CN115274309B - Nickel-cobalt double hydroxide/oxidized active carbon composite material and preparation method thereof - Google Patents
Nickel-cobalt double hydroxide/oxidized active carbon composite material and preparation method thereof Download PDFInfo
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- CN115274309B CN115274309B CN202210857643.2A CN202210857643A CN115274309B CN 115274309 B CN115274309 B CN 115274309B CN 202210857643 A CN202210857643 A CN 202210857643A CN 115274309 B CN115274309 B CN 115274309B
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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
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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
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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
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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
- H01G11/84—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
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- 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 nickel-cobalt double hydroxide/oxidized active carbon composite material and a preparation method thereof, and also provides an application of the composite material as an electrode material of a supercapacitor. The composite material disclosed by the invention has the advantages that the oxidized active carbon subjected to oxidation modification is used as a carrier for in-situ growth of NiCo-DH, and the NiCo-DH nanoneedle is uniformly loaded on the oxidized active carbon, so that the composite material has a good interconnection and a highly ordered structure and has more active sites, thereby effectively improving the utilization rate of active substances. Due to the synergistic effect of the high specific capacity of the NiCo-DH and the stable structure of the oxidized active carbon, the NiCo-DH/oxidized active carbon composite material shows extremely excellent electrochemical performance.
Description
Technical Field
The invention belongs to the field of materials, and relates to an electrode material for a super capacitor, in particular to a NiCo-DH/oxidized active carbon composite material, and a preparation method and application thereof.
Background
Supercapacitors are ideal for next generation applications because of their fast charge and discharge rates, high power density, and ultra-high cycling stability. However, the super capacitor is limited in practical application due to lower specific capacitance and energy density, wherein the electrode material is a key factor for determining the performance of the super capacitor, so that the search for a novel electrode material with excellent electrochemical performance and easy large-scale synthesis is an important point of research.
Compared with the carbon materials which are most widely used in the supercapacitor electrode materials nowadays, the nickel-cobalt double hydroxide is paid attention to due to excellent electrochemical activity, environmental friendliness, high theoretical capacitance and good synergistic effect of two substances of nickel and cobalt. But its rate capability and cyclic stability are limited due to its chemical instability and poor conductivity. Therefore, how to improve the structural stability and conductivity of the nickel cobalt double hydroxide, and further obtain a high-performance electrode material is an important research point in the field.
Disclosure of Invention
In order to solve the problems of poor cycling stability of a metal oxide material in a supercapacitor electrode material and low specific capacitance and energy density of a carbon material in the related art, the embodiment of the invention provides a NiCo-DH/oxidized active carbon composite material, a preparation method thereof and application thereof in a supercapacitor.
The preparation method of the NiCo-DH/oxidized active carbon composite material comprises the following steps of:
s1: adding anthracite coal powder into hydrofluoric acid solution, carrying out water bath ash removal to obtain first suspension, carrying out suction filtration and water washing on the first suspension, and drying a filter cake to obtain ashless coal;
s2: uniformly mixing the ashless coal and an alkali activator, grinding into powder, placing in a calciner, heating to 700-900 ℃ from room temperature under nitrogen atmosphere, and then preserving heat for 1-3h to obtain a calcination product;
s3: placing the calcined product in a strong acid solution to obtain a second suspension, and carrying out suction filtration, water washing and filter cake drying on the second suspension to obtain activated carbon;
s4: placing the activated carbon in a strong oxidizing solution, performing hydrothermal oxidation at 100-140 ℃ for 2-6h, cooling to obtain a third suspension, and performing suction filtration, water washing and filter cake drying on the third suspension to obtain oxidized activated carbon;
s5: placing the oxidized active carbon, urea, nickel nitrate hexahydrate and cobalt nitrate hexahydrate into an alcohol aqueous solution for ultrasonic treatment, performing hydrothermal reaction at 160-200 ℃ for 10-14h, and cooling to obtain a fourth suspension;
s6: and centrifuging the fourth suspension with alcohol for multiple times, centrifuging with water for multiple times, and drying the centrifuged substrate to obtain the NiCo-DH/oxidized active carbon composite material.
The method of the embodiment of the invention realizes the interface modification of the carbon carrier in the composite material, introduces oxygen-containing groups on the surface of the active carbon, enhances the interaction between NiCo-DH and oxidized active carbon, and has excellent electrochemical performance and good cycle stability when being used as the electrode material of the super capacitor.
In some embodiments, in the step S1, the mass concentration of the hydrofluoric acid solution is 40-60%, the dosage ratio of the anthracite coal dust to the hydrofluoric acid solution is 1g:8-13mL, the temperature of the water bath ash removal is 50-70 ℃ and the time is 5-7h.
In some embodiments, in step S2, the mass ratio of the ashless coal to the alkali activator is 1 (3-5), and the alkali activator is potassium hydroxide or sodium hydroxide.
In some embodiments, the alkali activator is preferably potassium hydroxide.
In some embodiments, the temperature of step S2 is increased using a temperature programmed with a rate of 3-7deg.C/min.
In some embodiments, in step S3, the strong acid solution is one of a hydrochloric acid solution, a nitric acid solution, and a sulfuric acid solution.
In some embodiments, the strong acid solution has a concentration of 2 to 4mol/L.
In some embodiments, the strong acid solution is preferably a hydrochloric acid solution of 2-4mol/L concentration.
