CN116364449A - Preparation method of cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon electrode material for super capacitor - Google Patents
Preparation method of cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon electrode material for super capacitor Download PDFInfo
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- CN116364449A CN116364449A CN202310388701.6A CN202310388701A CN116364449A CN 116364449 A CN116364449 A CN 116364449A CN 202310388701 A CN202310388701 A CN 202310388701A CN 116364449 A CN116364449 A CN 116364449A
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- enzymatic hydrolysis
- manganese sulfide
- nickel manganese
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229920005610 lignin Polymers 0.000 title claims abstract description 99
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 96
- MBUJIFHANTWAKB-UHFFFAOYSA-N [S-2].[Mn+2].[Co+2].[Ni+2].[S-2].[S-2] Chemical compound [S-2].[Mn+2].[Co+2].[Ni+2].[S-2].[S-2] MBUJIFHANTWAKB-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 230000007071 enzymatic hydrolysis Effects 0.000 title claims abstract description 61
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 52
- 239000007772 electrode material Substances 0.000 title claims abstract description 32
- 239000003990 capacitor Substances 0.000 title claims abstract description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 19
- 238000003763 carbonization Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 34
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 26
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 15
- 229940011182 cobalt acetate Drugs 0.000 claims description 15
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 15
- 229940078494 nickel acetate Drugs 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 229940071125 manganese acetate Drugs 0.000 claims description 13
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 11
- 239000012498 ultrapure water Substances 0.000 claims description 11
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- 108091022623 Formins Proteins 0.000 claims description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 2
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- KAEHZLZKAKBMJB-UHFFFAOYSA-N cobalt;sulfanylidenenickel Chemical compound [Ni].[Co]=S KAEHZLZKAKBMJB-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 18
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- 230000004913 activation Effects 0.000 abstract 1
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- 239000012535 impurity Substances 0.000 description 9
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000002041 carbon nanotube Substances 0.000 description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 description 8
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- 229910052723 transition metal Inorganic materials 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- -1 transition metal sulfide Chemical class 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- LXKIIAIRNCIFBQ-UHFFFAOYSA-N [S].[Co].[Mn].[Ni] Chemical compound [S].[Co].[Mn].[Ni] LXKIIAIRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
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- 229910001453 nickel ion Inorganic materials 0.000 description 1
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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
-
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- 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, 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
- H01G11/40—Fibres
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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 discloses a preparation method of a cobalt nickel manganese sulfide/enzymolysis lignin carbon electrode material for a supercapacitor, and belongs to the field of electrochemistry. The invention adopts the following technical scheme: firstly, preparing an enzymolysis lignin carbon material by using a potassium hydroxide activation carbonization method, and then preparing a cobalt nickel manganese sulfide/enzymolysis lignin carbon composite material by using a solvothermal method. The invention adopts the enzymolysis lignin as the carbon precursor, has high carbon content, is widely derived from natural plants, has rich reserves, can obviously reduce the preparation cost when being applied to the super capacitor, and meets the long-term targets of green environmental protection and sustainable development. In addition, the cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon composite material prepared by adopting the solvothermal method combines the advantages of high specific capacitance of the transition metal compound and good conductivity of the enzymatic hydrolysis lignin carbon, and the obtained composite material has good conductivity, excellent electrochemical performance, strong overall stability, simple preparation process, low energy consumption and safer process. The invention provides a new thought and a method for producing the enzymatic hydrolysis lignin carbon-based electrode material with good electrical property, and is expected to be widely applied to electrode materials of super capacitors and even other energy storage devices.
Description
Technical Field
The invention relates to the field of electrochemistry, in particular to a preparation method of a cobalt nickel manganese sulfide/enzymolysis lignin carbon electrode material for a supercapacitor.
