CN111029166A - Brown coal-based porous carbon/CoNi for supercapacitor2S4Composite electrode and preparation method and application thereof - Google Patents
Brown coal-based porous carbon/CoNi for supercapacitor2S4Composite electrode and preparation method and application thereof Download PDFInfo
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
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- 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
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Abstract
The invention discloses brown coal-based porous carbon/CoNi for a supercapacitor2S4A composite electrode and a preparation method and application thereof belong to the technical field of super capacitor anodes. The preparation method comprises the following steps: lignite is extracted through alkaline solution dipping to obtain an extract, lignite-based porous carbon is obtained after activation, hydrothermal reaction is carried out on the lignite-based porous carbon, a cobalt source and a nickel source in water after pickling to obtain a precursor, and the precursor and a sulfur source are subjected to secondary hydrothermal synthesis in the water solution to obtain the lignite-based porous carbon/CoNi2S4Composite material, and different brown coal-based porous carbon/CoNi prepared from the composite material2S4A composite material; then brown coal-based porous carbon/CoNi2S4Uniformly mixing the composite material, a polytetrafluoroethylene aqueous solution, acetylene black and deionized water, coating a plate, and drying to obtain the brown coal-based porous carbon/CoNi2S4And (3) a composite electrode. The invention has the advantages ofThe obtained electrode material has high specific capacitance and stable cycle performance, and has good application prospect in the field of energy storage electrodes.
Description
Technical Field
The invention belongs to the technical field of positive electrode materials of supercapacitors, and particularly relates to brown coal-based porous carbon/CoNi for a supercapacitor2S4A composite electrode and a preparation method and application thereof.
Background
Along with the development of society, the energy structure problem is increasingly prominent. The most important characteristic of the energy structure in China is that the coal accounts for a very high percentage, about 60%. The clean utilization of traditional energy sources is also the focus of research. The super capacitor has the advantages of high charging and discharging speed, high power density, high specific capacity, long service life, environmental friendliness and the like. CoNi2S4The electrode material has the advantages of low manufacturing cost, high theoretical capacitance and the like. But CoNi2S4Usually accompanied by large volume changes and mechanical deformations during rapid redox processes, ultimately leading to rapid capacity decay. Two existing approaches solve the problem, namely constructing CoNi2S4Nanostructures, e.g. CoNi2S4Nanosphere, CoNi2S4Nano-plate and other nano-structure, CoNi of different structure2S4The nano material has excellent pseudo capacitance performance. Another method is to prepare carbon/CoNi2S4The composite material is easy to agglomerate and mechanically deform, complicated in preparation process and difficult to produce on a large scale. Thus producing carbon/CoNi2S4The base material is a method with more practical value and prospect.
The brown coal-based porous carbon is an activated carbon material prepared by using coal as a raw material through different activation methods. The brown coal-based porous carbon has simple preparation process and low cost, and can be industrially produced on a large scale. The brown coal-based porous carbon has excellent conductivity with extremely high specific surface area, is mainly used as a solid adsorbate, and is widely applied to chemical industry, medicine and environmentAnd so on in various industries. The derivative materials of some activated carbon are widely applied to the directions of spaceflight, electronics, communication, energy, bioengineering and the like. As the brown coal-based porous carbon has very excellent cycle stability and good structure retentivity, the brown coal-based porous carbon/CoNi is prepared2S4The composite material can effectively improve CoNi2S4The material has poor cycle performance caused by agglomeration and mechanical deformation in the charging and discharging process.
In the preparation method of the brown coal-based porous carbon, physical activation is mostly used for preparing activated carbon, lignite is soaked by using an alkali solution, brown coal-based porous carbon is prepared by activating a lignite extract, and the activated carbon is applied to preparation of electrode materials of a super capacitor. In the preparation process, firstly, cobalt nickel hydroxide is dispersed on the surface of coal-based porous carbon to obtain a precursor, and then a sulfur source is added to prepare the brown coal-based porous carbon/CoNi2S4The structure of the composite material is more stable, and CoNi can be effectively inhibited2S4A volume change occurs. The brown coal-based porous carbon is prepared by the method, and the brown coal-based porous carbon/CoNi is prepared2S4Composite electrode materials have not been reported publicly at present.