In some embodiments, in step S4, the strong oxidizing solution is one of a nitric acid solution, a sulfuric acid solution, and a hydrogen peroxide solution.
In some embodiments, the highly oxidizing solution is preferably a 1-5mol/L nitric acid solution.
In some embodiments, in the step S5, the mass ratio of the oxidized active carbon, urea, nickel nitrate hexahydrate and cobalt nitrate hexahydrate is 0.03:0.6 (0.29-0.87): 0.29-0.87.
In some embodiments, the alcohol in the aqueous alcohol solution is one of ethanol, methanol, isopropanol.
In some embodiments, preferably, the volume ratio of alcohol to water in the alcohol-water solution is 1:1, and the alcohol is ethanol.
In some embodiments, in steps S1, S3, S4, the method of drying the filter cake is: vacuum drying at 70-90deg.C for 20-28h.
In some embodiments, the method of washing with water is: washing with deionized water until the filtrate had a pH of 7.
In some embodiments, the alcohol in step S6 is the same alcohol selected in the aqueous alcohol solution in step S5.
The embodiment of the invention also provides the NiCo-DH/oxidized active carbon composite material prepared by the method.
The NiCo-DH/oxidized active carbon composite material provided by the embodiment of the invention has the advantages that the oxidized active carbon subjected to oxidation modification is used as a carrier for in-situ growth of the NiCo-DH, and the NiCo-DH nanoneedle is uniformly loaded on the oxidized active carbon, so that the composite material has a good interconnection and a highly ordered structure and has more active sites, and the utilization rate of active substances is effectively improved. Due to the synergistic effect of the high specific capacity of the NiCo-DH and the stable structure of the oxidized active carbon, the NiCo-DH/oxidized active carbon composite material shows extremely excellent electrochemical performance.
The embodiment of the invention also provides application of the NiCo-DH/oxidized active carbon composite material as an electrode material of the supercapacitor.
The NiCo-DH/oxidized active carbon composite material provided by the embodiment of the invention is used as an electrode material of a supercapacitor, so that the supercapacitor has excellent durability and cycle stability.
The embodiment of the invention has the following advantages and beneficial effects:
(1) According to the embodiment of the invention, anthracite is used as a carbon source, active carbon is prepared by a one-step activation method, then the active carbon is subjected to hydrothermal oxidation treatment to obtain oxidized active carbon, and a NiCo-DH/oxidized active carbon composite material with a three-dimensional heterostructure is prepared by loading NiCo-DH by a hydrothermal method. The oxidized active carbon subjected to oxidation modification is used as a carrier for in-situ growth of NiCo-DH, and the NiCo-DH nanoneedle is uniformly loaded on the oxidized active carbon, so that the oxidized active carbon has a good interconnection and a highly ordered structure and has more active sites, and the utilization rate of active substances is effectively improved. Due to the synergistic effect of the high specific capacity of the NiCo-DH and the stable structure of the oxidized active carbon, the NiCo-DH/oxidized active carbon composite material shows extremely excellent electrochemical performance.
(2) According to the embodiment of the invention, the nickel cobalt double hydroxide and the carbon material are assembled into the three-dimensional structure composite material, so that the aggregation of the low-dimensional nano material can be prevented. The anthracite is used for preparing the active carbon by a chemical activation method, and the anthracite has the advantages of adjustable pore diameter, good porosity and high carbon content under the condition of not affecting the high specific surface area, and is an ideal carbon carrier of the composite material. By treating the activated carbon, more oxygen-containing functional groups are introduced to the surface of the activated carbon, the functional groups can adjust the skeleton structure of the activated carbon, the surface wettability of the activated carbon is increased, the size, the morphology and the dispersibility of the in-situ grown nickel-cobalt double hydroxide are determined, the interaction between NiCo-DH and oxidized activated carbon is enhanced, and the chemical stability and the charge transfer rate of the composite material are increased.
(3) The NiCo-DH/oxidized active carbon composite material provided by the embodiment of the invention is used as an electrode material of a supercapacitor, so that the supercapacitor has excellent durability and high energy density.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings, in which:
FIG. 1 is an XRD pattern of the NiCo-DH/oxidized activated carbon composite material prepared in example 1;
FIG. 2 is an SEM image of a NiCo-DH/oxidized activated carbon composite material prepared in example 1;
FIG. 3 is an XPS diagram of a NiCo-DH/oxidized activated carbon composite material prepared in example 1;
FIG. 4 is a Cyclic Voltammetry (CV) graph of different scan rates for the working electrode three electrode system prepared in example 4 over a voltage window of 0-0.5V;
FIG. 5 is a constant current charge-discharge (GCD) plot of the working electrode three electrode system prepared in example 4 at different current densities;
FIG. 6 is a graph of the rate performance of the button-type asymmetric supercapacitor prepared in example 7;
FIG. 7 is a Lagong diagram of example 7 for preparing a button-type asymmetric supercapacitor;
FIG. 8 is a graph of capacitance retention and coulombic efficiency after ten thousand cycles for the button asymmetric supercapacitor prepared in example 7;
FIG. 9 is an SEM image of a NiCo-DH/activated carbon composite material prepared in comparative example 1;
FIG. 10 is an XPS diagram of the NiCo-DH/activated carbon composite material prepared in comparative example 1;
FIG. 11 is a graph showing the rate performance of the button-type asymmetric supercapacitor prepared in comparative example 1;
fig. 12 is a Lagong diagram of comparative example 1 for preparing a button-type asymmetric supercapacitor.