Background
Supercapacitors (Supercapacitors) serve as a new type of energy storage device. The super capacitor electrode material has a plurality of types, such as carbon materials, conductive polymers, metal oxides, composite materials and the like, and plays a vital role in the capacitance performance of the super capacitor. These carbon materials are mostly prepared from coal or fossil petroleum materials, which are not renewable and sustainable. Therefore, enzymatic lignin has attracted research attention as a carbon material precursor due to reproducibility, low cost and biodegradability. Surprisingly, lignin has high carbon content and good thermal stability, and thus, the production of supercapacitors using lignin has been widely studied. On the other hand, since transition metals have various oxidation states, have good conductivity and high specific capacitance, various compounds of transition metals and other composite materials have been widely used for electrode materials. The better conductivity and higher electrochemical activity of the transition metal sulfide electrodes compared to metal oxides and hydroxides greatly improves their redox kinetics as electrodes, and their rich and controllable microscopic morphology and structure ensures rapid electron conduction and ion transport. The conductivity of nickel cobalt manganese sulfide is about 2 orders of magnitude higher than its metal oxide. More importantly, due to the synergistic effect and complementary advantages of nickel ions, cobalt ions and manganese ions, the material has good electrochemical performance. Therefore, the composite electrode material prepared by combining the carbon material and the nickel-cobalt-manganese sulfide is applied to the supercapacitor, and the advantages of different materials can be simultaneously exerted, so that the overall performance of the supercapacitor is improved. Meanwhile, the method has important significance for building an environment-friendly and resource-saving society.
Disclosure of Invention
The invention aims to solve the problems of the background technology and provides a preparation method of a cobalt nickel manganese sulfide/enzymolysis lignin carbon electrode material for a supercapacitor.
In order to achieve the above purpose, the invention provides a cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon electrode material for a supercapacitor and a preparation method thereof, wherein the preparation method of the cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon electrode for the supercapacitor comprises the following steps:
step S1 is executed: preparation of enzymatic hydrolysis lignin carbon material
Dissolving the enzymatic hydrolysis lignin in potassium hydroxide solution, stirring for 1h, performing ultrasonic treatment for 1h, and drying in a drying oven; grinding after drying, carbonizing, washing with hydrochloric acid, and drying to obtain enzymatic lignin carbon;
step S2 is executed: preparation of cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon material
And (3) dissolving the enzymatic hydrolysis lignin carbon obtained in the step (S1), nickel acetate, cobalt acetate and manganese acetate in ethylene glycol together, stirring for 3 hours, transferring to a high-pressure reaction kettle, centrifuging after reaction to obtain a precipitate, washing with ultrapure water and absolute ethyl alcohol for multiple times, and drying to obtain a cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon sample.
Based on the technical scheme, in the step (1), the ratio of the lignin to the potassium hydroxide is 1:1-1:3.
Based on the technical scheme, in the step (1), the drying temperature is 80-100 ℃.
Based on the above technical solution, in step (1), further, the carbonization conditions are: the temperature is 600-800 ℃ and the heat preservation time is 2-3 hours.
Based on the technical proposal, in the step (1), the carbonization condition is performed under the protection of nitrogen, and the temperature rising rate is 1-10 ℃ for min -1 。
Based on the technical proposal, in the step (1), the concentration of the hydrochloric acid solution is 3 to 6mol L -1 。
Based on the technical scheme, in the step (2), the amount of nickel acetate in the mixed solution of nickel acetate and cobalt acetate is 1-2 mmol, the amount of cobalt acetate is 2-4 mmol, the amount of manganese acetate is 0.1-1 mmol, the amount of thiourea is 4-10 mmol, and the mass of the enzymatic hydrolysis lignin carbon is 10-100 mg.
Based on the technical scheme, in the step (2), the solvothermal temperature is 120-200 ℃.
Based on the technical scheme, in the step (2), the drying temperature is 60-80 ℃.
An electrode material for super capacitor of cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon, characterized in that it is prepared by the method of any one of the above claims 1-9.
Compared with the prior art, the invention has the following advantages:
(1) The invention selects the enzymolysis lignin as the carbon precursor, the raw materials are widely derived from natural plants, the cost is low, the preparation cost can be obviously reduced when the enzymolysis lignin is applied to the super capacitor, and the enzymolysis lignin meets the long-term targets of green environmental protection and sustainable development. Meanwhile, the enzymatic hydrolysis lignin has a natural porous structure, and the prepared enzymatic hydrolysis lignin carbon contains rich macropores, mesopores and micropores, and has large specific surface area, so that compared with other carbon materials, the electrode material prepared by the enzymatic hydrolysis lignin carbon has excellent overall performance.
(2) The method for preparing the cobalt nickel manganese sulfide/enzymolysis lignin carbon composite material by the solvothermal method is simple, low in energy consumption and easy to regulate and control the microstructure, the particle size distribution and the dispersibility.
(3) The cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon composite material prepared by the invention combines the advantages of high specific capacitance of transition metal compounds and good conductivity of enzymatic hydrolysis lignin carbon, and the large specific surface area of the enzymatic hydrolysis lignin carbon can obviously improve the condition that cobalt nickel manganese sulfide is easy to agglomerate, effectively improves the microscopic morphology of the cobalt nickel manganese sulfide, and is beneficial to improving the electrochemical performance and the cycling stability of the composite electrode material. The nickel-cobalt-manganese-based trimetallic sulfide is adopted to provide pseudo-capacitance, has good electrochemical reactivity and high specific capacitance, and combines the advantages of the carbon-based material and the nickel-cobalt-manganese-based trimetallic sulfide.
Drawings
FIG. 1 is an X-ray diffraction pattern of the cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon composite material prepared in example 1 as an electrode material.
FIG. 2 is a scanning electron microscope spectrum of the cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon composite material prepared in example 1 as an electrode material.
FIG. 3 shows that the cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon composite material prepared in example 1 is used as an electrode material at 6 mol.L 1 Cyclic voltammograms at different scan rates in KOH electrolyte.
FIG. 4 shows that the cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon composite material prepared in example 1 is used as an electrode material at 6mol L 1 Constant current charge and discharge curves at different current densities in the KOH electrolyte.
FIG. 5 shows that the cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon composite material prepared in example 1 is used as an electrode material at 6 mol.L 1 Ac impedance plot in KOH electrolyte.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and are all performed in accordance with the operation or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagents available commercially without the manufacturer's knowledge.
In order to more intuitively disclose the technical scheme of the invention and highlight the beneficial effects of the invention, the electrochemical performance and the like of the invention based on cobalt sulfide nickel manganese/enzymatic hydrolysis lignin carbon are described by combining the specific embodiments.
As a specific embodiment, in step S1, preparing an enzymatic lignin carbon material, further includes:
step S11 is performed: adopting enzymolysis lignin as a carbon material, and taking lignin: potassium hydroxide=1:2 ratio, dissolved in water, stirred for 1h, sonicated for 1h, in oven at 110 ℃ overnight;
step S12 is performed: drying the above sample at 5deg.C in nitrogen atmosphere for min -1 Is maintained at 800 ℃ for 3 hours;
step S13 is performed: after carbonization, the sample obtained was subjected to a reaction with 6mol L -1 Is soaked by HCl;
step S14 is performed: washing the sample with deionized water to neutrality, and drying for use.
In step S2, the preparation of the cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon sample and the electrode further includes:
step S21 is performed: the preparation of the precursor solution specifically comprises the following steps: firstly, weighing nickel acetate, cobalt acetate, manganese acetate and thiourea, ultrasonically dissolving in 40ml of ethylene glycol, weighing 30mg of enzymolysis lignin carbon, adding into the solution, and uniformly stirring;
step S22 is performed: transferring the solution into a 100ml high-pressure reaction kettle for reaction, naturally cooling to room temperature, separating by a centrifuge to obtain precipitate, washing by ultrapure water and absolute ethyl alcohol for multiple times, and removing surface impurities. And drying the solid product at 60 ℃ for 12 hours to obtain a cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon sample.
Example 1
Step S1 is executed: preparation of enzymatic hydrolysis lignin carbon material
Step S11 is performed: adopting enzymolysis lignin as a carbon material, and taking lignin: potassium hydroxide=1:2 ratio, dissolved in water, stirred for 1h, sonicated for 1h, in oven at 110 ℃ overnight;
step S12 is performed: drying the above sample at 5deg.C in nitrogen atmosphere for min -1 Is maintained at 800 ℃ for 3 hours;
step S13 is performed: after carbonization, the sample obtained was subjected to a reaction with 6mol L -1 Is soaked by HCl;
step S14 is performed: the sample was washed to neutrality with deionized water and dried at 80 ℃.
Step S2 is executed: preparation of cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon
Step S21 is performed: the preparation of the precursor solution specifically comprises the following steps: firstly, 0.92mmol of nickel acetate, 1.83mmol of cobalt acetate, 0.25mmol of manganese acetate and 10mmol of thiourea are weighed and ultrasonically dissolved in 40ml of ethylene glycol, 30mg of enzymolysis lignin carbon is weighed and added into the solution, and the solution is stirred uniformly.
Step S22 is performed: transferring the solution to a 100ml reaction kettle for reaction for 6 hours at 180 ℃, cooling to room temperature, separating by a centrifuge to obtain precipitate, washing by ultrapure water and absolute ethyl alcohol for multiple times, and removing surface impurities. And drying the solid product at 60 ℃ for 12 hours to obtain a cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon sample.
Example 2
Step S1 is executed: preparation of enzymatic hydrolysis lignin carbon material
Step S11 is performed: adopting enzymolysis lignin as a carbon material, and taking lignin: potassium hydroxide=1:2 ratio, dissolved in water, stirred for 1h, sonicated for 1h, in oven at 110 ℃ overnight;
step S12 is performed: drying the above sample at 5deg.C in nitrogen atmosphere for min -1 Is maintained at 800 ℃ for 3 hours;
step S13 is performed: after carbonization, the sample obtained was subjected to a reaction with 6mol L -1 Is soaked by HCl;
step S14 is performed: the sample was washed to neutrality with deionized water and dried at 80 ℃.
Step S2 is executed: preparation of cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon
Step S21 is performed: the preparation of the precursor solution specifically comprises the following steps: firstly, 0.92mmol of nickel acetate, 1.83mmol of cobalt acetate, 0.25mmol of manganese acetate and 10mmol of thiourea are weighed and ultrasonically dissolved in 40ml of ethylene glycol, 50mg of enzymolysis lignin carbon is weighed and added into the solution, and the solution is stirred uniformly.
Step S22 is performed: transferring the solution to a 100ml reaction kettle for reaction for 6 hours at 180 ℃, cooling to room temperature, separating by a centrifuge to obtain precipitate, washing by ultrapure water and absolute ethyl alcohol for multiple times, and removing surface impurities. And drying the solid product at 60 ℃ for 12 hours to obtain a cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon sample.
Example 3
Step S1 is executed: preparation of enzymatic hydrolysis lignin carbon material
Step S11 is performed: adopting enzymolysis lignin as a carbon material, and taking lignin: potassium hydroxide=1:2 ratio, dissolved in water, stirred for 1h, sonicated for 1h, in oven at 110 ℃ overnight;
step S12 is performed: drying the above sample at 5deg.C in nitrogen atmosphere for min -1 Is maintained at 800 ℃ for 3 hours;
step S13 is performed: after carbonization, the sample obtained was subjected to a reaction with 6mol L -1 Is soaked by HCl;
step S14 is performed: the sample was washed to neutrality with deionized water and dried at 80 ℃.
Step S2 is executed: preparation of cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon
Step S21 is performed: the preparation of the precursor solution specifically comprises the following steps: firstly, 0.92mmol of nickel acetate, 1.83mmol of cobalt acetate, 0.25mmol of manganese acetate and 10mmol of thiourea are weighed and ultrasonically dissolved in 40ml of ethylene glycol, 70mg of enzymolysis lignin carbon is weighed and added into the solution, and the solution is stirred uniformly.
Step S22 is performed: transferring the solution to a 100ml reaction kettle for reaction for 6 hours at 180 ℃, cooling to room temperature, separating by a centrifuge to obtain precipitate, washing by ultrapure water and absolute ethyl alcohol for multiple times, and removing surface impurities. And drying the solid product at 60 ℃ for 12 hours to obtain a cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon sample.
A method for preparing a finished electrode of cobalt nickel manganese sulfide/enzymatically hydrolyzed lignin carbon for a supercapacitor of claim 1, comprising:
step S1 is executed: treating the current collector, cutting the conductive substrate foam nickel into 1cm 2 Then sequentially with acetone and 3mol L -1 Ultrasonic cleaning with hydrochloric acid, absolute ethanol and deionized water for 15min, and drying at 60deg.C for 12 hr.
Step S2 is executed: the active substances (cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon), the conductive agent (acetylene black) and the binder (polytetrafluoroethylene concentrated solution (10 wt%)) are respectively weighed according to the mass ratio of 80:10:10, are mixed into uniform solid by absolute ethyl alcohol, are coated on clean and dry foam nickel (the coating amount of the active substances is generally about 3 mg), are dried in vacuum at 60 ℃ for 12 hours, and are tabletted under 10MPa, so that the working electrode is obtained.
Comparative example 1
Step S1 is executed: in this comparative example, commercial petroleum coke-based activated carbon was used as the carbon source and had a specific surface area of 3122m 2 /g; in the pore size distribution, micropores smaller than 2nm account for 89%; the remainder being mesopores greater than 2nm and less than 50 nm.
Step S2 is executed: preparation of cobalt nickel manganese sulfide/petroleum coke based activated carbon
Step S21 is performed: the preparation of the precursor solution specifically comprises the following steps: firstly, weighing 100mg of petroleum coke-based active carbon, adding the petroleum coke-based active carbon into 40ml of ethylene glycol, and uniformly stirring; then, 0.92mmol of nickel acetate, 1.83mmol of cobalt acetate, 0.25mmol of manganese acetate and 10mmol of thiourea were weighed and stirred for 30min to obtain a uniformly mixed solution.
Step S22 is performed: transferring the solution to a 100ml reaction kettle for reaction for 6 hours at 180 ℃, cooling to room temperature, separating by a centrifuge to obtain precipitate, washing by ultrapure water and absolute ethyl alcohol for multiple times, and removing surface impurities. And (3) carrying out vacuum drying on the solid product at 60 ℃ for 12 hours to obtain a cobalt nickel manganese sulfide/petroleum coke-based activated carbon sample.
A preparation method of a finished electrode of cobalt nickel manganese sulfide/petroleum coke based active carbon for a supercapacitor comprises the following steps:
step S1 is executed: the preparation procedure is as in example 1.
Step S2 is executed: the active material is cobalt nickel manganese sulfide/petroleum coke based active carbon, and other preparation processes are the same as in example 1.
Comparative example 2
Step S1 is executed: in this comparative example, commercial mesophase carbon microbeads were used as the carbon source.
Step S2 is executed: preparation of cobalt nickel manganese sulfide/mesophase carbon microsphere
Step S21 is performed: the preparation of the precursor solution specifically comprises the following steps: firstly, weighing 100mg of mesophase carbon microspheres, adding the mesophase carbon microspheres into 40ml of ethylene glycol, and uniformly stirring; then, 0.92mmol of nickel acetate, 1.83mmol of cobalt acetate, 0.25mmol of manganese acetate and 10mmol of thiourea were weighed and stirred for 30min to obtain a uniformly mixed solution.
Step S22 is performed: transferring the solution to a 100ml reaction kettle for reaction for 6 hours at 180 ℃, cooling to room temperature, separating by a centrifuge to obtain precipitate, washing by ultrapure water and absolute ethyl alcohol for multiple times, and removing surface impurities. And (3) drying the solid product in vacuum at 60 ℃ for 12 hours to obtain a cobalt nickel manganese sulfide/mesophase carbon microsphere sample.
A preparation method of a finished electrode of cobalt nickel manganese sulfide/mesophase carbon microsphere for a supercapacitor comprises the following steps:
step S1 is executed: the preparation procedure is as in example 1.
Step S2 is executed: the active material is cobalt nickel manganese sulfide/mesophase carbon microsphere, and other preparation processes are the same as in example 1.
Comparative example 3
Step S1 is executed: in this comparative example, commercial carbon cloth was used as a carbon source. The carbon cloth was cut to a size of 1cm×2cm, immersed in concentrated nitric acid for 12 hours, washed three times, and dried.
Step S2 is executed: preparation of cobalt nickel manganese sulfide/carbon cloth
Step S21 is performed: the preparation of the precursor solution specifically comprises the following steps: firstly, taking 3 pieces of treated carbon cloth, and adding the carbon cloth into 40ml of ethylene glycol; then, 0.92mmol of nickel acetate, 1.83mmol of cobalt acetate, 0.25mmol of manganese acetate and 10mmol of thiourea were weighed and stirred for 30min to obtain a uniformly mixed solution.
Step S22 is performed: transferring the solution to a 100ml reaction kettle for reaction for 6 hours at 180 ℃, cooling to room temperature, separating by a centrifuge to obtain precipitate, washing by ultrapure water and absolute ethyl alcohol for multiple times, and removing surface impurities. And (3) carrying out vacuum drying on the solid product at 60 ℃ for 12 hours to obtain a cobalt nickel manganese sulfide/carbon cloth sample.
A preparation method of a finished electrode of cobalt nickel manganese sulfide/carbon cloth for a supercapacitor comprises the following steps:
step S1 is executed: the preparation procedure is as in example 1.
Step S2 is executed: the active material is cobalt nickel manganese sulfide/carbon cloth, and other preparation processes are the same as in example 1.
Comparative example 4
Step S1 is executed: in this comparative example, commercial carbon nanotubes were used as a carbon source.
Step S2 is executed: preparation of cobalt nickel manganese sulfide/carbon nano tube
Step S21 is performed: the preparation of the precursor solution specifically comprises the following steps: firstly, weighing 100mg of carbon nano tubes, adding the carbon nano tubes into 40ml of ethylene glycol, and uniformly stirring; then, 0.92mmol of nickel acetate, 1.83mmol of cobalt acetate, 0.25mmol of manganese acetate and 10mmol of thiourea were weighed and added to the above solution, and stirring was continued in a water bath at 50℃for 30 minutes to obtain a uniformly mixed solution.
Step S22 is performed: transferring the solution to a 100ml reaction kettle for reaction for 6 hours at 180 ℃, cooling to room temperature, separating by a centrifuge to obtain precipitate, washing by ultrapure water and absolute ethyl alcohol for multiple times, and removing surface impurities. And (3) drying the solid product in vacuum at 60 ℃ for 12 hours to obtain a cobalt nickel manganese sulfide/carbon nanotube sample.
A method for preparing a finished electrode of cobalt nickel manganese sulfide/carbon nano tube for a super capacitor, comprising the following steps:
step S1 is executed: the preparation procedure is as in example 1.
Step S2 is executed: the active material is cobalt nickel manganese sulfide/carbon nano tube, and other preparation processes are the same as in example 1.
Comparative example 5
Step S1 is executed: preparation of graphene oxide
Step S11 is performed: 2g of graphene raw material is placed in a 500mL beaker, 35mL of concentrated sulfuric acid (with a concentration of 98%) is added into the beaker, and the mixture is stirred for 2h.
Step S12 is performed: 8g of potassium permanganate (analytically pure) was weighed, then slowly added to the above mixed solution while stirring, and after the completion of this, the beaker was placed in a 35℃thermostat water bath for reaction for 6 hours.
Step S13 is performed: adding 100mL of deionized water, continuously stirring for 30min, adding 20mL of 30% hydrogen peroxide, stirring for 30min, finally adding 30mL of concentrated hydrochloric acid and 200mL of deionized water, stirring for 30min, and removing residual substances in the solution.
Step S14 is performed: washing with deionized water to neutrality, freezing and agglomerating the obtained precipitate in a refrigerator, and freeze-drying for 24h to obtain graphene oxide powder.
Step S2 is executed: preparation of cobalt nickel manganese sulfide/graphene oxide
Step S21 is performed: the preparation of the precursor solution specifically comprises the following steps: firstly, weighing 100mg of graphene oxide, adding the graphene oxide into 40ml of ethylene glycol, and uniformly stirring; then, 0.92mmol of nickel acetate, 1.83mmol of cobalt acetate, 0.25mmol of manganese acetate and 10mmol of thiourea were weighed and added to the above solution, and stirring was continued in a water bath at 50℃for 30 minutes to obtain a uniformly mixed solution.
Step S22 is performed: transferring the solution to a 100ml reaction kettle for reaction for 6 hours at 180 ℃, cooling to room temperature, separating by a centrifuge to obtain precipitate, washing by ultrapure water and absolute ethyl alcohol for multiple times, and removing surface impurities. And (3) carrying out vacuum drying on the solid product at 60 ℃ for 12 hours to obtain a cobalt nickel manganese sulfide/graphene oxide sample.
A preparation method of a finished electrode of cobalt nickel manganese sulfide/graphene oxide for a supercapacitor comprises the following steps:
step S1 is executed: the preparation procedure is as in example 1.
Step S2 is executed: the active material is cobalt nickel manganese sulfide/graphene oxide, and other preparation processes are the same as in example 1.
For further explanation of the present invention, the materials prepared in example 1 were tested and electrochemically tested, and the results are shown in Table 1 and the accompanying drawings.
Wherein, fig. 1 is an X-ray diffraction pattern of cobalt-nickel-manganese sulfide/enzymatic hydrolysis lignin carbon prepared by a solvothermal method in example 1, and the test result shows that the diffraction peak of cobalt-nickel-manganese sulfide is obvious, which indicates that the cobalt-nickel-manganese sulfide/enzymatic hydrolysis lignin carbon composite material is successfully synthesized.
FIG. 2 is a graph of a-b Scanning Electron Microscope (SEM) of cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon prepared by a solvothermal method in example 1. FIGS. 2a-b show that the enzymatically hydrolyzed lignin carbon exhibits a rich three-dimensional layered porous structure with cobalt nickel manganese sulfide nanoparticles uniformly grown on the surface of a carbon matrix, as shown in FIG. 2, the enzymatically hydrolyzed lignin carbon as a matrix to support cobalt nickel manganese sulfide and prevent aggregation of the nano-components, enabling the electrolyte to diffuse easily in a stable carbon matrix, thereby significantly improving electrochemical performance.
FIG. 3 is a cyclic voltammogram of cobalt nickel manganese sulfide/enzymatically hydrolyzed lignin char at various scan rates using the solvothermal method of example 1, showing significant redox peaks with increasing scan rate, indicating good electrochemical performance.
Fig. 4 is a graph of the charge and discharge patterns of cobalt nickel manganese sulfide/enzymatically hydrolyzed lignin carbon prepared in example 1 using a solvothermal method at different scanning current densities, all of which show approximately symmetrical characteristic shapes, indicating excellent reversibility and good coulombic efficiency of the electrode. At 1, 2, 5, 10 and 20A g -1 The specific capacitance values are 1220, 1168, 1058, 867.2 and 627.2F g respectively -1 。
Fig. 5 is an ac impedance spectrum of the cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon prepared by the solvothermal method in example 1, in which it can be seen that the charge transfer resistance of the composite material is very small, indicating that the electron charge transfer process is faster.
As can be seen from table 1, the cobalt nickel manganese sulfide/enzymatic lignin char (example 1) prepared by the simple coprecipitation method has a high specific capacitance and excellent electrochemical properties. The enzymatic hydrolysis lignin carbon can provide larger specific surface area, can obviously improve the condition that cobalt sulfide, nickel and manganese are easy to agglomerate, and is beneficial to improving the electrochemical performance of the composite electrode material. In addition, nickel, cobalt and manganese have synergistic effect, and the composite electrode material can provide a larger diffusion coefficient, is favorable for intercalation and deintercalation of anions and cations in electrolyte, promotes the transmission of ions in the electrode, accelerates the oxidation-reduction reaction of electroactive substances and is more favorable for energy storage. The coprecipitation method has the advantages of simple preparation process, low energy consumption and safer process. The invention selects the enzymolysis lignin as the carbon precursor, has wide raw material sources and low cost, can obviously reduce the preparation cost when being applied to the super capacitor, and more highlights the advantage of green energy.