Disclosure of Invention
The invention provides brown coal-based porous carbon/CoNi for a supercapacitor2S4Composite electrode, preparation method and application thereof, aiming at solving the problems of lower specific capacity of super capacitor electrode in the prior art and the prior CoNi2S4The active material is easy to agglomerate and has poor conductivity.
In order to achieve the purpose, the invention adopts the technical scheme that:
brown coal-based porous carbon/CoNi for supercapacitor2S4The composite electrode comprises the following components in parts by weight:
brown coal-based porous carbon/CoNi2S4100 parts of the composite material is prepared by mixing the components,
8-14 parts of acetylene black,
100-150 parts of polytetrafluoroethylene aqueous solution with the mass fraction of 10%, namely 10g of polytetrafluoroethylene is dissolved in 90g of water to form aqueous solution,
100-120 parts of deionized water.
Brown coal-based porous carbon/CoNi for supercapacitor2S4The preparation method of the composite electrode comprises the steps of dipping and extracting lignite by using an alkali solution to obtain an extract, activating to obtain brown coal-based porous carbon, carrying out hydrothermal reaction on the brown coal-based porous carbon, a cobalt source and a nickel source in water after pickling to obtain a precursor, and carrying out secondary hydrothermal synthesis on the precursor and a sulfur source in an aqueous solution to obtain the brown coal-based porous carbon/CoNi2S4The brown coal-based porous carbon/CoNi is prepared from the composite material2S4A composite material; then brown coal-based porous carbon/CoNi2S4Uniformly mixing the composite material, aqueous solution of polytetrafluoroethylene, acetylene black and deionized water, coating a plate, and drying to obtain brown coal-based porous carbon/CoNi2S4And (3) a composite electrode.
Further, the brown coal-based porous carbon/CoNi2S4The preparation method of the composite material comprises the following steps:
step one, adding distilled water into a liner of a hydrothermal kettle, and then adding CoCl into the kettle2·6H2O、Ni(NO3)2·6H2O, Urea and NH4F, adding brown coal-based porous carbon after complete dissolution, and ultrasonically stirring for 10-20 min;
step two, sealing and screwing the hydrothermal kettle, putting the hydrothermal kettle into an oven, and putting the hydrothermal kettle in the oven at a temperature of 100-150 DEG CoC, reacting for 6 hours, carrying out suction filtration to obtain a precipitate, washing the precipitate with water, and drying to obtain a precursor;
adding distilled water into the inner container of the hydrothermal kettle, adding the precursor into the kettle, stirring for 1 min, and adding Na2S·9H2O, stirring for 1 min, sealing and screwing the hydrothermal kettle, putting the hydrothermal kettle into an oven, and heating the hydrothermal kettle to 150-200 DEG CoC, reacting for 12 hours, filtering to obtain precipitate, washing the precipitate with water, and drying to obtain brown coal-based porous carbon/CoNi2S4A composite material.
Further, in the step one, the volume of distilled water, CoCl2·6H2Mass of O, Ni (NO)3)2·6H2Mass of O, mass of Urea, NH4The mass ratio of the F to the brown coal-based porous carbon is 80 mL, 0.4-0.6 g, 1.1-1.2 g, 1.5-2.0 g, 0.4-0.6 g and 0.03-0.06 g.
Furthermore, in the third step, the dosage of the distilled water is 80 mL, and the precursor and Na are added2S·9H2The mass ratio of O is 0.5-0.8: 1.
Further, the preparation method of the brown coal-based porous carbon comprises the following steps:
adding distilled water into a beaker, adding KOH, adding lignite after KOH is dissolved, stirring for 24 hours on a magnetic stirrer at the stirring temperature of 20-70 ℃, performing centrifugal separation after stirring is finished, drying supernate to obtain lignite extract, putting the lignite extract into a tubular furnace, and placing the lignite extract in a nitrogen atmosphere for 700-850 DEG CoC activating for 1 h, grinding the obtained product, and adding HNO3And (3) ultrasonically stirring for 25-35 min, then continuing magnetically stirring for 24 h, and performing suction filtration, washing and drying to obtain the brown coal-based porous carbon.