Detailed Description
The following detailed description of embodiments of the invention is exemplary and intended to be illustrative of the invention and not to be construed as limiting the invention.
The preparation method of the NiCo-DH/oxidized active carbon composite material comprises the following steps of:
s1: adding anthracite coal powder into hydrofluoric acid solution, carrying out water bath ash removal to obtain a first suspension, carrying out suction filtration and water washing on the first suspension, and drying a filter cake to obtain ashless coal;
s2: uniformly mixing ashless coal and an alkali activator, grinding into powder, placing in a calciner, heating to 700-900 ℃ from room temperature under nitrogen atmosphere, and then preserving heat for 1-3h to obtain a calcination product;
s3: placing the calcined product in a strong acid solution to obtain a second suspension, and carrying out suction filtration, water washing and filter cake drying on the second suspension to obtain activated carbon;
s4: placing activated carbon in a strong oxidizing solution, performing hydrothermal oxidation at 100-140 ℃ for 2-4h, cooling to obtain a third suspension, and performing suction filtration, water washing and filter cake drying on the third suspension to obtain oxidized activated carbon;
s5: placing oxidized active carbon, urea, nickel nitrate hexahydrate and cobalt nitrate hexahydrate into an alcohol aqueous solution for ultrasonic treatment, performing hydrothermal reaction at 160-200 ℃ for 10-14h, and cooling to obtain a fourth suspension;
s6: and centrifuging the fourth suspension with alcohol for multiple times, centrifuging with water for multiple times, and drying the centrifuged substrate to obtain the NiCo-DH/oxidized active carbon composite material.
The method of the embodiment of the invention realizes the interface modification of the carbon carrier in the composite material, introduces oxygen-containing groups on the surface of the active carbon, enhances the interaction between NiCo-DH and oxidized active carbon, and has excellent electrochemical performance and good cycle stability when being used as the electrode material of the super capacitor.
In some embodiments, in step S1, the mass concentration of the hydrofluoric acid solution is 40-60%. Non-limiting examples are: the mass concentration may be 40%, 50%, 60%, etc.
In some embodiments, the ratio of anthracite coal fines to hydrofluoric acid solution is 1g:8-13mL, as non-limiting examples: the dosage ratio may be 1g:8mL, 1g:9mL, 1g:9.5mL, 1g:10mL, 1g:12.5mL, etc.
In some embodiments, the temperature of the ash removal in the water bath is 50-70 ℃ for 5-7 hours. Non-limiting examples are: the temperature may be: drying at 50deg.C, 52deg.C, 55deg.C, 60deg.C, 63deg.C, 65deg.C, 70deg.C, etc., for a drying time of either; 5h, 5.5h, 6h, 6.5h, 7h, etc.
In some embodiments, in step S2, the mass ratio of ashless coal to alkali activator is 1 (3-5), such as, by way of non-limiting example: the mass ratio may be: 1:3, 1:3.5, 1:4, 1:5, etc.
In some embodiments, the alkali activator is potassium hydroxide or sodium hydroxide. Preferably, the alkali activator is preferably potassium hydroxide.
In some embodiments, the calcination temperature of step S2 is not limited as exemplified by: examples of the heat-retaining time include, but are not limited to, 700 ℃, 750 ℃, 780 ℃, 800 ℃, 850 ℃, 880 ℃, 900 ℃, and the like: 1h, 1.2h, 1.5h, 2h, 2.5h, 3h, etc.
In some embodiments, the temperature of step S2 is increased using a temperature programmed with a rate of 3-7deg.C/min. Non-limiting examples are: the heating rate can be 3 ℃/min, 4 ℃/min, 5.5 ℃/min, 6 ℃/min, 7 ℃/min, etc.
In some embodiments, the calciner in step S2 may be a horizontal tube furnace.
In some embodiments, in step S3, the strong acid solution is one of a hydrochloric acid solution, a nitric acid solution, and a sulfuric acid solution.
In some embodiments, the concentration of the strong acid solution is 2-4mol/L. Non-limiting examples are: the concentration may be 2mol/L, 2.5mol/L, 3mol/L, 4mol/L, etc.
In some embodiments, the strong acid solution is preferably a 2-4mol/L hydrochloric acid solution.
In some embodiments, in step S4, the strong oxidizing solution is one of a nitric acid solution, a sulfuric acid solution, and a hydrogen peroxide solution.
In some embodiments, the strong oxidizing solution is preferably a 1-5mol/L nitric acid solution, such as, by way of non-limiting example: 1mol/L nitric acid solution, 2mol/L nitric acid solution, 3mol/L nitric acid solution, 4mol/L nitric acid solution or 5mol/L nitric acid solution.
In some embodiments, the hydrothermal oxidation temperature of step S4 is not limited as follows: examples of the time include, but are not limited to, 100 ℃, 110 ℃, 125 ℃, 130 ℃, 135 ℃,140 ℃, and the like: 2h, 2.5h, 3h, 3.2h, 3.5h, 4h, 5h, 6h, etc.
In some embodiments, in step S5, the mass ratio of the oxidized activated carbon, urea, nickel nitrate hexahydrate, cobalt nitrate hexahydrate is 0.03:0.6 (0.29-0.87): 0.29-0.87. Non-limiting examples are: the mass ratio may be: 0.03:0.6:0.29:0.58, 0.03:0.6:0.58:0.29, 0.03:0.6:0.58:0.58, 0.03:0.6:0.58:0.87, 0.03:0.6:0.44:0.58, 0.03:0.6:0.87:0.58.
