CN108172411B - A kind of preparation method of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material - Google Patents
A kind of preparation method of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material Download PDFInfo
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- CN108172411B CN108172411B CN201810038664.5A CN201810038664A CN108172411B CN 108172411 B CN108172411 B CN 108172411B CN 201810038664 A CN201810038664 A CN 201810038664A CN 108172411 B CN108172411 B CN 108172411B
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- sulfur
- doped graphene
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- alloy oxide
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 83
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 70
- 239000011593 sulfur Substances 0.000 title claims abstract description 61
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 59
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910000914 Mn alloy Inorganic materials 0.000 title claims abstract description 37
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 17
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 9
- 239000011833 salt mixture Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 12
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- -1 nitrogenous compound Chemical class 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 6
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000003945 anionic surfactant Substances 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 150000001868 cobalt Chemical class 0.000 claims description 5
- 150000002696 manganese Chemical class 0.000 claims description 5
- 229940126062 Compound A Drugs 0.000 claims description 4
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical group [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 17
- 229910020632 Co Mn Inorganic materials 0.000 abstract description 3
- 229910020678 Co—Mn Inorganic materials 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 239000002131 composite material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 238000001548 drop coating Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention provides a kind of preparation method of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material, preparation method specifically includes that sulphur nitrogen is prepared with hydro-thermal method at the beginning of doped graphene, sulfur and nitrogen co-doped graphene is made in the secondary doping process through high-temperature heat treatment again, Co-Mn metal salt mixture and ammonium hydroxide are introduced in sulfur and nitrogen co-doped graphene, hydro-thermal reaction realizes the preparation of cobalt manganese alloy oxide nano-slice/sulfur and nitrogen co-doped graphene nanocomposite material later.Nanocomposite prepared by the present invention can be applicable on electrode of super capacitor, show the capacitor of superelevation, outstanding high rate performance and good cyclical stability, provide the route inexpensively easily extended for using energy source.
Description
Technical field
The invention belongs to new energy and field of material technology, specifically a kind of cobalt manganese alloy oxide-sulfur and nitrogen co-doped stone
The preparation method of black alkene nanocomposite.
Background technique
Graphene possesses huge potential because of its unique electronic property in the respective applications.It is atom doped to change
The part composition and electronic structure of graphene, change its Electronic Performance.Recently, nitrogen-doped graphene because its in electronic device it is good
Performance cause the very big attention graphene nitrating of people usually there are three types of implementation method: increase at chemical vapor deposition (CVD)
It is added during length, the high-temperature heat treatment or decomposition of nitrogen containing species, NH3/N2The high-temperature heat treatment or decomposition of plasma.These sides
For method because of the limitation of reaction condition and equipment, cost is excessively high, can not carry out large-scale application.
The characteristics of due to business carbon electricity double layer capacitor low-voltage capacity, the faradic fake capacitance electricity of metal oxide base
Pole is considered as a kind of most promising electrode of super capacitor.Metal oxide resistor usually contains lower conductivity, with
The hydridization of conductance bracket is expected to improve the electronics transfer of electrode and capacitive property.N- graphene is because the doping of N improves it
Electronic conductivity, and possess two-dimensional structure.In terms of making hybrid super capacitor electrode, N- graphene is one good
Selection.
Summary of the invention
In view of the above-mentioned problems, the present invention provides a kind of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nano composite wood
The preparation method of material, cobalt manganese alloy oxide nano-slice/sulfur and nitrogen co-doped graphite that this method can carry out in low temperature and solution
The preparation method of alkene nanocomposite, during overcoming tradition to prepare nitrogen-doped graphene the shortcomings that complex process, higher cost,
Gained nanocomposite shows capacitance (the 1551F g of superelevation-1), outstanding high rate performance and good stable circulation
Property.
A kind of technical solution provided by the invention: cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material
Preparation method, include the following steps:
(1) it takes the graphite oxide powder of certain mass to be dissolved in deionized water, adds sulfur-containing compound, anionic surface
Activating agent, nitrogenous compound A are dried to obtain the just doping of sulphur nitrogen after ultrasonic disperse dissolves, then by being filtered after hydro-thermal reaction
Graphene；
(2) the first doped graphene of the resulting sulphur nitrogen of step (1) is mixed with nitrogenous compound B, after tube furnace is calcined
To sulfur and nitrogen co-doped graphene (S, N- graphene)；
(3) cobalt salt and manganese salt mixed configuration cobalt-manganese salt mixture are taken, then by itself and step (2) resulting sulfur and nitrogen co-doped stone
Black alkene is dissolved in deionized water, is mixed evenly to obtain mixed liquor；
(4) ammonium hydroxide is added into step (3) resulting mixed liquor, it is dry through filtering in hydrothermal reaction kettle after heating reaction
It is dry to obtain cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material.