Further, in the preparation method of the brown coal-based porous carbon, the using amount of distilled water is 80-100 mL, the mass ratio of KOH to lignite is 1-3: 1, and HNO is added3The mass fraction of (B) is 10%.
Furthermore, the brown coal-based porous carbon/CoNi can be added by changing the adding proportion of the brown coal-based porous carbon in the precursor2S4CoNi in composite material2S4Content control, brown coal-based porous carbon/CoNi prepared by the method and the proportion provided by the invention2S4CoNi in composite material2S4The mass content of (A) is more than 70%.
Further, brown coal-based porous carbon/CoNi2S4Stirring the composite material, aqueous solution of polytetrafluoroethylene, acetylene black and deionized water at room temperature to form uniform paste, uniformly coating the paste on foamed nickel, and then stirring at 60 DEG CoAnd C, drying to obtain the composite electrode.
Further, the brown coal-based porous carbon/CoNi for the super capacitor prepared according to the preparation method2S4The composite electrode is used for a super capacitor electrode.
Compared with the prior art, the invention has the following beneficial effects:
due to the adoption of the scheme, the brown coal-based porous carbon/CoNi2S4When the composite material is prepared, brown coal-based porous carbon/CoNi composite material solid powder is used as a precursor, and then the second step of hydrothermal reaction is carried out to add a sulfur source to prepare the brown coal-based porous carbon/CoNi composite material2S4A composite material. CoNi can be prepared by this preparation method2S4Is uniformly attached to the surface of the brown coal-based porous carbon, and the brown coal-based porous carbon can effectively avoid CoNi as a support2S4Agglomeration during charging and discharging process to improve CoNi2S4The bonding force between the material and the brown coal-based porous carbon enables the materials to be compounded more stably, on one hand, the volume change of the electrode material in the charge and discharge process can be reduced, and on the other hand, CoNi can be effectively prevented from being generated in the charge and discharge process2S4Due to the volume change, the brown coal-based porous carbon is detached from the surface.
The super capacitor electrode prepared by the method has high specific capacitance and excellent rate capability, and has good application prospect in the field of high specific volume super capacitors.
Drawings
FIG. 1 is a brown coal based porous carbon/CoNi of the invention2S4XRD pattern of the composite.
FIG. 2 is a brown coal based porous carbon/CoNi of the invention2S4SEM image of the composite material.
FIG. 3 is a brown coal based porous carbon/CoNi of the invention2S4Cyclic voltammograms of the composite electrode.
FIG. 4 is a brown coal based porous carbon/CoNi of the invention2S4Composite electrode and CoNi2S4Rate performance graph of the nano-electrode.
FIG. 5 is a brown coal based porous carbon/CoNi of the invention2S4GCD plot of the composite electrode.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Brown coal-based porous carbon/CoNi for supercapacitor2S4The composite electrode comprises the following components in parts by weight: brown coal-based porous carbon/CoNi2S4100 parts of a composite material, 8-14 parts of acetylene black and 100-150 parts of polytetrafluoroethylene aqueous solution with the mass fraction of 10%, namely 10g of polytetrafluoroethylene is dissolved in 90g of water to form an aqueous solution, and 100-120 parts of deionized water.
The brown coal-based porous carbon in the embodiment is prepared by adopting the prior art.
Example 2
The difference between this embodiment and specific embodiment 1 is that the preparation method of the brown coal-based porous carbon comprises: adding 100mL of distilled water into a beaker, adding 10g of KOH, adding 5 g of lignite after the KOH is dissolved, stirring for 24 hours on a magnetic stirrer at the stirring temperature of 20 ℃, performing centrifugal separation after the stirring is finished, drying the supernatant to obtain a lignite extract, activating the lignite extract in a tubular furnace, and performing 700 g of activation under the protection of nitrogenoActivating for 1 h under C, grinding activated carbon, and adding diluted HNO3Washing, adding diluted HNO3And then ultrasonically stirring for 30 min, then continuing magnetically stirring for 24 h, carrying out suction filtration to obtain a precipitate, and washing and drying the precipitate to obtain the brown coal-based porous carbon.