It will be appreciated by those skilled in the art that various modifications and variations can be made to the invention without departing from the spirit or scope of the invention. Accordingly, the present invention is deemed to cover any modifications and variations, if they fall within the scope of the appended claims and their equivalents.
Table 1 list of electrochemical properties of examples 1 to comparative example 5
| Electrode material | Electrolyte solution | Specific capacitance (F/g) | |
| Example 1 | Cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon | 6M KOH | 1220 |
| Example 2 | Cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon | 6M KOH | 890 |
| Example 3 | Cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon | 6M KOH | 690 |
| Comparative example 1 | Cobalt nickel manganese sulfide/petroleum coke based activated carbon | 6M KOH | 415 |
| Comparative example 2 | Cobalt nickel manganese sulfide/mesophase carbon microsphere | 6M KOH | 512 |
| Comparative example 3 | Cobalt nickel manganese sulfide/carbon cloth | 6M KOH | 625 |
| Comparative example 4 | Cobalt nickel manganese sulfide/carbon nano tube | 6M KOH | 714 |
| Comparative example 5 | Cobalt nickel manganese sulfide/oxygenChemical graphene | 6M KOH | 1008 |
Claims (10)
1. The preparation method of the cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon electrode material for the super capacitor is characterized by comprising the following steps of:
(1) Preparing an enzymolysis lignin carbon material:
dissolving the enzymatic hydrolysis lignin in potassium hydroxide solution, stirring for 1h, performing ultrasonic treatment for 1h, and drying in a drying oven; grinding after drying, carbonizing, washing with hydrochloric acid, and drying to obtain enzymatic lignin carbon;
(2) Preparing cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon material:
and (3) dissolving the enzymatic hydrolysis lignin carbon obtained in the step (1), nickel acetate, cobalt acetate, manganese acetate and thiourea in ethylene glycol together, ultrasonically stirring to obtain a uniform solution, transferring the uniform solution into a high-pressure reaction kettle for reaction, washing the centrifuged solid with ultrapure water and absolute ethyl alcohol for multiple times, and drying to obtain a cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon sample.
2. The method for preparing the cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon electrode material for the supercapacitor according to claim 1, wherein in the step (1), the ratio of lignin to potassium hydroxide is 1:1-1:3.
3. The method for preparing the cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon electrode material for the super capacitor according to claim 1, wherein in the step (1), the drying temperature is 80-100 ℃.
4. The method for preparing cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon electrode material for super capacitor according to claim 1, wherein in the step (1), the carbonization conditions are as follows: the temperature is 600-800 ℃ and the heat preservation time is 2-3 hours.
5. The method for preparing cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon electrode material for super capacitor as claimed in claim 1, wherein in step (1), the carbonization is performed under nitrogen protection, and the heating rate is 1-10 ℃ for min -1 。
6. The method for preparing cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon electrode material for super capacitor according to claim 1, wherein in step (1), the concentration of the hydrochloric acid solution is 3-6 mol L -1 。
7. The preparation method of the cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon electrode material for the super capacitor according to claim 1, wherein in the step (2), the amount of nickel acetate in the mixed solution of nickel acetate and cobalt acetate is 1-2 mmol, the amount of cobalt acetate is 2-4 mmol, the amount of manganese acetate is 0.1-1 mmol, the amount of thiourea is 4-10 mmol, and the mass of enzymatic hydrolysis lignin carbon is 10-100 mg.
8. The method for preparing the cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon electrode material for the super capacitor according to claim 1, wherein in the step (2), the reaction temperature of the high-pressure reaction kettle is 120-200 ℃.
9. The method for preparing the nickel cobalt sulfide/enzymatic hydrolysis lignin carbon electrode material for the super capacitor according to claim 1, wherein in the step (2), the drying temperature is 60-80 ℃.
10. The cobalt nickel manganese sulfide/enzymatic hydrolysis lignin carbon electrode material for the super capacitor is characterized by being prepared by adopting the method of any one of the claims 1-9.
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