CN111115613A - 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
- Publication number
- CN111115613A CN111115613A CN201911416219.9A CN201911416219A CN111115613A CN 111115613 A CN111115613 A CN 111115613A CN 201911416219 A CN201911416219 A CN 201911416219A CN 111115613 A CN111115613 A CN 111115613A
- Authority
- CN
- China
- Prior art keywords
- cobalt
- polymer
- coated
- manganese
- coated carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 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 60
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 229910000428 cobalt oxide Inorganic materials 0.000 title claims abstract description 35
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 93
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 18
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- -1 cobalt ion compound Chemical class 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 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 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 55
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 50
- 238000003756 stirring Methods 0.000 claims description 38
- 229940018563 3-aminophenol Drugs 0.000 claims description 25
- 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 15
- 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
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 9
- 230000000379 polymerizing effect Effects 0.000 claims description 9
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 8
- 239000011324 bead Substances 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
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 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
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- 239000011565 manganese chloride 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
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 229920002521 macromolecule Polymers 0.000 claims 4
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims 1
- 238000001354 calcination Methods 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 7
- 150000001722 carbon compounds Chemical class 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 description 11
- 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
- 238000007600 charging Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 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
- 239000007832 Na2SO4 Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004090 dissolution Methods 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
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- 239000002002 slurry Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic 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
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000006260 foam Substances 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
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 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
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- 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
-
- 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
-
- 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
- H01G11/46—Metal oxides
-
- 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
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- Y02E60/10—Energy storage using batteries
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
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 the polymer spheres to obtain polymer sphere/cobalt ion compounds; s2, reacting the polymer sphere/cobalt ion compound with a carbon precursor to obtain a polymer sphere @ cobalt ion @ polymer compound; s3, adsorbing manganese ions by using the polymer sphere @ cobalt ion @ polymer compound to obtain a polymer sphere @ 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 @ CoxThe @ carbon @ MnOx composite is the spherical manganese oxide coated carbon-coated cobalt oxide coated carbon composite. Compared with the prior art, the invention has the advantages of simple equipment process, low cost and higher conductivity of the composite material, and can be used as an electrode material of a super capacitor or an electrode material of a lithium ion battery.
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 millions of times of charging and discharging circulation 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 on the surfaces 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 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 conductive performance, and the metal oxide and the carbon material are combined to form the composite material of the metal oxide and the carbon, so that the composite material can be used as the positive electrode material of a super capacitor and a lithium ion battery. At present, various C/MnO have been synthesized2Or 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 @ CoxThe @ 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 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 12-48 h.
In an embodiment of the present invention, in step S1, adsorption of cobalt ions on the polymer spheres is achieved by dispersing APF polymer spheres 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 spheres to the cobalt salt is 1:3.0 to 6.0.
In one embodiment of the present invention, in step S1, the stirring and adsorbing time is 12-48 h.
As an embodiment of the present invention, step S1 further includes the processes of filtering, washing, and drying after stirring and adsorbing.
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 12-24 h.
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 1:0.08-0.4:0.128-0.64:25.6-51.2:64-128: 0.32-0.16.
In one embodiment of the present invention, in step S2, after adding formaldehyde, stirring is continued for 12 to 48 hours.
In step S3, the polymer beads @ cobalt ions @ polymer composite is dispersed in an aqueous solution of manganese salt and stirred to allow the polymer beads @ cobalt ions @ polymer composite to adsorb 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 one embodiment of the present invention, in step S3, the mass ratio of the polymer beads @ cobalt ions @ polymer composite to the manganese salt is 1:3.0 to 6.0.
In one embodiment of the present invention, the stirring time in step S3 is 2-4 h.
In one embodiment of the present invention, in step S4, the inert gas atmosphere is a nitrogen gas atmosphere.
As an embodiment of the present invention, in step S4, the carbonization is performed at 600-800 ℃.
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 a 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: carbonizing the polymer ball @ cobalt ion @ polymer @ manganese ion compound in an inert atmosphere to obtain spherical carbon @ CoxThe @ 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 aqueous ammonia solution is 9 to 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: 3.0-6.0. The time for stirring and adsorbing is preferably 12-48 h. Preferably, step S1 further includes the steps of filtering, washing and drying after stirring and adsorbing. Further preferred is washingAnd washing with deionized water for multiple times. Further preferably, the drying is carried out in an oven at 50-100 ℃ for 12-24 h.
More specifically, step S2 includes the following procedures: 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 to the m-aminophenol to the formaldehyde to the ethanol to the water to the ammonia water is 1:0.08-0.4:0.128-0.64:25.6-51.2:64-128: 0.32-0.16. Preferably, after the formaldehyde is added, stirring is continued for 12-48 h.
More specifically, in step S3, the polymer beads @ cobalt ions @ polymer composite is dispersed in the manganese salt aqueous solution and stirred, so that the polymer beads @ cobalt ions @ polymer composite adsorbs the 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: 3.0-6.0. The stirring time is preferably 2-4 h.