In this embodiment, the method for preparing the brown coal-based porous carbon is not limited to the above-described method, and any conventionally disclosed preparation method can be used for preparing the brown coal-based porous carbon.
Example 3
This embodiment differs from embodiment 1 or 2 in that: the preparation method of the brown coal-based porous carbon comprises the following steps: adding 100mL of distilled water into a beaker, adding 10g of KOH, adding 5 g of lignite after the KOH is dissolved, stirring for 24 hours on a magnetic stirrer at the stirring temperature of 35 ℃, performing centrifugal separation after the stirring is finished, drying the supernatant to obtain a lignite extract, activating the lignite extract in a tubular furnace, and activating the lignite extract under the protection of nitrogen by 800 goActivating for 1 h under C, grinding activated carbon, and adding diluted HNO3Washing, adding diluted HNO3Then ultrasonically stirring for 30 min, and then continuing to magnetically stirStirring for 24 h, carrying out suction filtration to obtain a precipitate, and washing and drying the precipitate to obtain the brown coal-based porous carbon.
Example 4
The present embodiment differs from one of embodiments 1 to 3 in that: the brown coal-based porous carbon/CoNi2S4The preparation method of the composite material comprises the following steps: firstly, adding 80 mL of distilled water into a 100mL hydrothermal kettle liner, and then adding 0.475 g of CoCl into the kettle2·6H2O、1.163 g Ni(NO3)2·6H2O, 1.8 g Urea and 0.445 g NH4And F, after complete dissolution, adding 0.05 g of the brown coal-based porous carbon prepared in the example 2, and carrying out ultrasonic stirring for 10 min. Secondly, sealing and screwing the hydrothermal kettle, putting the hydrothermal kettle into an oven and heating the hydrothermal kettle at 120 DEG CoAnd C, reacting for 6 hours, and performing suction filtration, washing and drying to obtain a precursor. Adding 80 mL of distilled water into a 100mL hydrothermal kettle liner, adding 0.06 g of precursor into the kettle, stirring for 1 min, and adding 0.6 g of Na2S·9H2O, stirring for 1 min, sealing the hydrothermal kettle, screwing, putting into an oven, and stirring at 180 DEGoC, reacting for 12 hours, filtering to obtain precipitate, washing the precipitate with water, and drying to obtain brown coal-based porous carbon/CoNi2S4A composite material.
Example 5
This example differs from one of examples 1 to 4 in that the lignite-based porous carbon/CoNi is2S4The preparation method of the composite material comprises the following steps: firstly, adding 80 mL of distilled water into a 100mL hydrothermal kettle liner, and then adding 0.475 g of CoCl into the kettle2·6H2O、1.163 g Ni(NO3)2·6H2O, 1.8 g Urea and 0.445 g NH4And F, after complete dissolution, adding 0.05 g of the brown coal-based porous carbon prepared in the example 3, and carrying out ultrasonic stirring for 10 min. Secondly, sealing and screwing the hydrothermal kettle, putting the hydrothermal kettle into an oven and heating the hydrothermal kettle at 120 DEG CoAnd C, reacting for 6 hours, and performing suction filtration, washing and drying to obtain a precursor. Adding 80 mL of distilled water into a 100mL hydrothermal kettle liner, adding 0.06 g of precursor into the kettle, stirring for 1 min, and adding 0.6 g of Na2S·9H2O, stirring for 1 min, sealing the hydrothermal kettle, screwing, putting into an oven, and stirring at 180 DEGoC, reacting for 12 hours under the condition of C,carrying out suction filtration to obtain a precipitate, washing and drying the precipitate to obtain the brown coal-based porous carbon/CoNi2S4A composite material.
Brown coal-based porous carbon/CoNi prepared by the embodiment2S4The XRD pattern of the composite material is shown in figure 1. As can be seen from FIG. 1, all diffraction peaks of the composite material correspond to CoNi of cubic system2S4(JCPDS card No. 24-0334) demonstrates the success of preparing composites by hydrothermal methods. In addition, there were no other significant peaks, indicating that the brown coal-based porous carbon in the composite was amorphous.
