial to buffering and storing ions and effectively shortens the diffusion distance of the ions. The cobalt nitrate is thoroughly decomposed into cobalt oxide crystals at the carbonization temperature, and the cobalt oxide crystals are firmly attached to the surface and the interior of the biochar.
The synthesis method is simple, takes biomass as an electrode substrate, and has the advantages of rich raw materials, environmental friendliness and low price. Cobalt is doped into the biomass material by using an in-situ growth mode, and the obtained product has uniform appearance and large specific surface area.
The invention also provides a cobalt oxide-aloe derived porous layer carbon composite electrode material which is synthesized according to the synthesis method of the cobalt oxide-aloe derived porous layer carbon composite electrode material, comprises carbonized aloe gel and cobalt oxide attached to the carbonized aloe gel and is applied to preparing electrodes of supercapacitors.
The composite electrode material disclosed by the invention combines the advantages of a biomass material with a larger specific surface area and a layered porous structure, introduces heteroatoms to form pseudo-capacitance, can effectively improve the surface structure of carbon atoms, and obviously improves the specific capacitance. When the composite electrode material is manufactured into the electrode of the super capacitor, the electrode has larger capacitance, longer service life and good conductivity and rate capability.
The embodiment of the present invention will be specifically described below by way of examples and comparative examples.
Example 1
This example synthesizes a cobalt oxide-aloe derived porous carbon composite electrode material as follows.
(1) Taking a plurality of aloe gel leaves, removing the skin of the aloe gel leaves, cutting the aloe gel with the skin removed into small sections, weighing a certain amount of aloe gel, recording the mass of the aloe gel, and then putting the aloe gel into a drying box for drying at the temperature of 120 ℃ for 6-8 hours. And taking out the dried aloe gel, weighing, and calculating the mass ratio of the dried aloe gel to the aloe gel before drying.
(2) Weighing a certain amount of aloe gel in a beaker, calculating the dried mass according to the ratio of the step (1), wherein the mass ratio of the dried aloe gel to the cobalt nitrate is 1: 1.5, adding a corresponding amount of cobalt nitrate into the beaker, and stirring uniformly by using a glass rod.
(3) Pouring the uniformly stirred materials into a high-pressure reaction kettle, adding a proper amount of deionized water, submerging the materials to two thirds of the inner wall of the high-pressure reaction kettle, and screwing down the high-pressure reaction kettle; putting the mixture into an oven for hydrothermal reaction, wherein the hydrothermal temperature is 180 ℃, and the hydrothermal time is 12 hours; and after the hydrothermal reaction is finished, naturally cooling.
(4) And after cooling, filtering out a solid product, washing with alcohol once, washing with ultrapure water for 3 times, drying at 80 ℃, then putting into a crucible, putting the crucible into a tubular furnace for anaerobic carbonization at 700 ℃ for 50min, and grinding a sample after carbonization to obtain the cobalt oxide-aloe derived porous layer carbon composite electrode material, wherein the obtained product is recorded as ALC-700.
Comparative example 1
This comparative example provides a Co3O4The sample is obtained by the following steps:
independently pouring cobaltosic oxide into a high-pressure reaction kettle, adding a proper amount of deionized water, submerging two thirds of the inner wall of the high-pressure reaction kettle, and screwing down the high-pressure reaction kettle; heating in an oven at 180 deg.C for 12 hr; after heating, naturally cooling; filtering to obtain solid sample, washing with alcohol once, washing with ultrapure water for 3 times, drying at 80 deg.C, placing into crucible, and placing into crucibleAnaerobic heating in a tube furnace at 600 deg.C for 50min, grinding the heated sample to obtain Co product3O4。
The samples obtained in example 1 and comparative example 1 were characterized and analyzed as follows.
Experimental example 1 SEM analysis
FIG. 1 is an SEM image of sample ALC-700 from example 1, from which it can be seen that the sample activated by carbonization has a certain pore size structure. The different pore size structures of the layered porous carbon structure have different influences on the electrochemical performance of the supercapacitor: the micropores can improve the specific surface area of the material and enhance the electric double layer capacitance; the mesoporous channel provides a passage for ion transmission; the formation of large pores is beneficial to buffering and storing ions and effectively shortens the diffusion distance of the ions.
To further confirm the successful incorporation of Co element in sample ALC-700, EDS imaging was performed on sample ALC-700, and the results are shown in FIG. 2. The distribution of Co, O, C, N elements is evident from the figure.
Experimental example 2 XRD and Raman test analysis
FIG. 3(a) shows ALC-700 sample and Co3O4XRD pattern of (a). The diffraction peaks of the ALC-700 are (111), (220), (311), (400), (422), (511) and (440) all correspond to cubic crystal Co3O4The plane of (JCPDS 43-1003) corresponds to the index of a Selected Area Electron Diffraction (SAED) ring. The strength of the low-angle area is greatly enhanced, indicating that the material is rich in channels, and an unobvious peak appears at 20 degrees, indicating that the ALC-700 sample is mainly based on amorphous structure carbon.
FIG. 3(b) shows ALC-700 sample and Co3O4From which a Raman spectrum at 1359cm was observed-1And 1560cm-1The ALC-700 sample is different from Co3O4Which correspond to the D and G bands, respectively. The D band is related to the degree of carbon structural disorder, and the G band is related to the degree of graphitization regularity. Intensity ratio of D and G bands in the spectrum [ I (D)/I (G)]Reflecting the higher degree of amorphism of the carbon structure of the ALC-700 sample.
Test example 3 electrochemical Performance test
Under the present test item, ALC-700 Material and Co3O4The electrochemical performance test of (2) is carried out in 6mol/L KOH electrolyte, and the related electrochemical test characterization methods are as follows: cyclic voltammetry, constant current charge and discharge, and electrochemical impedance spectroscopy. Wherein:
FIG. 4(a) shows ALC-700 sample and Co3O4At 10mV · s-1CV curve at scan rate; FIG. 4(b) is a CV curve of the ALC-700 sample at different scan rates; FIG. 4(c) shows ALC-700 sample and Co3O4At 1 A.g-1Constant current discharge curve at current density; FIG. 4(d) is a charge-discharge curve of the ALC-700 sample at different current densities; FIG. 4(e) shows ALC-700 sample and Co3O4At 10-2–105Electrochemical impedance spectroscopy in the frequency range of Hz; FIG. 4(f) is the cycling stability of a symmetric supercapacitor device assembled with ALC-700. The system for testing adopts a three-electrode testing system, the electrolyte is 6mol/L KOH, and the working voltage window is 0-0.6V (reference Hg/HgO).
In FIG. 4(a), ALC-700 sample and Co3O4All exhibit a pair of redox peaks, indicating that the measured capacitance is mainly due to the surface faradaic reaction of Co ions:
the CV integrated area of the ALC-700 sample was significantly larger than that of Co3O4Showing ALC-700 sample to Co3O4Has better pseudocapacitance performance.
Fig. 4(b) is a graph showing similar profiles of CV curves of ALC-700 at different scan rates, showing high rate capability and reversible faradaic reaction between the active species and the electrolyte. The result shows that the ALC-700 electrode material has good rate performance.
FIG. 4(c) shows that ALC-700 maintains a larger specific capacitance at the same current density, and also shows that the pseudocapacitance of ALC-700 is better than that of Co3O4The pseudocapacitance of (2). In particular, with Co3O4Compared with the ALC-700, the specific capacitance is improved, and the introduction of Co atoms can further improve the specific capacitance.
FIG. 4(d) shows the charge-discharge curve (GCD) of ALC-700 at different current densities with no significant difference in charge and discharge times, indicating excellent coulombic efficiency. Specific capacitances were calculated for ALC-700 based supercapacitor devices at current densities of 1, 2, 4, 8, 12 and 20A · g-1The specific capacitance of the sample is: 1345.2, 1206.4, 1035.2, 867.2, 758.4, and 656F g-1. Even at high current density (20A g)-1) Next, ALC-700 still provided 656 Fg-1Indicating that it has excellent rate performance. In addition, the current density of 5A g was measured in this test example-1In the meantime, the cycle stability of the symmetrical supercapacitor device based on the ALC-700 (as shown in FIG. 5) is shown in FIG. 4(f), and the result of the test shows that the symmetrical supercapacitor device based on the ALC-700 has good cycle stability, the initial capacitance retention rate is 92.7% and the coulomb efficiency is 95.8% after 10,000 times of charge and discharge.