More specifically, in step S4, the inert atmosphere is preferably a nitrogen atmosphere. The carbonization is preferably carried out at 600-800 ℃.
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-1In cobalt chloride solution. 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 @ Co2+And (c) a complex.
APF @ Co2+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, and stirringAfter dissolution, 0.16 g of 37% formaldehyde was added, stirring was continued for 24 hours, then filtration was carried out, and oven drying was carried out at 100 ℃ for 24 hours. Obtaining APF @ Co2+@ APF complex.
APF @ Co2+@ APF Complex continuously dispersed to 2 mol. L of 20 ml-1Manganese 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 of prepared spherical manganese oxide coated carbon-coated cobalt oxide coated carbon composite, uniformly mixing the spherical manganese oxide coated carbon-coated cobalt oxide coated carbon composite with acetylene black and polytetrafluoroethylene according to a mass ratio of 80:10:10, adding 1-2 drops of 1-methyl-2-pyrrolidone solvent, slightly stirring and grinding to prepare uniformly mixed bonding slurry, then uniformly coating the uniformly mixed bonding slurry on pre-prepared 1cm x 2cm rectangular foam nickel to enable the coating area to be 1cm x 1cm, then placing the mixture in a 120 ℃ vacuum drying box for overnight drying, and finally performing tabletting treatment on a tabletting machine for 3s under the pressure of 10Mpa to finally obtain the working electrode plate. Before testing, the prepared electrode plate is placed in 0.5M Na2SO4The 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 testing of the super capacitor:
spherical manganese oxide-coated carbon-coated cobalt oxide-coated carbon composite samples prepared by research using electrochemical workstation-CHI 660E were 0.5M Na2SO4Electrochemical behavior in electrolyte solutions, using a conventional three-electrode system in terms of electrodes, namely: a saturated calomel electrode as a reference electrode and a platinum electrode as a counter electrodeThe prepared working electrode sheet was 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) carrying out 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 be 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-1In 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 @ Co2+And (c) a complex.
APF @ Co2+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 @ Co2+@ APF complex.
APF @ Co2+@ 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 is 0.5A/g according to a charge and discharge curve.
Example 3
Dispersing 1.0 g APF polymer ball into 20 ml 2.0mol.L-1In 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 @ Co2+And (c) a complex.
APF @ Co2+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 @ Co2+@ APF complex.
APF @ Co2+@ APF Complex dispersed in 20 ml of 2 mol. L-1Manganese chloride solution, after stirring for 24 hours, filtered, washed and programmed to 600 ℃ under nitrogen atmosphere (1 ℃/min) 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 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-1In 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 @ Co2+And (c) a complex.
APF @ Co2+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 @ Co2+@ APF complex.
APF @ Co2+@ APF Complex dispersed in 20 ml of 2.5 mol. L-1Manganese acetate solution, after stirring for 24 hours, filtration, washing, and temperature programming under nitrogen atmosphere (1 c/min) to 600 c for 2 hours. Finally, the spherical manganese oxide coated carbon-coated cobalt oxide coated carbon compound is obtained.
Performing cyclic voltammetry tests and constant current charge and discharge tests 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 (10)
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 @ CoxThe @ carbon @ MnOx composite is the spherical manganese oxide coated carbon-coated cobalt oxide coated carbon composite.
2. The method of claim 1, wherein in step S1, the polymer beads are APF polymer beads obtained by polymerizing m-aminophenol and formaldehyde.
3. The method for preparing the spherical manganese oxide-coated carbon-coated cobalt oxide-coated carbon composite according to claim 2, wherein the step of polymerizing m-aminophenol with formaldehyde to obtain APF polymer spheres comprises 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.
4. The method of claim 2, wherein in step S1, the adsorption of cobalt ions on the APF polymer spheres is achieved by dispersing the APF polymer spheres in an aqueous solution of cobalt salt and stirring for adsorption.
5. The method for preparing the spherical manganese oxide-coated carbon-coated cobalt oxide-coated carbon composite according to claim 4, 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) the concentration of cobalt ions in the aqueous solution of a cobalt salt is 0.5 to 3 mol.L-1；
(III) the mass ratio of the APF polymer spheres to the cobalt salt is 1: 3.0-6.0;
(IV) the stirring and adsorbing time is 12-48 h.
6. The method of claim 2, wherein step S2 includes 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.
7. The method for preparing the spherical manganese oxide-coated carbon-coated cobalt oxide-coated carbon composite according to claim 6, 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 to the formaldehyde to the ethanol to the water to the ammonia water is 1:0.08-0.4:0.128-0.64:25.6-51.2:64-128: 0.32-0.16;
(II) adding formaldehyde, and continuing stirring for 12-48 h.
8. The method for preparing the spherical manganese oxide coated carbon-coated cobalt oxide coated carbon composite according to claim 2, 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.
9. The method for preparing the spherical manganese oxide-coated carbon-coated cobalt oxide-coated carbon composite according to claim 8, 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: 3.0-6.0;
(IV) stirring for 2-4 h.