Brown coal based porous carbon/CoNi prepared in this example2S4SEM image of the composite material, as shown in FIG. 2, from which it can be seen that CoNi2S4The nano particles are uniformly covered on the surface of the brown coal-based porous carbon or are tightly combined with the brown coal-based porous carbon, and CoNi is added2S4Is compounded with brown coal-based porous carbon, is favorable for improving CoNi2S4The conductivity of (2) promotes the penetration of the electrolyte into the electrode, and further promotes the diffusion of ions.
Example 6
The present embodiment differs from one of embodiments 1 to 5 in that: the CoNi2S4The preparation method of the nano material comprises the following steps: first, add 80 mL of distilled water to the 100mL hydrothermal kettle liner, and add 0.475 g of CoCl to the kettle2·6H2O、1.163 g Ni(NO3)2·6H2O, 1.8 g Urea and 0.445 g NH4And F, ultrasonic stirring for 10 min after complete dissolution. Secondly, sealing and screwing the hydrothermal kettle, putting the hydrothermal kettle into an oven and heating the hydrothermal kettle at 120 DEG CoAnd C, reacting for 6 hours, and performing suction filtration, washing and drying to obtain a precursor. Adding 80 mL of distilled water into a 100mL hydrothermal kettle liner, adding 0.06 g of precursor into the kettle, stirring for 1 min, and adding 0.6 g of Na2S·9H2O, stirring for 1 min, sealing the hydrothermal kettle, screwing, putting into an oven, and stirring at 180 DEGoC, reacting for 12 hours, filtering to obtain precipitate, washing the precipitate with water, and drying to obtain CoNi2S4And (3) nano materials.
Example 7
This example differs from one of examples 1 to 6 in that the lignite-based porous carbon/CoNi is2S4The preparation method of the composite electrode is realized by the following steps: weighing 100 parts by weight of brown coal-based porous carbon/CoNi prepared in example 42S4The composite material comprises 8-14 parts of acetylene black, 100-150 parts of 10% aqueous solution of polytetrafluoroethylene and 100-120 parts of water. Stirring at room temperature, making into uniform paste, uniformly coating on foamed nickel, and stirring at 60 deg.CoC, drying to obtain brown coal-based porous carbon/CoNi2S4And (3) a composite electrode.
Example 8
This example differs from one of the specific examples 1 to 7 in that the lignite-based porous carbon/CoNi is2S4The preparation method of the composite electrode is realized by the following steps: 0.02 g of brown coal-based porous carbon/CoNi prepared in example 4 was weighed out2S4Mixing the composite material, 0.0025 g acetylene black, 0.025 g aqueous solution of 10% polytetrafluoroethylene by mass and 0.025 g water at room temperature for 20 min, uniformly coating the mixture on foamed nickel at 60%oC, drying to obtain brown coal-based porous carbon/CoNi2S4And (3) a composite electrode.
Example 9
This example differs from one of examples 1 to 8 in that the lignite-based porous carbon/CoNi is2S4The preparation method of the composite electrode is realized by the following steps: weighing 100 parts by weight of brown coal-based porous carbon/CoNi prepared in example 52S4The composite material comprises 8-14 parts of acetylene black, 100-150 parts of 10% aqueous solution of polytetrafluoroethylene and 100-120 parts of water. Stirring at room temperature, making into uniform paste, uniformly coating on foamed nickel, and stirring at 60 deg.CoC, drying to obtain brown coal-based porous carbon/CoNi2S4And (3) a composite electrode.
Example 10
This example differs from one of the specific examples 1 to 9 in that the lignite-based porous carbon/CoNi is2S4The preparation method of the composite electrode is realized by the following steps: 0.02 g of example 5 was weighed outBrown coal-based porous carbon/CoNi prepared2S4Mixing the composite material, 0.0025 g acetylene black, 0.025 g aqueous solution of 10% polytetrafluoroethylene by mass and 0.025 g water at room temperature for 20 min, uniformly coating the mixture on foamed nickel at 60%oC, drying to obtain brown coal-based porous carbon/CoNi2S4And (3) a composite electrode.
Example 11
The difference between this example and one of the embodiments 1 to 10 is that CoNi2S4The preparation method of the nano electrode is realized by the following steps: 0.02 g CoNi was weighed2S4Mixing nanometer materials, 0.0025 g acetylene black, 0.025 g 10 wt% aqueous solution of polytetrafluoroethylene, 0.025 g water at room temperature for 20 min, uniformly coating on foamed nickel at 60 deg.CoC drying to obtain CoNi2S4And (4) a nano electrode.
Example 12
The difference between this embodiment and embodiments 1 to 11 is that the supercapacitor three-electrode test system is implemented by the following steps: the brown coal-based porous carbon/CoNi obtained in example 10 and example 11 respectively2S4Composite electrodes or CoNi2S4The nano electrode is a working electrode, the platinum electrode is used as a counter electrode, the Ag/AgCl electrode is used as a reference electrode, and 6M KOH solution is used as electrolyte to form a three-electrode testing system. Brown coal based porous carbon/CoNi prepared in example 102S4The cyclic voltammogram of the composite electrode is shown in FIG. 3, from which it can be seen that brown coal-based porous carbon/CoNi2S4Composite electrode at 5 mV s-1At the scan rate of (a), it is clear that a series of redox peaks are observed, corresponding respectively to the following faradaic reactions:
CoS + OH–↔ CoSOH + e–(1)
CoSOH + OH–↔ CoSO + H2O + e–(2)
NiS + OH–↔ NiSOH + e–(3)
brown coal-based porous carbon/CoNi prepared in examples 10 and 112S4Composite electrode and CoNi2S4The cycle life of the nanoelectrodes is plotted in FIG. 4, where the test was performed at 4A g-1The cycle performance of the electrode under the current density is shown in the figure, the specific capacitance and the cycle performance of the electrode are not greatly different in the initial hundreds of cycles, and after 1000 cycles, the composite material inhibits CoNi due to the existence of the brown coal-based porous carbon2S4The agglomeration and the volume change of the nano particles in the circulating process show better circulating performance. After 4000 cycles, CoNi2S4And lignite-based porous carbon/CoNi2S4The specific capacitances of the composites were 892 and 1064F g, respectively–1。
Brown coal based porous carbon/CoNi prepared in example 102S4The rate capability of the composite electrode is shown in fig. 5, and it can be seen that the composite material exhibits excellent rate capability at current densities of 6, 8, 10 and 12A g, respectively–1The specific capacitances of the composite materials were 1290, 1095, 925 and 775F g, respectively–1. Because of the addition of the brown coal-based porous carbon, CoNi can be effectively inhibited2S4Due to the deformation generated in the charging and discharging process, electron transfer is promoted to a limited extent, so that the brown coal-based porous carbon/CoNi2S4The cycle performance and the rate performance of the composite electrode are more excellent, and the composite electrode has a good application prospect in the field of high specific volume supercapacitors.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (10)
1. Brown coal-based porous carbon/CoNi for supercapacitor2S4The composite electrode is characterized by comprising the following components in parts by weight:
brown coal-based porous carbon/CoNi2S4100 parts of the composite material is prepared by mixing the components,
8-14 parts of acetylene black,
100-150 parts of polytetrafluoroethylene aqueous solution with the mass fraction of 10%,
100-120 parts of deionized water.
2. The lignite-based porous carbon/CoNi for a supercapacitor according to claim 12S4The preparation method of the composite electrode is characterized by comprising the following steps: lignite is extracted through alkaline solution dipping to obtain an extract, lignite-based porous carbon is obtained after activation, hydrothermal reaction is carried out on the lignite-based porous carbon, a cobalt source and a nickel source in water after pickling to obtain a precursor, and the precursor and a sulfur source are subjected to secondary hydrothermal synthesis in the water solution to obtain the lignite-based porous carbon/CoNi2S4The brown coal-based porous carbon/CoNi is prepared from the composite material2S4A composite material; then brown coal-based porous carbon/CoNi2S4Uniformly mixing the composite material, aqueous solution of polytetrafluoroethylene, acetylene black and deionized water, coating a plate, and drying to obtain brown coal-based porous carbon/CoNi2S4And (3) a composite electrode.