In some embodiments, the alcohol in the aqueous alcohol solution is one of ethanol, methanol, isopropanol.
In some embodiments, preferably, the volume ratio of alcohol to water in the aqueous alcohol solution is 1:1, and the alcohol is ethanol.
In some embodiments, the hydrothermal oxidation temperature of step S5 is not limited as follows: 160 ℃, 170 ℃, 175 ℃,180 ℃, 190 ℃,200 ℃, etc., examples of the time are not limited: 10h, 11.5h, 12h, 13.5h, 14h, etc.
In some embodiments, in steps S1, S3, S4, the method of drying the filter cake is: vacuum drying at 70-90deg.C for 20-28h. Non-limiting examples are: the drying temperature may be: drying at 70deg.C, 72deg.C, 75deg.C, 80deg.C, 83 deg.C, 85deg.C, 90deg.C, etc., for a drying time of optionally; 20h, 22h, 24h, 25h, 26.5h, 28h, etc.
In some embodiments, the method of washing with water is: washing with deionized water until the filtrate had a pH of 7.
In some embodiments, the alcohol in step S6 is the same alcohol selected in the aqueous alcohol solution in step S5.
In some embodiments, in step S6, the centrifugation is performed 2-5 times with alcohol, which may be 2 times, 3 times, 5 times, for example.
In some embodiments, in step S6, the centrifugation is performed 2-5 times with water, which may be 2 times, 3 times, 5 times, for example.
The embodiment of the invention also provides the NiCo-DH/oxidized active carbon composite material prepared by the method.
The NiCo-DH/oxidized active carbon composite material provided by the embodiment of the invention has the advantages that the oxidized active carbon subjected to oxidation modification is used as a carrier for in-situ growth of the NiCo-DH, and the NiCo-DH nanoneedle is uniformly loaded on the oxidized active carbon, so that the composite material has a good interconnection and a highly ordered structure and has more active sites, and the utilization rate of active substances is effectively improved. Due to the synergistic effect of the high specific capacity of the NiCo-DH and the stable structure of the oxidized active carbon, the NiCo-DH/oxidized active carbon composite material shows extremely excellent electrochemical performance.
The embodiment of the invention also provides application of the NiCo-DH/oxidized active carbon composite material as an electrode material of the supercapacitor.
The NiCo-DH/oxidized active carbon composite material provided by the embodiment of the invention is used as an electrode material of a supercapacitor, so that the supercapacitor has excellent durability and cycle stability.
The following are non-limiting examples of the invention.
Example 1
The embodiment provides a preparation method of a NiCo-DH/oxidized active carbon composite material for a super capacitor, which comprises the following steps:
placing 8g of anthracite coal dust in a plastic beaker filled with 80mL of hydrofluoric acid solution with mass concentration of 40%, heating in a water bath at 60 ℃ for 5 hours to obtain a first suspension, carrying out suction filtration on the obtained first suspension, flushing with deionized water until the pH value of the filtrate is 7, and placing the obtained filter cake in a vacuum drying box for drying at 80 ℃ for 24 hours to obtain anthracite coal;
taking 1g of ashless coal dust, placing 4g of potassium hydroxide into a horizontal tube furnace for activation, heating to 800 ℃ in a temperature programming mode under a nitrogen atmosphere at a heating rate of 5 ℃/min, preserving heat for 2 hours at 800 ℃, taking out after cooling to room temperature, and placing in a hydrochloric acid solution with a concentration of 2mol/L of 50mL to obtain a second suspension;
carrying out suction filtration on the obtained second suspension, washing with deionized water until the pH value of the filtrate is 7, and drying the obtained filter cake in a vacuum drying oven at 80 ℃ for 24 hours to obtain activated carbon;
weighing 0.1g of activated carbon, putting the activated carbon into 50mL of nitric acid solution with the concentration of 3mol/L, performing ultrasonic treatment for 30min, transferring the activated carbon into a 150mL polytetrafluoroethylene-lined hydrothermal kettle, preserving heat for 4h at 120 ℃, and cooling to obtain a third suspension;
carrying out suction filtration on the obtained third suspension, washing with deionized water until the pH value of the filtrate is 7, and drying the obtained filter cake in a vacuum drying oven at 80 ℃ for 24 hours to obtain oxidized active carbon;
weighing 0.03g of oxidized active carbon, 0.6g of urea, 0.58g of nickel nitrate hexahydrate and 0.29g of cobalt nitrate hexahydrate, putting into a mixed solution of 20mL of deionized water and 20mL of ethanol, stirring for 30min, performing ultrasonic treatment for 30min, transferring into a hydrothermal kettle with a polytetrafluoroethylene lining of 100mL, preserving heat at 180 ℃ for 12h, and cooling to obtain a fourth suspension;
and centrifuging the obtained fourth suspension with ethanol for three times, centrifuging with deionized water for three times, and drying the centrifugated substrate in a vacuum drying oven at 80 ℃ for 24 hours to obtain the NiCo-DH/oxidized active carbon composite material.
The XRD patterns of the NiCo-DH/oxidized activated carbon composite material prepared in this example are shown in FIG. 1, and two main characteristic peaks appear at 11.9℃and 60.3℃respectively corresponding to. Alpha. -Ni (OH) 2 (JCPDS No. 38-0715) and (110) crystal planes, and two characteristic peaks at 19.9 DEG and 33.3 DEG, corresponding to Co (OH) 2 (JCPDS No. 51-1731) and (012) crystal planes.
