CN111115613B - Preparation method of spherical manganese oxide-coated carbon-coated cobalt oxide-coated carbon composite - Google Patents
Preparation method of spherical manganese oxide-coated carbon-coated cobalt oxide-coated carbon composite Download PDFInfo
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- CN111115613B CN111115613B CN201911416219.9A CN201911416219A CN111115613B CN 111115613 B CN111115613 B CN 111115613B CN 201911416219 A CN201911416219 A CN 201911416219A CN 111115613 B CN111115613 B CN 111115613B
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 68
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 229910000428 cobalt oxide Inorganic materials 0.000 title claims abstract description 36
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 90
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 cobalt ion compound Chemical class 0.000 claims abstract description 11
- 150000001722 carbon compounds Chemical class 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 239000007833 carbon precursor Substances 0.000 claims abstract description 6
- 229910016978 MnOx Inorganic materials 0.000 claims abstract description 5
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 49
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 38
- 229940018563 3-aminophenol Drugs 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 150000001868 cobalt Chemical class 0.000 claims description 12
- 150000002696 manganese Chemical class 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000001179 sorption measurement Methods 0.000 claims description 9
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 6
- 229920002521 macromolecule Polymers 0.000 claims description 6
- 229940071125 manganese acetate Drugs 0.000 claims description 6
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- HRVYXNXPWHUJHF-UHFFFAOYSA-N 3-aminophenol;formaldehyde Chemical compound O=C.NC1=CC=CC(O)=C1 HRVYXNXPWHUJHF-UHFFFAOYSA-N 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 3
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 229910002451 CoOx Inorganic materials 0.000 claims 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 8
- 239000007772 electrode material Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 11
- 239000011324 bead Substances 0.000 description 9
- 238000002484 cyclic voltammetry Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000007600 charging Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910002090 carbon oxide Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229940021013 electrolyte solution Drugs 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 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
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
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- C01G51/00—Compounds of cobalt
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- 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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- 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
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- 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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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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Abstract
The invention relates to a preparation method of a spherical manganese oxide coated carbon-coated cobalt oxide coated carbon compound, which comprises the following steps: s1, adsorbing cobalt ions on a polymer ball to obtain a polymer ball/cobalt ion compound; s2, reacting the polymer ball/cobalt ion compound with a carbon precursor to obtain a polymer ball @ cobalt ion @ polymer compound; s3, adsorbing manganese ions by using the polymer ball @ cobalt ion @ polymer compound to obtain a polymer ball @ cobalt ion @ polymer @ manganese ion compound; s4, carbonizing the polymer ball @ cobalt ion @ polymer @ manganese ion compound in an inert atmosphere to obtain spherical carbon @ Co x The @ carbon @ MnOx composite is the spherical manganese oxide coated carbon-coated cobalt oxide coated carbon composite. Compared with the prior art, the invention has simple equipment process and low cost, the composite material has higher conductivity, and can be used as the electrode material of a super capacitor or the electrode of a lithium ion batteryA material.
Description
Technical Field
The invention belongs to the field of nano material electrochemistry and nano catalysis, and particularly relates to a preparation method of a spherical manganese oxide coated carbon-coated cobalt oxide coated carbon composite.
Background
The super capacitor is a novel component for storing energy through an interface double layer formed between an electrode and an electrolyte, is a novel energy storage device between a traditional capacitor and a secondary battery, has the characteristics of high charging and discharging speed, high energy storage density and the like, can complete charging and discharging within second-level time and realize more than million times of charging and discharging circulating operation. When the electrode contacts with the electrolyte, the solid-liquid interface generates stable double-layer charges with opposite signs under the action of coulomb force, intermolecular force and interatomic force, and the double-layer charges are called as interface double layers. The electric double layer supercapacitor is considered to be 2 inactive porous plates suspended in an electrolyte, and a voltage is applied to the 2 plates. The potential applied to the positive plate attracts negative ions in the electrolyte and the negative plate attracts positive ions, thereby forming an electric double layer capacitor at the surface of the two electrodes.