3. Lignite-based porous carbon/CoNi for a supercapacitor according to claim 1 or 22S4The preparation method of the composite electrode is characterized in that the brown coal-based porous carbon/CoNi2S4The preparation method of the composite material comprises the following steps:
step one, adding distilled water into a liner of a hydrothermal kettle, and then adding CoCl into the kettle2·6H2O、Ni(NO3)2·6H2O, Urea and NH4F, adding brown coal-based porous carbon after complete dissolution, and ultrasonically stirring for 10-20 min;
step two, sealing and screwing the hydrothermal kettle, putting the hydrothermal kettle into an oven, and putting the hydrothermal kettle in the oven at a temperature of 100-150 DEG CoC, reacting for 6 hours, carrying out suction filtration to obtain a precipitate, washing the precipitate with water, and drying to obtain a precursor;
adding distilled water into the inner container of the hydrothermal kettle, adding the precursor into the kettle, stirring for 1 min, and adding Na2S·9H2O, stirring for 1 min, sealing and screwing the hydrothermal kettle, putting the hydrothermal kettle into an oven, and heating the hydrothermal kettle to 150-200 DEG CoReacting for 12 hours under C, filtering to obtain precipitate,washing and drying the precipitate to obtain brown coal-based porous carbon/CoNi2S4A composite material.
4. The lignite-based porous carbon/CoNi for a supercapacitor according to claim 32S4The preparation method of the composite electrode is characterized in that in the step one, the volume of distilled water and CoCl2·6H2Mass of O, Ni (NO)3)2·6H2Mass of O, mass of Urea, NH4The mass ratio of the F to the brown coal-based porous carbon is 80 mL, 0.4-0.6 g, 1.1-1.2 g, 1.5-2.0 g, 0.4-0.6 g and 0.03-0.06 g.
5. The lignite-based porous carbon/CoNi for a supercapacitor according to claim 32S4The preparation method of the composite electrode is characterized in that in the third step, the using amount of distilled water is 80 mL, and the precursor and Na are added2S·9H2The mass ratio of O is 0.5-0.8: 1.
6. The lignite-based porous carbon/CoNi for a supercapacitor according to claim 32S4The preparation method of the composite electrode is characterized in that the preparation method of the brown coal-based porous carbon comprises the following steps:
adding distilled water into a beaker, adding KOH, adding lignite after KOH is dissolved, stirring for 24 hours on a magnetic stirrer at the stirring temperature of 20-70 ℃, performing centrifugal separation after stirring is finished, drying supernate to obtain lignite extract, putting the lignite extract into a tubular furnace, and placing the lignite extract in a nitrogen atmosphere for 700-850 DEG CoC activating for 1 h, grinding the obtained product, and adding HNO3And (3) ultrasonically stirring for 25-35 min, then continuing magnetically stirring for 24 h, and performing suction filtration, washing and drying to obtain the brown coal-based porous carbon.
7. The lignite-based porous carbon/CoNi for the supercapacitor according to claim 62S4The preparation method of the composite electrode is characterized in that in the preparation method of the brown coal-based porous carbon, the amount of distilled water is 80-100 mL, KOH and brown are addedThe mass ratio of coal is 1-3: 1, HNO3The mass fraction of (B) is 10%.
8. The lignite-based porous carbon/CoNi for a supercapacitor according to claim 32S4The preparation method of the composite electrode is characterized in that the prepared brown coal-based porous carbon/CoNi2S4CoNi in composite material2S4The mass content of (A) is more than 70%.
9. The lignite-based porous carbon/CoNi for a supercapacitor according to claim 32S4The preparation method of the composite electrode is characterized in that brown coal-based porous carbon/CoNi2S4Stirring the composite material, aqueous solution of polytetrafluoroethylene, acetylene black and deionized water at room temperature to form uniform paste, uniformly coating the paste on foamed nickel, and then stirring at 60 DEG CoAnd C, drying to obtain the composite electrode.
10. Brown coal-based porous carbon/CoNi for super capacitor prepared by the preparation method according to claim 22S4The composite electrode is used for a super capacitor electrode.
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| CN115246670A (en) * | 2021-12-28 | 2022-10-28 | 榆林学院 | Cobalt-loaded coal-based electrode material, preparation method and application thereof |
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