10. 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;
(II) carbonization refers to calcination at 600-800 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911416219.9A CN111115613B (en) | 2019-12-31 | 2019-12-31 | Preparation method of spherical manganese oxide-coated carbon-coated cobalt oxide-coated carbon composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911416219.9A CN111115613B (en) | 2019-12-31 | 2019-12-31 | Preparation method of spherical manganese oxide-coated carbon-coated cobalt oxide-coated carbon composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111115613A true CN111115613A (en) | 2020-05-08 |
| CN111115613B CN111115613B (en) | 2023-02-10 |
Family
ID=70506697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911416219.9A Active CN111115613B (en) | 2019-12-31 | 2019-12-31 | Preparation method of spherical manganese oxide-coated carbon-coated cobalt oxide-coated carbon composite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111115613B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115724420A (en) * | 2022-09-30 | 2023-03-03 | 重庆长安新能源汽车科技有限公司 | Bimetal doped porous carbon material, preparation method, application, coated positive electrode material and preparation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105084422A (en) * | 2014-05-19 | 2015-11-25 | 中国科学院过程工程研究所 | Three-dimensional multi-structural cobaltosic oxide/carbon/manganese dioxide composite micro-nanomaterial and in-situ controllable preparation method thereof |
| 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 |
-
2019
- 2019-12-31 CN CN201911416219.9A patent/CN111115613B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105084422A (en) * | 2014-05-19 | 2015-11-25 | 中国科学院过程工程研究所 | Three-dimensional multi-structural cobaltosic oxide/carbon/manganese dioxide composite micro-nanomaterial and in-situ controllable preparation method thereof |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| YU ZHANG 等: "Hierarchical Fe2O3@C@MnO2@C Multishell Nanocomposites for High Performance Lithium Ion Batteries and Catalysts", 《LANGMUIR》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115724420A (en) * | 2022-09-30 | 2023-03-03 | 重庆长安新能源汽车科技有限公司 | Bimetal doped porous carbon material, preparation method, application, coated positive electrode material and preparation method |
| CN115724420B (en) * | 2022-09-30 | 2024-04-16 | 深蓝汽车科技有限公司 | Bimetal doped porous carbon material, preparation method, application and coated anode material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111115613B (en) | 2023-02-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9985273B2 (en) | Three-dimensional nanosized porous metal oxide electrode material of lithium ion battery and preparation method thereof | |
| CN106229498B (en) | Cathode material suitable for water-based metal ion battery and preparation method thereof | |
| CN108054019B (en) | NiCo of laminated structure2S4@NixCo(1-x)(OH)2Preparation method and application of composite material | |
| CN103545123A (en) | Hybrid energy storage device with zinc ion battery and supercapacitor | |
| CN110518202B (en) | Self-supporting V2O5rGO nano array sodium ion battery material and preparation method thereof | |
| CN107325295B (en) | Copper metal organic framework material with super-capacitive performance and preparation method and application thereof | |
| CN108963207A (en) | A kind of carbon composite material and its preparation method and application of porous metals doping | |
| CN108899522A (en) | A kind of high-volume silicon-carbon negative electrode material, preparation method and application | |
| CN112886134A (en) | Preparation method of diaphragm modification material for lithium-sulfur battery | |
| CN108565127B (en) | Electrode material capable of improving specific capacity of supercapacitor, preparation method and application | |
| CN110970226A (en) | Composite electrode material, preparation method and super capacitor | |
| CN111463020A (en) | Preparation and application of nickel-based three-dimensional graphene/manganese dioxide composite material | |
| CN110071282B (en) | Bismuth phosphate composite reduced graphene oxide material and preparation method and application thereof | |
| CN112086642A (en) | Graphitized carbon-coated high-specific-surface-area porous carbon sphere and preparation method and application thereof | |
| CN110634688A (en) | Preparation method and application of composite film electrode with CoZn-S nano particles inserted in graphene | |
| CN112751008B (en) | Polyphenol modified zinc-iron based heterojunction oxide carbon nano lithium ion battery cathode composite material and preparation method thereof | |
| CN111115613B (en) | Preparation method of spherical manganese oxide-coated carbon-coated cobalt oxide-coated carbon composite | |
| CN113496823B (en) | Symmetric hybrid supercapacitor and application thereof | |
| CN111029163B (en) | Spherical cobalt oxide/carbon/manganese oxide/carbon compound and preparation method and application thereof | |
| CN108666144A (en) | A kind of three-dimensional flower-shaped cobalt hydroxide-graphene composite material and preparation method thereof | |
| CN112420401B (en) | Bismuth oxide/manganese oxide composite supercapacitor and preparation method thereof | |
| CN115621525A (en) | Durable lithium battery | |
| CN103280340A (en) | Nickel-based electrode material and preparation method thereof | |
| CN109119255A (en) | Trimanganese tetroxide nano piece is embedded in graphene nanometer sheet composite material and preparation method altogether | |
| CN110060880B (en) | Prussian blue analogue and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |