CN114446670A - Nickel-cobalt hydrotalcite composite material with liquorice residue porous carbon as substrate and preparation method and application thereof - Google Patents
Nickel-cobalt hydrotalcite composite material with liquorice residue porous carbon as substrate and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 92
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 79
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 79
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 76
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 239000000758 substrate Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- LPLVUJXQOOQHMX-QWBHMCJMSA-N glycyrrhizinic acid Chemical group O([C@@H]1[C@@H](O)[C@H](O)[C@H](O[C@@H]1O[C@@H]1C([C@H]2[C@]([C@@H]3[C@@]([C@@]4(CC[C@@]5(C)CC[C@@](C)(C[C@H]5C4=CC3=O)C(O)=O)C)(C)CC2)(C)CC1)(C)C)C(O)=O)[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O LPLVUJXQOOQHMX-QWBHMCJMSA-N 0.000 title claims description 28
- 235000006200 Glycyrrhiza glabra Nutrition 0.000 claims abstract description 111
- 235000001453 Glycyrrhiza echinata Nutrition 0.000 claims abstract description 73
- 235000017382 Glycyrrhiza lepidota Nutrition 0.000 claims abstract description 73
- 229940010454 licorice Drugs 0.000 claims abstract description 73
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004202 carbamide Substances 0.000 claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 239000007772 electrode material Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 7
- 244000303040 Glycyrrhiza glabra Species 0.000 claims description 106
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 235000017443 Hedysarum boreale Nutrition 0.000 claims description 31
- 235000007858 Hedysarum occidentale Nutrition 0.000 claims description 31
- 239000001947 glycyrrhiza glabra rhizome/root Substances 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 18
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- 239000007833 carbon precursor Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
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- 239000000843 powder Substances 0.000 claims description 12
- 238000010000 carbonizing Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 9
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
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- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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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
-
- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, 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
- H01G11/32—Carbon-based
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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
- H01G11/84—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
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Abstract
The invention belongs to the technical field of preparation of electrode materials of supercapacitors, and discloses a nickel-cobalt hydrotalcite composite material taking licorice residue porous carbon as a substrate, and a preparation method and application thereof. According to the invention, firstly, a KOH activation method is used for preparing a porous carbon material from licorice pomace, and then a simple one-step hydrothermal method is used for preparing a licorice pomace porous carbon/nickel-cobalt hydrotalcite composite material, wherein the composite material contains a core-shell structure of two-dimensional nanosheets and hydrangeal microspheres. The apparent form, the layering porosity and the active site can be obviously changed by adjusting the content of urea in the synthesis process of the composite material, so that the electrochemical performance is influenced. The result shows that the licorice residue porous carbon/nickel-cobalt hydrotalcite composite material can benefit from the synergistic effect of the carbon materials of the nickel-cobalt hydrotalcite and the licorice residue porous carbon, and has great potential as an electrode material of an energy storage device.
Description
Technical Field
The invention relates to the technical field of preparation of electrode materials of supercapacitors, in particular to a nickel-cobalt hydrotalcite composite material taking licorice root residue porous carbon as a substrate, and a preparation method and application thereof.
Background
With the continuous depletion of fossil fuels, the world energy crisis is worsening. In order to meet the continuous development of high-efficiency energy storage devices, advanced materials having excellent energy storage properties are urgently required. Supercapacitors are promising energy storage systems because they have superior instantaneous power densities compared to conventional batteries and also have greatly improved energy densities compared to conventional dielectric capacitors. In addition, superior charge storage, high energy density and long durability are also reasons why supercapacitors are favored. The unique two-dimensional nano-layered structure and the excellent pseudocapacitance behavior of the hydrotalcite ensure the wide application of the hydrotalcite in the electrochemical field. But generally suffer from relatively poor conductivity, low rate capability and poor stability due to agglomeration during charge and discharge reactions, which is a limiting factor in the entry of this technology into practical energy storage applications.