A lithium ion battery is a secondary battery (rechargeable battery) that mainly operates by movement of lithium ions between a positive electrode and a negative electrode. During charging and discharging, li + is inserted and extracted back and forth between the two electrodes: during charging, li + is extracted from the positive electrode and is inserted into the negative electrode through the electrolyte, and the negative electrode is in a lithium-rich state; the opposite is true during discharge.
The application of super capacitors and lithium ion batteries is very wide, and the electrode material has great influence on the electrochemical performance of the super capacitors and the lithium ion batteries. Metal oxides such as cobalt oxide, manganese dioxide and the like have high specific capacitance and are important electrode materials of electrochemical super capacitors and lithium ion batteries. However, as metal oxides, they themselves are relatively poor in conductivity. Thereby suppressing further improvement in electrochemical performance. The carbon material has good conductivity, and metal oxide is mixed withThe carbon materials are combined to form a composite material of metal oxide and carbon, and the composite material can be used as a positive electrode material of a super capacitor and a lithium ion battery. At present, various C/MnO have been synthesized 2 Or a C/Cox composite material to improve the conductivity of the electrode material, such as cobalt oxide prepared as a carbon/cobalt oxide composite by in-situ growth, co-precipitation, hydrothermal, electrodeposition, and the like.
The preparation method of the cobalt oxide/carbon composite material reported in the patent and literature at present mainly comprises the steps of synthesizing porous carbon, soaking cobalt precursors such as cobalt nitrate, cobalt chloride and other solutions, and then roasting at high temperature to obtain the carbon/cobalt oxide composite material. However, the electrochemical performance of such cobalt oxide/carbon composites is not yet satisfactory.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a spherical manganese oxide coated carbon-coated cobalt oxide coated carbon composite.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a preparation method of a spherical manganese oxide coated carbon-coated cobalt oxide coated carbon composite, which comprises the following steps:
s1: adsorbing cobalt ions on the polymer spheres to obtain polymer sphere/cobalt ion compounds;
s2: reacting the polymer ball/cobalt ion compound with a carbon precursor to obtain a polymer ball @ cobalt ion @ polymer compound;
s3: adsorbing manganese ions by using a polymer ball @ cobalt ion @ polymer compound to obtain a polymer ball @ cobalt ion @ polymer @ manganese ion compound;
s4: carbonizing the polymer ball @ cobalt ion @ polymer @ manganese ion compound in an inert atmosphere to obtain spherical carbon @ Co x The @ carbon @ MnOx composite is the spherical manganese oxide coated carbon-coated cobalt oxide coated carbon composite.
In an embodiment of the present invention, in step S1, the polymer beads are APF polymer beads, and are obtained by polymerizing m-aminophenol and formaldehyde.
As an embodiment of the invention, the APF polymer ball obtained by polymerizing m-aminophenol and formaldehyde adopts the following steps: adding m-aminophenol and formaldehyde into an ammonia water solution, stirring, and filtering to obtain spherical m-aminophenol formaldehyde resin, namely the APF high polymer ball.
In one embodiment of the present invention, in the process of polymerizing m-aminophenol and formaldehyde to obtain APF polymer beads, the m-aminophenol and the formaldehyde are in an equimolar ratio.
In the process of polymerizing m-aminophenol and formaldehyde to obtain the APF polymer spheres, the pH value of the ammonia water solution is 9-11.
As an embodiment of the invention, in the process of polymerizing m-aminophenol and formaldehyde to obtain APF polymer spheres, the stirring time is 12-48h.
In one embodiment of the present invention, in step S1, adsorption of cobalt ions on the polymer beads is achieved by dispersing APF polymer beads in an aqueous cobalt salt solution and stirring and adsorbing.
In one embodiment of the present invention, in step S1, the cobalt salt is at least one of cobalt acetate and cobalt chloride.
In one embodiment of the present invention, in step S1, the concentration of cobalt ions in the aqueous solution of cobalt salt is 0.5 to 3 mol. L -1 。
In one embodiment of the present invention, in step S1, the mass ratio of the APF polymer beads to the cobalt salt is 1.
In one embodiment of the present invention, the time for stirring and adsorbing in step S1 is 12 to 48 hours.
As an embodiment of the present invention, the step S1 further includes processes of filtering, washing, and drying after the stirring and the adsorption.
As an embodiment of the present invention, in step S1, the washing is performed multiple times with deionized water.
In one embodiment of the present invention, in step S1, the drying is performed in an oven at 50-100 ℃ for 12-24h.
As an embodiment of the present invention, step S2 includes the following processes:
dispersing the polymer ball/cobalt ion compound into a mixed solution of ethanol, water and ammonia water, adding m-aminophenol, stirring for dissolving, adding formaldehyde, and continuing stirring.
In step S2, the mass ratio of the polymer beads/cobalt ion complex, the m-aminophenol, the formaldehyde, the ethanol, the water, and the ammonia water is 1.
As an embodiment of the invention, in the step S2, after the formaldehyde is added, the stirring is continued for 12 to 48 hours.
In step S3, the polymer beads @ cobalt ions @ polymer composite is dispersed in the manganese salt aqueous solution and stirred to realize that the polymer beads @ cobalt ions @ polymer composite adsorbs manganese ions.
In one embodiment of the present invention, in step S3, the manganese salt is at least one of manganese acetate or manganese chloride.
In one embodiment of the present invention, in step S3, the concentration of manganese ions in the aqueous solution of manganese salt is 0.5 to 2.5 mol.L -1 。
In step S3, the mass ratio of the polymer spheres @ cobalt ions @ polymer composite to the manganese salt is 1.
In one embodiment of the present invention, the stirring time in step S3 is 2-4h.
In one embodiment of the present invention, in step S4, the inert gas atmosphere is a nitrogen gas atmosphere.
In one embodiment of the present invention, the carbonization in step S4 is performed at 600 to 800 ℃.
The invention provides a spherical oxide coated carbon composite material which is formed by using an amino-containing spherical macromolecular carbon precursor as a template, adsorbing one metal oxide as a core, separating a carbon precursor layer in the middle and continuously adsorbing another metal oxide as a shell to coat another oxide coated carbon for the first time. The spherical manganese oxide-coated carbon-coated cobalt oxide-coated carbon composite is very beneficial to improving the specific surface area, the energy density and the conductivity of the supercapacitor due to the unique structural characteristics of the spherical manganese oxide-coated carbon-coated cobalt oxide-coated carbon composite.
Compared with the prior art, the equipment has simple process and low cost. The prepared spherical manganese oxide-coated carbon-coated cobalt oxide-coated carbon composite material has high conductivity and can be used as an electrode material of a supercapacitor or an electrode material of a lithium ion battery.
Drawings
Fig. 1 is a scanning electron microscope image of the spherical manganese oxide-coated carbon-coated cobalt oxide-coated carbon composite prepared in example 1;
FIG. 2 is a graph of Cyclic Voltammograms (CVs) of samples prepared in example 1 at different scan rates;
FIG. 3 is a plot of constant current charge and discharge for the samples prepared in example 1.
Detailed Description
The purpose of the invention can be realized by the following technical scheme:
a spherical manganese oxide-coated carbon-coated cobalt oxide-coated carbon composite is prepared by the following steps:
s1: adsorbing cobalt ions on the polymer spheres to obtain polymer sphere/cobalt ion compounds;
s2: reacting the polymer ball/cobalt ion compound with a carbon precursor to obtain a polymer ball @ cobalt ion @ polymer compound;
s3: adsorbing manganese ions by using a polymer ball @ cobalt ion @ polymer compound to obtain a polymer ball @ cobalt ion @ polymer @ manganese ion compound;
s4: the macromolecule ball @ cobalt ion @ macromolecule @ manganese ion compound is put in an inert atmosphereCarbonizing to obtain spherical carbon @ Co x The @ carbon @ MnOx composite is the spherical manganese oxide coated carbon-coated cobalt oxide coated carbon composite.
More specifically, in step S1, the polymer beads are APF polymer beads obtained by polymerizing m-aminophenol and formaldehyde. The method preferably adopts the following steps of polymerizing m-aminophenol and formaldehyde to obtain the APF polymer spheres: adding m-aminophenol and formaldehyde into an ammonia water solution, stirring, and filtering to obtain spherical m-aminophenol formaldehyde resin, namely the APF high polymer ball. It is further preferred that the m-aminophenol and formaldehyde are in an equimolar ratio. Further preferably, the pH value of the ammonia water solution is 9-11. It is further preferred that the stirring time is 12 to 48 hours.
More specifically, in step S1, adsorption of cobalt ions on the polymer spheres is achieved by dispersing the APF polymer spheres in an aqueous cobalt salt solution and stirring for adsorption. Preferably, the cobalt salt is at least one of cobalt acetate or cobalt chloride. Preferably, the concentration of cobalt ions in the aqueous solution of cobalt salt is 0.5-3 mol.L -1 . The mass ratio of the APF polymer spheres to the cobalt salt is preferably 1. The time for stirring and adsorbing is preferably 12-48h. Preferably, the step S1 further comprises the processes of filtering, washing and drying after stirring and adsorption. It is further preferable that the washing is carried out plural times with deionized water. Further preferably, the drying is carried out in an oven at 50-100 ℃ for 12-24h.
More specifically, step S2 includes the following processes: dispersing the polymer ball/cobalt ion compound into a mixed solution of ethanol, water and ammonia water, adding m-aminophenol, stirring for dissolving, adding formaldehyde, and continuing stirring. Preferably, the mass ratio of the polymer ball/cobalt ion compound, the m-aminophenol, the formaldehyde, the ethanol, the water and the ammonia water is 1. Preferably, after the formaldehyde is added, stirring is continued for 12-48h.
More specifically, in step S3, the polymer spheres @ cobalt ions @ polymer composite is dispersed in the manganese salt aqueous solution and stirred to realize that the polymer spheres @ cobalt ions @ polymer composite adsorbs manganese ions. Preferably, the manganese salt is at least one of manganese acetate or manganese chloride. The concentration of manganese ions in the aqueous solution of manganese salt is preferably 0.5 to 2.5 mol.L -1 . The mass ratio of the polymer spheres @ cobalt ions @ polymer compound to the manganese salt is preferably 1.0-6.0. The stirring time is preferably 2-4h.
More specifically, in step S4, the inert atmosphere is preferably a nitrogen atmosphere. The carbonization is preferably carried out at 600 to 800 ℃.
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
(1) Preparing APF polymer spheres: 2.0 g of 25% ammonia water and 0.71 g of m-aminophenol are added to a 30 ℃ solution containing 24 g of deionized water and 10 ml of absolute ethanol, and after stirring and dissolution, 1.0 g of 35% formaldehyde solution is added, stirring is continued for 24 hours, and centrifugal separation is performed. The sample was dried in an oven at 50 ℃ for 12 hours.
(2) Dispersing 1.0 g APF polymer ball into 20 ml 2.0mol.L -1 In the cobalt chloride solution of (1). Stirred for 24 hours and then taken out. The mixture was put into an oven at 100 ℃ and allowed to stand for 24 hours. Obtaining APF @ Co 2+ And (c) a complex.
APF @ Co 2+ Grinding 0.25 g of compound, dispersing into a mixed solution of 32 g of water, 12.8 g of ethanol and 0.4 g of concentrated ammonia water, adding 0.1 g of m-aminophenol, stirring to dissolve, adding 0.16 g of 37% formaldehyde, continuously stirring for 24 hours, filtering, and drying in an oven at 100 ℃ for 24 hours. Obtaining APF @ Co 2+ @ APF complex.
APF @ Co 2+ The @ APF complex was continuously dispersed to 20 ml of 2 mol. L -1 Manganese acetate solution, after stirring for 24 hours, filtered, washed and programmed to 600 ℃ under nitrogen atmosphere for 2 hours. Finally obtaining the spherical manganese oxide coated carbon-coated cobalt oxide coated carbon compound (spherical manganese oxide/carbon/cobalt oxide/carbon compound or spherical carbon @ Co) x @ carbon @ MnOx complex).
The appearance of the sample is observed by a scanning electron microscope, and the result is shown in figure 1, and the particle size can be seen to be about 1 micron.
Electrochemical testing:
(1) Preparation of working electrode
Firstly, accurately weighing a certain amount of 50mg preparedThe prepared spherical manganese oxide-coated carbon-coated cobalt oxide-coated carbon composite is uniformly mixed with acetylene black and polytetrafluoroethylene according to a mass ratio of 80. Before testing, the prepared electrode plate is placed in 0.5M Na 2 SO 4 The soaking treatment is carried out in the solution for not less than 12 hours, so as to ensure that the electrolyte solution can be fully soaked into the pore channels of the material.
(2) Cyclic voltammetry and constant current charge and discharge tests of the super capacitor:
the sample of the spherical manganese oxide-coated carbon-coated cobalt oxide-coated carbon composite prepared by utilizing the electrochemical workstation-CHI 660E to conduct research is 0.5M Na 2 SO 4 Electrochemical behavior in electrolyte solutions, using a conventional three-electrode system in terms of electrodes, namely: the saturated calomel electrode is used as a reference electrode, the platinum electrode is used as a counter electrode, and the working electrode slice prepared by the method is used as a working electrode. The specific capacitance of the prepared sample is tested by adopting two methods of Cyclic Voltammetry (CV) and constant current charge-discharge (GCD): the cyclic voltammetry tests are carried out at a series of different scanning speeds of 50mv/s, 100mv/s, 200mv/s and 500mv/s, and the constant current charging and discharging tests are carried out at a series of different current densities of 10A/g, 5A/g, 2A/g, 1A/g and 0.5A/g. According to the GCD curve of the material, the specific capacitance (including the mass specific capacity and the volume specific capacity) is calculated according to the formula (1-1).
Cg＝IΔt/ΔVm——(1-1)
Where Cg is the mass specific capacitance (F/g) and I is the discharge current (A). Δ t is a discharge time(s), Δ V is a discharge potential (V), and m is a mass (g) of the active material coated on the working electrode sheet.
And (3) performing electrochemical test on the sample, wherein the result is shown in a cyclic voltammetry curve of FIG. 2 and a charge-discharge curve of FIG. 3, and according to the charge-discharge curve, the specific capacitance of the sample is calculated to reach 634.2F/g under the condition that the current density is 0.5A/g.
Example 2
Dispersing 1.0 g APF polymer ball into 20 ml 2.0mol.L -1 In cobalt chloride solution. Stirred for 24 hours and then taken out. The mixture was put into an oven at 50 ℃ and allowed to stand for 24 hours. Obtaining APF @ Co 2+ And (c) a complex.
APF @ Co 2+ Grinding 0.25 g of compound, dispersing into a mixed solution of 32 g of water, 12.8 g of ethanol and 0.16 g of concentrated ammonia water, adding 0.04 g of m-aminophenol, stirring to dissolve, adding 0.64 g of 37% formaldehyde, continuously stirring for 24 hours, filtering, and drying in an oven at 50 ℃ for 24 hours. Obtaining APF @ Co 2+ @ APF complex.
APF @ Co 2+ @ APF complex was dispersed in 20 ml of a 1.5 mol. L-1 manganese acetate solution, stirred for 24 hours, filtered, washed, and temperature programmed (1 deg.C/min) to 600 deg.C under nitrogen for 2 hours. Finally, the spherical manganese oxide coated carbon-coated cobalt oxide coated carbon compound is obtained.
And (3) performing cyclic voltammetry tests and constant current charge and discharge tests on the sample at different scanning rates, and then calculating that the specific capacitance of the sample is high 624.6F/g under the condition that the current density of the sample is 0.5A/g according to a charge and discharge curve.
Example 3
1.0 g of APF polymer spheres were dispersed in 20 ml of 2.0mol.L -1 In cobalt acetate solution. Stirred for 24 hours and then taken out. The mixture was put into an oven at 50 ℃ and allowed to stand for 24 hours. Obtaining APF @ Co 2+ And (c) a complex.
APF @ Co 2+ Grinding 0.25 g of compound, dispersing into a mixed solution of 16 g of water, 6.4 g of ethanol and 0.08 g of strong ammonia water, adding 0.02 g of m-aminophenol, stirring to dissolve, adding 0.032 g of 37% formaldehyde, continuously stirring for 24 hours, filtering, and drying in an oven at 50 ℃ for 24 hours. Obtaining APF @ Co 2+ @ APF complex.
APF @ Co 2+ @ APF Complex dispersed in 20 ml of 2 mol. L -1 Stirring for 24 hr in manganese chloride solution, filtering, washing and reaction under nitrogen atmosphereThe temperature was programmed (1 ℃ C./min) to 600 ℃ and held for 2 hours. Finally, the spherical manganese oxide coated carbon-coated cobalt oxide coated carbon compound is obtained.
And (3) performing cyclic voltammetry tests and constant current charge and discharge tests on the sample at different scanning rates, and then calculating that the specific capacitance of the sample is high 534.5F/g under the condition that the current density of the sample is 0.5A/g according to a charge and discharge curve.
Example 4.
Dispersing 1.0 g APF polymer ball into 20 ml 2.0mol.L -1 In a cobalt sulfate solution. Stirred for 24 hours and then taken out. The mixture was put into an oven at 50 ℃ and allowed to stand for 24 hours. Obtaining APF @ Co 2+ And (c) a complex.
APF @ Co 2+ Grinding 0.25 g of compound, dispersing into a mixed solution of 16 g of water, 6.4 g of ethanol and 0.04 g of concentrated ammonia water, adding 0.01 g of m-aminophenol, stirring to dissolve, adding 0.016 g of 37% formaldehyde, continuously stirring for 24 hours, filtering, and drying in an oven at 50 ℃ for 24 hours. Obtaining APF @ Co 2+ @ APF complex.
APF @ Co 2+ @ APF Complex dispersed in 20 ml of 2.5 mol. L -1 Manganese acetate solution, after stirring for 24 hours, filtered, washed and programmed to 600 ℃ under nitrogen atmosphere for 2 hours. Finally, the spherical manganese oxide coated carbon-coated cobalt oxide coated carbon compound is obtained.
Performing cyclic voltammetry test and constant current charge and discharge test on the sample at different scanning rates, and then calculating the specific capacitance of the sample to be 644.5F/g under the condition that the current density of the sample is 0.5A/g according to a charge and discharge curve
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (8)
1. A preparation method of a spherical manganese oxide-coated carbon-coated cobalt oxide-coated carbon composite is characterized by comprising the following steps:
s1: adsorbing cobalt ions on the polymer spheres to obtain polymer sphere/cobalt ion compounds;
s2: reacting the polymer ball/cobalt ion compound with a carbon precursor to obtain a polymer ball @ cobalt ion @ polymer compound;
s3: adsorbing manganese ions by using a polymer ball @ cobalt ion @ polymer compound to obtain a polymer ball @ cobalt ion @ polymer @ manganese ion compound;
s4: carbonizing the polymer ball @ cobalt ion @ polymer @ manganese ion compound in an inert atmosphere to obtain spherical carbon @ CoOx @ carbon @ MnOx compound, namely the spherical manganese oxide coated carbon-coated cobalt oxide-coated carbon compound, wherein the specific capacitance of the spherical manganese oxide-coated carbon-coated cobalt oxide-coated carbon compound is as high as 534.5-644.5F/g under the condition that the current density is 0.5A/g;
in the step S1, the polymer spheres are APF polymer spheres and are obtained by polymerizing m-aminophenol and formaldehyde; the method comprises the following steps of: adding m-aminophenol and formaldehyde into an ammonia water solution, stirring, and filtering to obtain spherical m-aminophenol formaldehyde resin, namely the APF high polymer ball.
2. The method for preparing the spherical manganese oxide-coated carbon-coated cobalt oxide-coated carbon composite according to claim 1, wherein in step S1, the adsorption of cobalt ions on the polymer spheres is achieved by dispersing APF polymer spheres into an aqueous solution of cobalt salt and stirring for adsorption.
3. The method for preparing the spherical manganese oxide-coated carbon-coated cobalt oxide-coated carbon composite according to claim 2, wherein the step S1 comprises any one or more of the following conditions:
(I) The cobalt salt is at least one of cobalt acetate or cobalt chloride;
(II) cobalt ion in cobalt salt aqueous solutionHas a concentration of 0.5 to 3 mol.L -1 ；
(III) the mass ratio of the APF polymer spheres to the cobalt salt is 1.0-6.0;
(IV) the stirring and the adsorption time is 12-48h.
4. The method for preparing the spherical manganese oxide-coated carbon-coated cobalt oxide-coated carbon composite according to claim 1, wherein the step S2 comprises the following steps:
dispersing the polymer ball/cobalt ion compound into a mixed solution of ethanol, water and ammonia water, adding m-aminophenol, stirring for dissolving, adding formaldehyde, and continuing stirring.
5. The method for preparing the spherical manganese oxide-coated carbon-coated cobalt oxide-coated carbon composite according to claim 4, wherein the step S2 comprises any one or more of the following conditions:
(I) The mass ratio of the polymer ball/cobalt ion compound to the m-aminophenol, the formaldehyde, the ethanol, the water and the ammonia water is 1;
(II) continuously stirring for 12-48h after adding the formaldehyde.
6. The method for preparing the spherical manganese oxide coated carbon-coated cobalt oxide coated carbon composite according to claim 1, wherein in step S3, the macromolecule ball @ cobalt ion @ macromolecule composite is dispersed in the manganese salt aqueous solution and stirred to realize manganese ion adsorption of the macromolecule ball @ cobalt ion @ macromolecule composite.
7. The method for preparing the spherical manganese oxide coated carbon-coated cobalt oxide coated carbon composite according to claim 6, wherein the step S3 comprises any one or more of the following conditions:
(I) The manganese salt is at least one of manganese acetate or manganese chloride;
(II) the concentration of manganese ions in the aqueous solution of manganese salt is 0.5 to 2.5 mol.L -1 ；
(III) the mass ratio of the polymer spheres @ cobalt ions @ polymer compound to the manganese salt is 1;
(IV) stirring for 2-4h.
8. The method for preparing the spherical manganese oxide-coated carbon-coated cobalt oxide-coated carbon composite according to claim 1, wherein the step S4 comprises any one or more of the following conditions:
(I) The inert atmosphere is nitrogen atmosphere;
the carbonization (II) means that the roasting is carried out at 600-800 ℃.
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| KR101793938B1 (en) * | 2016-05-24 | 2017-12-04 | 순천대학교 산학협력단 | composite for electrode of electrochemical capacitor and manufacturing method thereof, electrode composition for electrochemical capacitor |
| CN109659145A (en) * | 2018-12-17 | 2019-04-19 | 上海应用技术大学 | A method of preparing porous spherical manganese oxide/carbon complex |
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| KR101793938B1 (en) * | 2016-05-24 | 2017-12-04 | 순천대학교 산학협력단 | composite for electrode of electrochemical capacitor and manufacturing method thereof, electrode composition for electrochemical capacitor |
| CN109659145A (en) * | 2018-12-17 | 2019-04-19 | 上海应用技术大学 | A method of preparing porous spherical manganese oxide/carbon complex |
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