FIG. 4(e) shows Co3O4And electrochemical impedance spectroscopy of ALC-700. The intercept of the nyquist plot with the real axis illustrates the equivalent series resistance (Rs) of the electrodes, which is low for all electrode materials. The approximate vertical lines in the low frequency region indicate that the prepared material has ideal capacitive behavior. And Co3O4Compared with ALC-700, the ALC-700 tends to be more vertical in a low frequency range, which shows that the introduction of Co impurity atoms improves the capacitance performance of the ALC-700 to a certain extent.
In organic electrolytes, carbon-based symmetric electrochemical double layer capacitor devices produce higher energy densities due to a larger operating voltage window than aqueous electrolytes. ALC-700 at 1A. g-1Specific capacity at current density of 1345.2F g-1The specific capacity after 10000 cycles is the initial specific capacity92.7% of (C), the coulombic efficiency was 95.8%, these values being Co3O430 times of the total weight of the powder. The prepared electrode can keep the original shape after charge and discharge treatment, and can not be seriously broken, thereby having good cyclability. In addition, the device has good cycling stability, and can still keep 87.92% of the original capacitance after 10000 cycles. The cobalt oxide-aloe-derived porous carbon composite electrode material prepared by the invention has wide prospect in the practical application of the super capacitor.
The above-described embodiments are merely some embodiments of the present invention and are not intended to be exhaustive or to limit the scope of the invention to the precise embodiments disclosed, and merely representative of selected embodiments of the invention. 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.
Claims (8)
1. A method for synthesizing a cobalt oxide-aloe derived porous carbon composite electrode material is characterized by comprising the following steps:
taking aloe gel as a carbon source and cobalt nitrate as a cobalt source, and carrying out hydrothermal reaction to grow cobalt oxide on the surface of the aloe gel in situ to obtain a compound; carbonizing the composite to obtain the cobalt oxide-aloe derived porous layer carbon composite electrode material.
2. The method of synthesizing a cobalt oxide-aloe derived porous layer carbon composite electrode material according to claim 1, wherein the composite is obtained by:
s1, obtaining aloe gel, adding cobalt nitrate, and uniformly mixing to obtain a mixture;
and S2, adding water into the mixture, placing the mixture into a high-pressure reactor for heating to perform hydrothermal reaction, and after the reaction is finished, cooling, cleaning and drying to obtain the compound.
3. The method of synthesizing a cobalt oxide-aloe derived porous layer carbon composite electrode material according to claim 1, wherein the carbonizing step of the accord comprises:
s3, cleaning the composite, drying and carbonizing in an oxygen-free mode to obtain the cobalt oxide-aloe derived porous layer carbon composite electrode material; wherein the cleaning process is water cleaning, or ethanol and water cleaning.
4. The method for synthesizing a cobalt oxide-aloe derived porous layer carbon composite electrode material according to claim 2, wherein in step S1: the aloe gel is obtained by removing skin from folium Aloe; the cobalt nitrate is added according to the mass ratio of 1: 1-2: 1 to the dried aloe gel product;
wherein the dried product of aloe vera gel is obtained by the following steps: cutting the aloe gel into small pieces, and baking for 6-8 hours at 100-140 ℃ to obtain the aloe gel.
5. The method of synthesizing a cobalt oxide-aloe derived porous layer carbon composite electrode material as claimed in claim 2, wherein: in step S2, the temperature of the hydrothermal reaction is 160-200 ℃ and the time is 10-14 h.
6. The method of synthesizing a cobalt oxide-aloe derived porous layer carbon composite electrode material according to claim 3, wherein: in step S3, the temperature of the oxygen-free carbonization of the compound is 600-800 ℃, and the time is 40-60 min.
7. A cobalt oxide-aloe derived porous layer carbon composite electrode material synthesized according to the synthesis method of any one of claims 1 to 6, comprising carbonized aloe gel and cobalt oxide attached to the carbonized aloe gel.
8. Use of the cobalt oxide-aloe derived porous layer carbon composite electrode material according to claim 7 in the preparation of an electrode for a supercapacitor.
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