Disclosure of Invention
In view of the above, the invention provides a nickel-cobalt hydrotalcite composite material using licorice residue porous carbon as a substrate, and a preparation method and application thereof, which effectively improve the conductivity of hydrotalcite and improve the rate capability and stability of the composite material.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a nickel-cobalt hydrotalcite composite material with liquorice residue porous carbon as a substrate, which comprises the following steps:
1) sequentially pre-carbonizing the licorice dregs, post-treating and drying to obtain licorice dreg pre-carbonized powder;
2) mixing KOH, the pre-carbonized powder of the licorice dregs prepared in the step 1) and deionized water, and then dipping to obtain a porous carbon precursor of the licorice dregs;
3) sequentially carbonizing, post-treating and drying the licorice residue porous carbon precursor in the step 2) to obtain licorice residue porous carbon;
4) adding CoCl2·5H2O、NiCl2·5H2O, urea, deionized water and the liquorice dreg porous carbon prepared in the step 3) are mixed,obtaining the liquorice residue porous carbon/nickel-cobalt hydrotalcite precursor fluid;
5) and 4) sequentially carrying out hydrothermal reaction on the licorice residue porous carbon/nickel-cobalt hydrotalcite precursor liquid prepared in the step 4), carrying out post-treatment, and drying to obtain the licorice residue porous carbon/nickel-cobalt hydrotalcite composite material.
Preferably, in the step 1), the temperature of the pre-carbonization is 600-700 ℃, the time of the pre-carbonization is 2-3 h, and the temperature rise rate of the pre-carbonization is 2-8 ℃/min; the post-treatment comprises the following steps: and leaching the pre-carbonized licorice dregs by using a mixed solution of deionized water and ethanol.
Preferably, in the step 2), the mass ratio of the KOH to the pre-carbonized licorice residue powder prepared in the step 1) is 2-4: 1, the mass-to-volume ratio of KOH to deionized water is 2-4 g: 20 mL; stirring and mixing are adopted for mixing, and the mixing time is 2-6 h; the dipping temperature is 60-100 ℃, and the dipping time is 20-24 h.
Preferably, in step 3), the carbonization includes the steps of: placing the licorice residue porous carbon precursor in the step 2) in a tubular furnace, heating to 800-900 ℃ at a heating rate of 2-8 ℃/min, and carbonizing for 2-2.5 h; the post-treatment comprises the following steps: and (3) regulating the PH value of the carbonized licorice residue porous carbon precursor to 6-8 by using 1-1.5M HCl solution, and then fully leaching by using deionized water and ethanol.
Preferably, in step 4), the CoCl is2·5H2O、NiCl2·5H2The mass ratio of O to urea is 1: 2-4: 2-8, the mass volume ratio of urea to deionized water is 0.03-0.6 g: 60mL, wherein the mass ratio of the liquorice residue porous carbon prepared in the step 3) to urea is 0.02-0.04: 0.03 to 0.6.
Preferably, in the step 5), the temperature of the hydrothermal reaction is 100-200 ℃, and the time of the hydrothermal reaction is 4-10 h; the post-treatment comprises the following steps: leaching the licorice residue porous carbon/nickel-cobalt hydrotalcite precursor liquid subjected to the hydrothermal reaction by using a mixed solution of deionized water and ethanol.
The invention also provides the nickel-cobalt hydrotalcite composite material with the licorice root residue porous carbon as the substrate, which is prepared by the preparation method of the nickel-cobalt hydrotalcite composite material with the licorice root residue porous carbon as the substrate.
The invention also provides application of the nickel-cobalt hydrotalcite composite material taking the licorice root residue porous carbon as the substrate in an electrode material.
The invention also provides application of the nickel-cobalt hydrotalcite composite material taking the licorice root residue porous carbon as the substrate in a super capacitor.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
according to the method, the substrate material with the porous structure is prepared by controlling the carbonization condition of the porous carbon of the licorice root decoction dregs, and the porous carbon/nickel cobalt hydrotalcite composite material with the morphology of the porous carbon substrate of the licorice root decoction dregs is directly synthesized by regulating the factors such as the urea content in the synthesis process of the porous carbon/nickel cobalt hydrotalcite composite material of the licorice root decoction dregs.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an electrical property curve of nickel-cobalt hydrotalcite obtained in example 4, wherein A is cyclic voltammetry curve of example 4 at different scanning speeds, B is constant current charging and discharging curve of example 4 at different current densities, and C is cyclic stability curve of example 4 at current density of 10A/g;
fig. 2 is SEM images of the liquorice residue porous carbon and the nickel-cobalt hydrotalcite composite material using the liquorice residue porous carbon as the substrate, wherein a and B are SEM images of the liquorice residue porous carbon, and C and D are SEM images of the nickel-cobalt hydrotalcite composite material using the liquorice residue porous carbon as the substrate;
FIG. 3 is an XRD diagram of nickel-cobalt hydrotalcite and a nickel-cobalt hydrotalcite composite material with licorice residue porous carbon as a substrate.
Detailed Description
The invention provides a preparation method of a nickel-cobalt hydrotalcite composite material with liquorice residue porous carbon as a substrate, which comprises the following steps:
1) sequentially pre-carbonizing the licorice dregs, post-treating and drying to obtain licorice dregs pre-carbonized powder;
2) mixing KOH, the pre-carbonized powder of the licorice dregs prepared in the step 1) and deionized water, and then dipping to obtain a porous carbon precursor of the licorice dregs;
3) sequentially carbonizing, post-treating and drying the licorice residue porous carbon precursor in the step 2) to obtain licorice residue porous carbon;
4) adding CoCl2·5H2O、NiCl2·5H2O, urea, deionized water and the porous carbon of the licorice medicine residue prepared in the step 3) are mixed to obtain a precursor body fluid of the porous carbon/nickel-cobalt hydrotalcite of the licorice medicine residue;
5) and 4) sequentially carrying out hydrothermal reaction on the licorice residue porous carbon/nickel-cobalt hydrotalcite precursor liquid prepared in the step 4), carrying out post-treatment, and drying to obtain the licorice residue porous carbon/nickel-cobalt hydrotalcite composite material.
In the invention, in the step 1), the pre-carbonization temperature is preferably 600-700 ℃, and more preferably 650 ℃; the pre-carbonization time is preferably 2-3 h, and more preferably 2.5 h; the pre-carbonization heating rate is preferably 2-8 ℃/min, and more preferably 5-6 ℃/min;
in the present invention, in step 1), the pre-carbonization comprises the steps of: weighing liquorice dregs and putting the liquorice dregs into a corundum boat, and putting the corundum boat into a tube furnace for pre-carbonization; after the tube furnace is completely cooled, taking out the corundum boat in the furnace for post-treatment; the post-treatment comprises the following steps: and leaching the pre-carbonized licorice dregs by using a mixed solution of deionized water and ethanol.
In the invention, in the step 2), the mass ratio of the KOH to the licorice root residue pre-carbonized powder prepared in the step 1) is preferably 2-4: 1, more preferably 3: 1; the mass-volume ratio of KOH to deionized water is preferably 2-4 g: 20mL, more preferably 3 g: 20 mL; stirring and mixing are adopted for mixing, and the mixing time is preferably 2-6 hours, and further preferably 3-4 hours; the dipping temperature is preferably 60-100 ℃, and further preferably 70-80 ℃; the time for dipping is preferably 20 to 24 hours, and more preferably 21 to 23 hours.
In the present invention, in step 3), the carbonization includes the steps of: placing the licorice residue porous carbon precursor in the step 2) in a tubular furnace, heating to 800-900 ℃ at a heating rate of 2-8 ℃/min, and carbonizing for 2-2.5 h; the carbonization temperature is preferably 800-900 ℃, and more preferably 850 ℃; the carbonization time is preferably 2-2.5 h, and more preferably 120 min; the temperature rise rate of carbonization is preferably 2-8 ℃/min, and more preferably 5-6 ℃/min; the post-treatment comprises the following steps: adjusting the pH value of the carbonized licorice residue porous carbon precursor to 6-8 by using 1-1.5M HCl solution, and then fully leaching by using deionized water and ethanol; the concentration of the HCl solution is preferably 1-1.5M, and more preferably 1.2-1.3M.
In the present invention, in step 4), the CoCl is2·5H2O、NiCl2·5H2The amount ratio of O to urea is preferably 1:2 to 4:2 to 8, more preferably 1:3:4 to 5; the mass volume ratio of the urea to the deionized water is preferably 0.03-0.6 g: 60mL, more preferably 0.06-0.3 g: 60 mL; the mass ratio of the liquorice residue porous carbon prepared in the step 3) to the urea is preferably 0.02-0.04: 0.06 to 0.3, and more preferably 0.03: 0.06 to 0.3.
In the invention, in the step 4), the mixing is ultrasonic mixing, and the ultrasonic mixing time is preferably 10-20 min, and more preferably 15 min.
In the present invention, in step 5), the hydrothermal reaction comprises the following steps: transferring the liquorice residue porous carbon/nickel-cobalt hydrotalcite precursor liquid prepared in the step 4) to a stainless steel reaction kettle with a 100ml polytetrafluoroethylene lining, placing the reaction kettle in an air-blast drying oven for hydrothermal reaction, and performing post-treatment after the reaction kettle is completely cooled; the post-treatment comprises the following steps: leaching the licorice residue porous carbon/nickel-cobalt hydrotalcite precursor liquid subjected to the hydrothermal reaction by using a mixed solution of deionized water and ethanol.
In the invention, in the step 5), the temperature of the hydrothermal reaction is preferably 100-200 ℃, and more preferably 150-180 ℃; the time for the hydrothermal reaction is preferably 4 to 10 hours, and more preferably 5 to 8 hours.
The invention also provides the nickel-cobalt hydrotalcite composite material with the licorice root residue porous carbon as the substrate, which is prepared by the preparation method of the nickel-cobalt hydrotalcite composite material with the licorice root residue porous carbon as the substrate.
The invention also provides application of the nickel-cobalt hydrotalcite composite material taking the licorice root residue porous carbon as the substrate in an electrode material.
In the invention, the preparation method of the electrode material comprises the following steps: taking the nickel-cobalt-hydrotalcite composite material prepared in the step 5) and taking the licorice residue porous carbon as the substrate as an active material, respectively weighing the active material, acetylene black and polytetrafluoroethylene according to the mass ratio of 8:1:1, adding a small amount of ethanol for mixing, carrying out ultrasonic treatment on the mixed solution for 30min until the mixed solution is fully dispersed, uniformly dripping the mixed solution on a foamed nickel current collector by using a liquid transfer gun, and carrying out vacuum drying for 24h at 60 ℃ to obtain the electrode material.
The invention also provides application of the nickel-cobalt hydrotalcite composite material taking the licorice root residue porous carbon as the substrate in a super capacitor.
In the invention, the preparation method of the supercapacitor comprises the following steps: the electrode material prepared by taking the nickel-cobalt-hydrotalcite composite material with the licorice residue porous carbon as the substrate as the active material is taken as the anode material, the active carbon is taken as the cathode material, and 6M KOH solution is taken as the electrolyte, so that the asymmetric supercapacitor device is assembled.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The embodiment provides a method for preparing a nickel-cobalt hydrotalcite composite material by taking liquorice residue porous carbon as a substrate, which is applied to a super capacitor and comprises the following steps:
pre-carbonization of licorice root dregs
3g of liquorice dregs are weighed and put into a corundum boat, the corundum boat is put into a tube furnace, and the mixture is pre-carbonized for 2 hours at 650 ℃, and the heating rate is 5 ℃/min. And (3) taking out the corundum boat in the tube furnace after the tube furnace is completely cooled, fully leaching the product by deionized water and ethanol, and drying to obtain the licorice residue pre-carbonized powder.
2) Impregnation of carbonized product of licorice residue
According to the mass ratio of 3: 1.5g of KOH and 0.5g of licorice residue pre-carbonized powder prepared in the step 1) are respectively weighed, 20ml of deionized water is added and fully stirred for 4 hours until the KOH is completely dissolved and the licorice residue pre-carbonized powder is completely dispersed, the dispersion liquid is placed in a forced air drying oven and is soaked for 24 hours at the temperature of 80 ℃, and the licorice residue porous carbon precursor is obtained.
3) Activation of licorice root residue
Putting the licorice residue porous carbon precursor in the step 2) into a tube furnace, heating to 850 ℃ at a heating rate of 5 ℃/min, and carbonizing for 2 h. And (3) taking out the product after the tubular furnace is completely cooled, adjusting the pH value of the product to 7 by using 1M HCl solution, then fully leaching the product by using deionized water and ethanol, and drying the product to obtain the licorice residue porous carbon.