The SEM image of the NiCo-DH/oxidized active carbon composite material prepared in this example is shown in fig. 2, and it can be seen from the image that NiCo-DH is tightly adhered to the surface of oxidized active carbon in the form of a nanoneedle, and when the composite material is used as an electrode material of a supercapacitor, the NiCo-DH nanoneedle provides a conductive network for electron transport, and can undergo a rapid reversible redox reaction with an electrolyte, thereby having a high specific capacitance.
The XPS spectrum of the NiCo-DH/oxidized active carbon composite material prepared in the embodiment is shown in figure 3, and four elements of C, O, ni and Co are arranged on the XPS spectrum, so that the NiCo-DH is proved to be successfully loaded on the oxidized active carbon.
Example 2
The embodiment provides a preparation method of a NiCo-DH/oxidized active carbon composite material for a super capacitor, which comprises the following steps:
placing 8g of anthracite coal dust in a plastic beaker filled with 70mL of hydrofluoric acid solution with mass concentration of 40%, heating in a water bath at 50 ℃ for 6 hours to obtain a first suspension, carrying out suction filtration on the obtained first suspension, flushing with deionized water until the pH value of the filtrate is 7, and placing the obtained filter cake in a vacuum drying box for drying at 70 ℃ for 20 hours to obtain anthracite coal;
taking 1g of ashless coal, placing 3g of potassium hydroxide in a grinding mode, grinding into powder, placing in a horizontal tube furnace for activation, heating to 700 ℃ in a temperature programming mode under a nitrogen atmosphere, keeping the temperature at the heating rate of 4 ℃/min for 3 hours at the temperature of 700 ℃, taking out after cooling to room temperature, and placing in a hydrochloric acid solution with the concentration of 1mol/L of 50mL to obtain a second suspension;
carrying out suction filtration on the obtained second suspension, washing with deionized water until the pH value of the filtrate is 7, and drying the obtained filter cake in a vacuum drying oven at 70 ℃ for 20 hours to obtain activated carbon;
weighing 0.1g of active carbon, putting the active carbon into 50mL of nitric acid solution with the concentration of 1mol/L, carrying out ultrasonic treatment for 30min, transferring the active carbon into a 150mL polytetrafluoroethylene-lined hydrothermal kettle, preserving heat for 2h at the temperature of 100 ℃, and cooling to obtain a third suspension;
carrying out suction filtration on the obtained third suspension, washing with deionized water until the pH value of the filtrate is 7, and drying the obtained filter cake in a vacuum drying oven at 70 ℃ for 20 hours to obtain oxidized active carbon;
weighing 0.03g of oxidized active carbon, 0.6g of urea, 0.29g of nickel nitrate hexahydrate and 0.58g of cobalt nitrate hexahydrate, putting into a mixed solution of 20mL of deionized water and 20mL of methanol, stirring for 30min, performing ultrasonic treatment for 30min, transferring into a hydrothermal kettle with a polytetrafluoroethylene lining of 100mL, preserving heat at 160 ℃ for 10h, and cooling to obtain a fourth suspension;
and centrifuging the obtained fourth suspension with methanol for three times, centrifuging with deionized water for three times, and drying the centrifugated substrate in a vacuum drying oven at 70 ℃ for 20 hours to obtain the NiCo-DH/oxidized active carbon composite material.
Example 3
The embodiment provides a preparation method of a NiCo-DH/oxidized active carbon composite material for a super capacitor, which comprises the following steps:
placing 8g of anthracite coal dust in a plastic beaker filled with 100mL of hydrofluoric acid solution with mass concentration of 60%, heating in a water bath at 70 ℃ for 7 hours to obtain a first suspension, carrying out suction filtration on the obtained first suspension, flushing with deionized water until the pH value of the filtrate is 7, and placing the obtained filter cake in a vacuum drying oven for drying at 90 ℃ for 28 hours to obtain anthracite coal;
taking 1g of ashless coal, placing 5g of potassium hydroxide in a grinding mill to be ground into powder, placing in a horizontal tube furnace to be activated, heating to 900 ℃ in a temperature programming mode under a nitrogen atmosphere, keeping the temperature at the heating rate of 6 ℃/min for 1h at the temperature of 900 ℃, taking out the powder after cooling to room temperature, and placing in a hydrochloric acid solution with the concentration of 3mol/L of 50mL to obtain a second suspension;
carrying out suction filtration on the obtained second suspension, washing with deionized water until the pH value of the filtrate is 7, and drying the obtained filter cake in a vacuum drying oven at 90 ℃ for 28 hours to obtain activated carbon;
weighing 0.1g of active carbon, putting the active carbon into 50mL of nitric acid solution with the concentration of 5mol/L, carrying out ultrasonic treatment for 30min, transferring the active carbon into a 150mL polytetrafluoroethylene-lined hydrothermal kettle, preserving heat for 6h at 140 ℃, and cooling to obtain a third suspension;
carrying out suction filtration on the obtained third suspension, washing with deionized water until the pH value of the filtrate is 7, and drying the obtained filter cake in a vacuum drying oven at 90 ℃ for 28 hours to obtain oxidized active carbon;
weighing 0.03g of oxidized active carbon, 0.6g of urea, 0.44g of nickel nitrate hexahydrate and 0.44g of cobalt nitrate hexahydrate, putting into a mixed solution of 20mL of deionized water and 20mL of isopropanol, stirring for 30min, performing ultrasonic treatment for 30min, transferring into a hydrothermal kettle with a polytetrafluoroethylene lining of 100mL, preserving heat at 200 ℃ for 14h, and cooling to obtain a fourth suspension;
and centrifuging the obtained fourth suspension with isopropanol for three times, centrifuging with deionized water for three times, and drying the centrifuged substrate in a vacuum drying oven at 90 ℃ for 28 hours to obtain the NiCo-DH/oxidized active carbon composite material.
Example 4
In the embodiment, the NiCo-DH/oxidation active carbon composite material obtained in the embodiment 1, polytetrafluoroethylene micropowder and acetylene black are weighed and mixed according to the mass ratio of 8:1:1, a few drops of ethanol solution are dripped into the mixed material, the mixed material is made into slurry by ultrasonic treatment, the slurry is uniformly coated on foam nickel with the specification of 10mm multiplied by 0.5mm, the pressure of 10MPa is applied to carry out tabletting, the material load on the foam nickel is about 2mg, and the pressed foam nickel is placed in a vacuum drying oven and dried for 12 hours at 80 ℃ to obtain the electrode of the NiCo-DH/oxidation active carbon composite material.
A three-electrode system is formed by taking the NiCo-DH/oxidized active carbon composite electrode prepared in the embodiment 4 as a working electrode, a platinum sheet electrode as a counter electrode, a Hg/HgO electrode as a reference electrode and a 6mol/L potassium hydroxide aqueous solution as electrolyte, and CV tests of different scanning rates of 10-100mV/s are carried out under a voltage window of 0-0.5V through an electrochemical workstation (Shanghai Chenhua, CHI-660E). As shown in fig. 4, the CV curve has a pair of redox peaks, indicating that its capacitance mechanism is mainly pseudocapacitance. When the scan rate was increased from 10mV/s to 100mV/s, the anode peak moved to positive potential and the cathode peak moved to negative potential, this shift was due to polarization of the NiCo-DH/oxidized activated carbon composite material at higher scan rates, indicating good reversibility of the working electrode.
GCD tests of different densities were performed on NiCo-DH/oxidized activated carbon composite working electrodes under a three electrode system using a battery detection system (new wei, CT-4000). As shown in FIG. 5, the discharge curve of the NiCo-DH/oxidized active carbon composite material shows a nonlinear discharge characteristic and has an obvious discharge platform, which indicates that reversible redox reaction occurs at the interface of the electrode and the electrolyte, and the discharge curve is pseudocapacitive. The specific capacitances of the NiCo-DH/oxidized active carbon composite electrode were calculated to be 1990F/g, 1820F/g, 1650F/g, 1580F/g and 1520F/g, respectively, at current densities of 1A/g, 2A/g, 5A/g, 10A/g and 20A/g, respectively, based on the discharge times.
Example 5
In this example, using the NiCo-DH/oxidized activated carbon composite material obtained in example 2, an electrode sheet prepared in the same manner as in example 4 was used as a working electrode, and electrochemical tests were conducted under the same test conditions as in example 4, and the specific capacitance of the working electrode prepared in the same manner as in example 4 at a current density of 1A/g was 1835F/g using the NiCo-DH/oxidized activated carbon composite material obtained in example 2.
Example 6
In this example, using the NiCo-DH/oxidized activated carbon composite material obtained in example 3, an electrode sheet prepared in the same manner as in example 4 was used as a working electrode, and electrochemical tests were conducted under the same test conditions as in example 4, and the specific capacitance of the working electrode prepared in the same manner as in example 4 at a current density of 1A/g was 1689F/g, using the NiCo-DH/oxidized activated carbon composite material obtained in example 3.
Example 7
In the embodiment, the NiCo-DH/oxidized active carbon composite material working electrode prepared in the embodiment 4 is used as a positive electrode, the oxidized active carbon prepared in the embodiment 1 is used as a negative electrode according to the oxidized active carbon working electrode preparation method in the embodiment 4, an aqueous filter membrane is used as a diaphragm, a 6mol/L potassium hydroxide aqueous solution is used as an electrolyte, a positive electrode plate and a negative electrode plate are placed in a button battery shell, the diaphragm is placed between the positive electrode plate and the negative electrode plate, and 5 drops of the 6mol/L potassium hydroxide aqueous solution are dripped on the diaphragm to assemble the button type asymmetric supercapacitor.
The button-type asymmetric supercapacitor prepared in example 7 was subjected to electrochemical performance test by means of an electrochemical workstation (Shanghai Chenhua, CHI-660E) and a battery detection system (Xinwei, CT-4000). FIG. 6 is a graph of the rate performance of a coin-type asymmetric supercapacitor, calculated as the specific capacitance values at different current densities, at a current density of 1A/g, the specific capacitance of the coin-type asymmetric supercapacitor reached 118.75F/g. Even at a large current density (20A/g), the specific capacitance can reach 100F/g, indicating that the button-type asymmetric supercapacitor assembled in example 7 has good rate capability. Fig. 7 is a drawing of a button-type asymmetric supercapacitor, from which it can be seen that the energy density of the button-type asymmetric supercapacitor can reach as high as 42.22Wh/kg when the power density is 800W/kg, and can also reach 33.56Wh/kg at a high power density of 16kW/kg, indicating that the button-type asymmetric supercapacitor assembled in example 7 has a high energy density. Fig. 8 is a ten-thousand charge-discharge cycle chart of the button-type asymmetric supercapacitor, and after ten-thousand cycles, the capacity retention rate and the coulomb efficiency of the button-type asymmetric supercapacitor are 95.3% and 100.0%, respectively, showing that the button-type asymmetric supercapacitor assembled in example 7 has very excellent electrochemical stability and cycle performance.
Example 8
In this example, a button-type asymmetric supercapacitor was assembled in the same manner as in example 7, except that the working electrode of NiCo-DH/oxidized activated carbon composite material prepared in example 5 was used as the positive electrode, the oxidized activated carbon working electrode prepared in example 2 was used as the negative electrode, the aqueous filter membrane was used as the separator, and a 6mol/L aqueous potassium hydroxide solution was used as the electrolyte. The button-type asymmetric supercapacitor prepared in example 8 was subjected to electrochemical performance test by means of an electrochemical workstation (Shanghai Chenhua, CHI-660E) and a battery detection system (Xinwei, CT-4000). The button type asymmetric supercapacitor prepared in example 8 had an energy density of 37.85Wh/kg at a power density of 800W/kg, and after cycling for ten thousand times, the button type asymmetric supercapacitor prepared in example 8 had a capacity retention rate and coulombic efficiency of 96.1% and 99.5%, respectively.
Example 9
In this example, a button-type asymmetric supercapacitor was assembled in the same manner as in example 7, using the NiCo-DH/oxidized activated carbon composite working electrode prepared in example 6 as the positive electrode, the oxidized activated carbon working electrode prepared in example 3 as the negative electrode, which was obtained by the method for preparing the working electrode in example 4, an aqueous filter membrane as the separator, and a 6mol/L aqueous potassium hydroxide solution as the electrolyte. The button-type asymmetric supercapacitor prepared in example 9 was subjected to electrochemical performance test by means of an electrochemical workstation (Shanghai Chenhua, CHI-660E) and a battery detection system (Xinwei, CT-4000). The button type asymmetric supercapacitor prepared in example 9 had an energy density of 32.72Wh/kg at a power density of 800W/kg, and after cycling for ten thousand times, the capacitor retention rate and coulomb efficiency of the button type asymmetric supercapacitor prepared in example 9 were 94.6% and 97.3%, respectively.
Comparative example 1
The comparative example provides a preparation method of a NiCo-DH/active carbon composite material for a super capacitor, which comprises the following steps:
placing 8g of anthracite coal dust in a plastic beaker filled with 80mL of hydrofluoric acid solution with mass concentration of 40%, heating in a water bath at 60 ℃ for 5 hours to obtain a first suspension, carrying out suction filtration on the obtained first suspension, flushing with deionized water until the pH value of the filtrate is 7, and placing the obtained filter cake in a vacuum drying box for drying at 80 ℃ for 24 hours to obtain anthracite coal;
taking 1g of ashless coal, placing 4g of potassium hydroxide in a grinding mode, grinding into powder, placing in a horizontal tube furnace for activation, heating to 800 ℃ in a temperature programming mode under a nitrogen atmosphere, keeping the temperature at the heating rate of 5 ℃/min for 2 hours at the temperature of 800 ℃, taking out after cooling to room temperature, and placing in a hydrochloric acid solution with the concentration of 2mol/L of 50mL to obtain a second suspension;
carrying out suction filtration on the obtained second suspension, washing with deionized water until the pH value of the filtrate is 7, and drying the obtained filter cake in a vacuum drying oven at 80 ℃ for 24 hours to obtain activated carbon;
weighing 0.03g of activated carbon, 0.6g of urea, 0.58g of nickel nitrate hexahydrate and 0.29g of cobalt nitrate hexahydrate, putting into a mixed solution of 20mL of deionized water and 20mL of ethanol, stirring for 30min, performing ultrasonic treatment for 30min, transferring into a hydrothermal kettle with a polytetrafluoroethylene lining of 100mL, preserving heat at 180 ℃ for 12h, and cooling to obtain a third suspension;
and centrifuging the obtained third suspension with ethanol for three times, centrifuging with deionized water for three times, and drying the centrifugated substrate in a vacuum drying oven at 80 ℃ for 24 hours to obtain the NiCo-DH/activated carbon composite material.
SEM images of the NiCo-DH/activated carbon composite material prepared in the comparative example are shown in FIG. 9, and the surface of the activated carbon can be seen from the images to be tightly wrapped by the NiCo-DH in the form of nanoneedles, which shows that the NiCo-DH is successfully loaded on the activated carbon.
The XPS spectrum of the NiCo-DH/activated carbon composite material prepared in the comparative example is shown in FIG. 10, and the four elements of C, O, ni and Co are present on the XPS spectrum, which shows that the NiCo-DH is successfully loaded on the activated carbon, wherein the O content is lower than that of the NiCo-DH/oxidized activated carbon composite material prepared in example 1, because the activated carbon is subjected to the oxidation modification in example 1. Using the NiCo-DH/active carbon composite material obtained in this comparative example, an electrochemical test was conducted under the same test conditions as in example 4, using the electrode sheet prepared in the same manner as in example 4 as a working electrode, and the specific capacitance at a current density of 1A/g was 1490F/g, which is lower than 1990F/g of the NiCo-DH/oxidized active carbon composite material prepared in example 1, indicating that the active carbon was capable of effectively increasing the charge transfer rate of the composite material after being subjected to oxidation modification, thereby increasing the specific capacitance.
The button-type asymmetric supercapacitor was assembled in the same manner as in example 7, using the NiCo-DH/activated carbon composite working electrode prepared in this comparative example as the positive electrode, the activated carbon working electrode prepared in this comparative example according to the working electrode preparation method in example 4 as the negative electrode, the aqueous filter membrane as the separator, and a 6mol/L aqueous potassium hydroxide solution as the electrolyte. The button-type asymmetric supercapacitor prepared in this comparative example was subjected to electrochemical performance test by an electrochemical workstation (Shanghai Chenhua, CHI-660E) and a battery detection system (Xinwei, CT-4000). FIG. 11 is a graph of the rate performance of a coin-type asymmetric supercapacitor, calculated as the specific capacitance values at different current densities, at a current density of 1A/g, the specific capacitance of the coin-type asymmetric supercapacitor reached 93.75F/g, which is lower than 118.75F/g of the coin-type asymmetric supercapacitor prepared in example 7. Fig. 12 is a drawing graph of a button-type asymmetric supercapacitor, and when the power density is 800W/kg, the energy density of the button-type asymmetric supercapacitor is 33.33Wh/kg, which is lower than 42.22Wh/kg of the button-type asymmetric supercapacitor prepared in example 7, and it can be seen by comparison that the activated carbon of the composite material has more excellent electrochemical properties when applied to the electrode material of the supercapacitor after oxidative modification.
For purposes of this disclosure, the terms "one embodiment," "some embodiments," "example," "a particular example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (12)
1. The preparation method of the NiCo-DH/oxidized active carbon composite material is characterized by comprising the following steps of:
s1: adding anthracite coal powder into hydrofluoric acid solution, carrying out water bath ash removal to obtain first suspension, carrying out suction filtration and water washing on the first suspension, and drying a filter cake to obtain ashless coal;
s2: uniformly mixing the ashless coal and an alkali activator, grinding into powder, placing in a calciner, heating to 700-900 ℃ from room temperature under nitrogen atmosphere, and then preserving heat for 1-3h to obtain a calcination product;
s3: placing the calcined product in a strong acid solution to obtain a second suspension, and carrying out suction filtration, water washing and filter cake drying on the second suspension to obtain activated carbon;
s4: placing the activated carbon in a strong oxidizing solution, performing hydrothermal oxidation at 100-140 ℃ for 2-6h, cooling to obtain a third suspension, and performing suction filtration, water washing and filter cake drying on the third suspension to obtain oxidized activated carbon;
s5: placing the oxidized active carbon, urea, nickel nitrate hexahydrate and cobalt nitrate hexahydrate into an alcohol aqueous solution for ultrasonic treatment, performing hydrothermal reaction at 160-200 ℃ for 10-14h, and cooling to obtain a fourth suspension;
s6: and centrifuging the fourth suspension with alcohol for multiple times, centrifuging with water for multiple times, and drying the centrifuged substrate to obtain the NiCo-DH/oxidized active carbon composite material.
2. The method for preparing a NiCo-DH/oxidized active carbon composite material according to claim 1, wherein in the step S1, the mass concentration of the hydrofluoric acid solution is 40-60%, the dosage ratio of the anthracite coal powder to the hydrofluoric acid solution is 1g:8-13mL, the temperature of the water bath ash removal is 50-70 ℃, and the time is 5-7h.
3. The method for preparing the NiCo-DH/oxidized active carbon composite material according to claim 1, wherein in the step S2, the mass ratio of the ashless coal to the alkali activator is 1 (3-5), and the alkali activator is potassium hydroxide or sodium hydroxide.
4. The method for preparing a NiCo-DH/oxidized activated carbon composite material according to claim 1, wherein in step S3, the strong acid solution is one of a hydrochloric acid solution, a nitric acid solution, and a sulfuric acid solution.
5. The method for preparing a NiCo-DH/oxidized activated carbon composite according to claim 1, wherein in step S4, the strong oxidizing solution is one of a nitric acid solution, a sulfuric acid solution, and a hydrogen peroxide solution.
6. The method for producing a NiCo-DH/oxidized activated carbon composite according to claim 5, wherein said strongly oxidizing solution is a nitric acid solution of 1 to 5 mol/L.
7. The preparation method of the NiCo-DH/oxidized active carbon composite material according to claim 1, wherein in the step S5, the mass ratio of the oxidized active carbon to the urea to the nickel nitrate hexahydrate to the cobalt nitrate hexahydrate is 0.03:0.6 (0.29-0.87).
8. The method for preparing a NiCo-DH/oxidized activated carbon composite material according to claim 1, wherein the alcohol in the aqueous alcohol solution is one of ethanol, methanol, and isopropanol.
9. The method for preparing the NiCo-DH/oxidized active carbon composite material of claim 1, wherein,
in the steps S1, S3 and S4, the method for drying the filter cake comprises the following steps: vacuum drying at 70-90deg.C for 20-28h.
10. The method for preparing the NiCo-DH/oxidized activated carbon composite material according to claim 9, wherein the water washing method comprises the following steps: washing with deionized water until the filtrate had a pH of 7.
11. A NiCo-DH/oxidized activated carbon composite material prepared by the method of any of claims 1-10.
12. Use of a NiCo-DH/oxidized activated carbon composite material as claimed in claim 11 as an electrode material for a supercapacitor.
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