Example 2
1) Pre-carbonization of licorice root dregs
3g of liquorice dregs are weighed and put into a corundum boat, the corundum boat is put into a tube furnace, and the mixture is pre-carbonized for 2 hours at 650 ℃ with the heating rate of 5 ℃/min. And (3) taking out the corundum boat in the tube furnace after the tube furnace is completely cooled, fully leaching the product by deionized water and ethanol, and drying to obtain the licorice residue pre-carbonized product.
2) Carbonization of licorice residue
Putting the pre-carbonized product of the licorice dregs in the step 1) into a tubular furnace, heating to 850 ℃ at the heating rate of 5 ℃/min, and carbonizing for 2 h. And (3) taking out the product after the tubular furnace is completely cooled, adjusting the pH value of the product to 7 by using 1M HCl solution, then fully leaching the product by using deionized water and ethanol, and drying the product to obtain the unactivated licorice residue porous carbon.
The specific surface area analysis and comparison of example 1 and example 2 show that KOH as an activator can greatly increase the specific surface area. The composite material is synthesized by taking the embodiment 1 as the substrate, so that an ion transmission channel can be provided for the composite material in an electrochemical redox reaction, and the electrochemical performance is improved.
Example 3
Preparation of liquorice residue porous carbon/nickel-cobalt hydrotalcite precursor fluid
1) 0.5mmol CoCl was weighed in a molar ratio of 1:3:4, respectively2·5H2O、1.5mmol NiCl2·5H2O and 2mmol urea, 60ml deionized water was added and stirred well until the mixture was completely dissolved. And weighing 30mg of the porous carbon of the licorice root residue prepared in the example 1, adding the porous carbon of the licorice root residue into the mixed solution, and carrying out ultrasonic treatment for 15min to obtain the precursor body fluid of the porous carbon/nickel-cobalt hydrotalcite of the licorice root residue.
2) Preparation of liquorice medicine residue porous carbon/nickel-cobalt hydrotalcite composite material
Transferring the liquorice residue porous carbon/nickel-cobalt hydrotalcite precursor liquid prepared in the step 1) to a stainless steel reaction kettle with a 100ml polytetrafluoroethylene lining, and placing the reaction kettle in an air-blast drying oven for hydrothermal reaction for 4 hours at 160 ℃. And after the reaction kettle is completely cooled, taking out the reaction kettle, sufficiently leaching the reaction kettle with deionized water and ethanol, and drying to obtain the licorice residue porous carbon/nickel-cobalt hydrotalcite composite material.
Example 4
1) Preparation of nickel cobalt hydrotalcite precursor liquid
0.5mmol of CoCl is weighed respectively according to the mol ratio of 1:3:82·5H2O、1.5mmol NiCl2·5H2And adding 60ml of deionized water into the O and 4mmol of urea, and fully stirring until the mixture is dissolved to obtain the nickel-cobalt hydrotalcite precursor fluid.
2) Preparation of nickel cobalt hydrotalcite
Transferring the liquorice residue porous carbon/nickel-cobalt hydrotalcite precursor liquid prepared in the step 1) to a stainless steel reaction kettle with a 100ml polytetrafluoroethylene lining, and placing the reaction kettle in an air-blast drying oven for hydrothermal reaction for 4 hours at 160 ℃. And when the reaction kettle is completely cooled, taking out the reaction kettle, sufficiently leaching the reaction kettle with deionized water and ethanol, and drying to obtain the nickel-cobalt hydrotalcite.
Example 5
1) Preparation of liquorice residue porous carbon/nickel-cobalt hydrotalcite precursor fluid
0.5mmol CoCl is weighed respectively according to the molar ratio of 1:3:82·5H2O、1.5mmol NiCl2·5H2O and 4mmol urea, 60ml deionized water was added and stirred well until the mixture was completely dissolved. And weighing 30mg of the porous carbon of the licorice root residue prepared in the example 1, adding the porous carbon of the licorice root residue into the mixed solution, and carrying out ultrasonic treatment for 15min to obtain the precursor body fluid of the porous carbon/nickel-cobalt hydrotalcite of the licorice root residue.
2) Preparation of liquorice medicine residue porous carbon/nickel-cobalt hydrotalcite composite material
Transferring the liquorice residue porous carbon/nickel-cobalt hydrotalcite precursor liquid prepared in the step 1) to a stainless steel reaction kettle with a 100ml polytetrafluoroethylene lining, and placing the reaction kettle in an air-blast drying oven for hydrothermal reaction for 4 hours at 160 ℃. And after the reaction kettle is completely cooled, taking out the reaction kettle, sufficiently leaching the reaction kettle with deionized water and ethanol, and drying to obtain the licorice residue porous carbon/nickel-cobalt hydrotalcite composite material.
3) Preparation of electrode materials
Taking the nickel-cobalt-hydrotalcite composite material prepared in the step 2) and taking the licorice residue porous carbon as the substrate as an active material, respectively weighing 5mg of the active material, 1mg of acetylene black and 1 mul of polytetrafluoroethylene dispersion liquid with the mass fraction of 60% according to the mass ratio of 8:1:1, adding a small amount of ethanol for mixing, carrying out ultrasonic treatment on the mixed liquid for 30 minutes until the mixed liquid is fully dispersed, uniformly and dropwisely coating the mixed liquid on a foamed nickel current collector with the thickness of 1cm multiplied by 1cm by using a liquid transfer gun, and carrying out vacuum drying for 24 hours at the temperature of 60 ℃.
4) Synthesis of asymmetric super capacitor
And (3) packaging the complete asymmetric super capacitor device in a button battery shell, and assembling the asymmetric super capacitor device by adopting the electrode material prepared in the step 3) as a positive electrode material, the activated carbon as a negative electrode material and the 6M KOH solution as an electrolyte.
The electrode material prepared in each example was used as a working electrode, a 1cm × 1cm platinum sheet was used as a counter electrode, Hg/HgO was used as a reference electrode to construct a three-electrode system, and a cyclic voltammetry test, a constant current charge and discharge test, and an alternating current impedance test were performed on an electrochemical workstation CHI760E, respectively, and a cyclic stability test was performed.
From the comparison between example 5 and example 3, the charging and discharging time of the nickel-cobalt hydrotalcite based on the porous carbon of the licorice residue is significantly improved compared with that of pure nickel-cobalt hydrotalcite. The composite material is synthesized by taking the liquorice residue porous carbon as the substrate, so that an ion transmission channel and a charge storage space can be provided for the composite material in electrochemical redox reaction, and the discharge time is prolonged, so that the electrochemical performance is improved.
From the comparison of example 5 with example 4, it can be seen that the increase in urea in a certain range favors the formation of the complete nickel cobalt hydrotalcite. However, too high urea levels promote the conversion of nickel cobalt hydrotalcite to Ni (HCO)3)2Thereby affecting the redox reaction of the electrode material during the charge and discharge processes, resulting in a difference in specific capacitance.
As can be seen from fig. 1, as the scanning rate increases, the cathode peak moves to the low point position, and the anode peak is reversed. This result may be due to the polarization of the electrodes at high scanning speeds. Particularly, under different scanning speeds, the cyclic voltammetry curve still keeps unchanged, which shows that the cyclic voltammetry curve has excellent rate capability; the composite material obtained by the invention has excellent electrochemical reversibility; after 2000 times of cycle tests, the specific capacitance can still keep 87% of the initial capacitance, and the cycling stability is excellent.
As can be seen from figure 2, the licorice residue porous carbon synthesized by the invention shows a good interconnected hierarchical porous framework, and the size of the macropores of the licorice residue porous carbon is 200 nm-2 μm. It was observed that porous carbon pore walls separate adjacent pores, while the presence of this structure also favors ion penetration; the synthesized licorice residue porous carbon/nickel-cobalt hydrotalcite composite material presents a sheet structure. As the urea content increases, the structure of the composite becomes more complete and refined.
As can be seen from FIG. 3, the porous carbon/nickel-cobalt hydrotalcite from the licorice root residue can be classified as alpha-NiCo LDH, and no other peak is observed, which indicates that the high-purity porous carbon/nickel-cobalt hydrotalcite composite material from the licorice root residue is synthesized. In addition, the licorice residue porous carbon/nickel-cobalt hydrotalcite composite material does not show any carbon diffraction peak, which is probably because the thick nickel-cobalt hydrotalcite shell layer is arranged around the licorice residue porous carbon to form a closed core-shell structure material.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of a nickel-cobalt hydrotalcite composite material taking licorice residue porous carbon as a substrate is characterized by comprising the following steps:
1) sequentially pre-carbonizing the licorice dregs, post-treating and drying to obtain licorice dreg pre-carbonized powder;
2) mixing KOH, the pre-carbonized powder of the licorice dregs prepared in the step 1) and deionized water, and then dipping to obtain a porous carbon precursor of the licorice dregs;
3) sequentially carbonizing, post-treating and drying the licorice residue porous carbon precursor in the step 2) to obtain licorice residue porous carbon;
4) adding CoCl2·5H2O、NiCl2·5H2Mixing O, urea, deionized water and the licorice root residue porous carbon prepared in the step 3) to obtain licorice root residue porous carbon/nickel-cobalt hydrotalcite precursor fluid;
5) and 4) sequentially carrying out hydrothermal reaction on the licorice residue porous carbon/nickel-cobalt hydrotalcite precursor liquid prepared in the step 4), carrying out post-treatment, and drying to obtain the licorice residue porous carbon/nickel-cobalt hydrotalcite composite material.
2. The preparation method of the nickel-cobalt hydrotalcite composite material based on the porous carbon of the licorice root residue as the substrate according to claim 1, wherein in the step 1), the pre-carbonization temperature is 600-700 ℃, the pre-carbonization time is 2-3 h, and the pre-carbonization temperature rise rate is 2-8 ℃/min; the post-treatment comprises the following steps: and leaching the pre-carbonized licorice dregs by using a mixed solution of deionized water and ethanol.
3. The preparation method of the nickel-cobalt hydrotalcite composite material with the licorice residue porous carbon as the substrate according to claim 2, wherein in the step 2), the mass ratio of the KOH to the licorice residue pre-carbonized powder prepared in the step 1) is 2-4: 1, the mass-to-volume ratio of KOH to deionized water is 2-4 g: 20 mL; stirring and mixing are adopted for mixing, and the mixing time is 2-6 h; the dipping temperature is 60-100 ℃, and the dipping time is 20-24 hours.
4. The preparation method of the nickel-cobalt hydrotalcite composite material with the licorice residue porous carbon as the substrate according to claim 2 or 3, wherein in the step 3), the carbonization comprises the following steps: placing the licorice residue porous carbon precursor in the step 2) in a tubular furnace, heating to 800-900 ℃ at a heating rate of 2-8 ℃/min, and carbonizing for 2-2.5 h; the post-treatment comprises the following steps: and (3) regulating the PH value of the carbonized licorice residue porous carbon precursor to 6-8 by using 1-1.5M HCl solution, and then fully leaching by using deionized water and ethanol.
5. The method for preparing the nickel-cobalt hydrotalcite composite material based on the porous carbon of the licorice root residue according to claim 1, wherein in the step 4), the CoCl is added2·5H2O、NiCl2·5H2The mass ratio of O to urea is 1: 2-4: 2-8, and the mass volume ratio of urea to deionized water is 120-481 g: 60mL, wherein the mass ratio of the liquorice residue porous carbon prepared in the step 3) to urea is 0.02-0.04: 120 to 481.
6. The preparation method of the nickel-cobalt hydrotalcite composite material with the licorice residue porous carbon as the substrate according to claim 5, wherein in the step 5), the temperature of the hydrothermal reaction is 100-200 ℃, and the time of the hydrothermal reaction is 4-10 h; the post-treatment comprises the following steps: leaching the licorice residue porous carbon/nickel-cobalt hydrotalcite precursor liquid subjected to the hydrothermal reaction by using a mixed solution of deionized water and ethanol.
7. The nickel-cobalt hydrotalcite composite material with the licorice root residue porous carbon as the substrate, which is prepared by the preparation method of the nickel-cobalt hydrotalcite composite material with the licorice root residue porous carbon as the substrate, according to any one of claims 1 to 6.
8. The application of the nickel-cobalt hydrotalcite composite material taking the licorice root residue porous carbon as the substrate in the electrode material is disclosed in claim 7.
9. The application of the nickel-cobalt hydrotalcite composite material taking the liquorice residue porous carbon as the substrate in the supercapacitor is disclosed in claim 7.
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