Further, sulfur-containing compound described in step (1) is selected from one of thioacetic acid, 2 mercapto ethanol or two
Kind, anionic surfactant be selected from neopelex, dodecyl sodium sulfate, lauryl sodium sulfate one kind or
It is a variety of.
Further, nitrogenous compound A described in step (1) is selected from ammonium hydroxide, hexamethylenetetramine, urea, melamine
One of or it is a variety of.
Further, graphite oxide powder, sulfur-containing compound, anionic surfactant, nitrogen described in step (1)
The mass ratio for closing object A is 1:(1~10): (0.5~5): (2~15).
Further, hydrothermal temperature is 60~250 DEG C in the step (1), 5~72h of reaction time.
Further, 0.5~5h of ultrasonic time in the step (1), drying condition are as follows: 60-80 DEG C of temperature, time 1-
12h。
Further, in the step (2) nitrogenous compound B in hexamethylenetetramine, urea, melamine one
Kind is a variety of, the mass ratio (1~20) of nitrogenous compound B and the first doped graphene of sulphur nitrogen: 1.
Further, the step (2) in tube furnace reaction temperature be 150~750 DEG C, the reaction time be 0.5~
10h。
Further, in the step (3), sulfur and nitrogen co-doped graphene concentration is 1~100mg/ml, and cobalt salt is nitric acid
One of cobalt, cobaltous sulfate, cobalt chloride, cobalt oxalate, manganese salt be one of manganese nitrate, manganese sulfate, manganese chloride, manganese oxalate, two
Person 1:1 in mass ratio mixing.
Further, in the step (4), the ratio of sulfur and nitrogen co-doped graphene, ammonia and cobalt-manganese salt mixture be (1~
5) g:(10~18) g:(0.01~0.05) mol, reaction temperature is 150~250 DEG C in hydrothermal reaction kettle, the reaction time is 2~
5h。
Sulfur and nitrogen co-doped graphene (S, N- graphene) is prepared with solwution method the present invention provides a kind of, is added at low temperature
The method of the laminated nano composition of cobalt manganese alloy.Co-Mn metal salt theoretically possesses very high capacitance, and sulfur-bearing is added
Reducing agent carries out redox reaction with graphene oxide, and the electronation graphene carried out in cryogenic fluid method also can
A large amount of doping of N are realized, in addition, cobalt manganese can be made to close by the way that negatively charged surfactant is added as the medium increased
Gold and S, N- graphene are in close contact.The especially secondary doping doping that increases nitrogen, so that prepared is sulfur and nitrogen co-doped
Graphene capacitor with higher and good high rate performance.Co-Mn metal salt mixture is introduced in sulfur and nitrogen co-doped graphene
When be added ammonium hydroxide be used as dispersing agent, guarantee hydro-thermal reaction sufficiently carry out, make made from composite property it is more stable.The layer of synthesis
The nanocomposite of shape structure shows capacitance (the 1551F g of superelevation-1), outstanding high rate performance and good circulation
Stability.In energy storage and conversion, this low temperature method, which can provide a kind of novel route, to be carried out large scale preparation and contains
The nanocomposite high-performance electrode of sulfur and nitrogen co-doped graphene.
Detailed description of the invention
Fig. 1 is S, transmission electron microscope (TEM) image of N- graphene.
Fig. 2 is cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material TEM image.
Fig. 3 is that cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanometer composite electrode, pure cobalt manganese alloy oxide are received
Rice piece crystalline electrode and cobalt manganese alloy oxide nano-slice/sulfur and nitrogen co-doped graphene mixture electrode are under different discharge currents
The comparison of capacitor.
Fig. 4 is calculated cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanometer composite under different scanning rates
The specific capacitor of electrode.
Fig. 5 is cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanometer composite electrode electrochemical cycle stability
Curve.
Specific embodiment
Doped graphene at the beginning of the present invention prepares sulphur nitrogen with hydro-thermal method using the reducing agent of sulfur-bearing, dispersing agent and some contains
Nitrogen compound completes the preliminary doping of sulphur nitrogen, then two through high-temperature heat treatment while promoting reaction to be normally carried out
Sulfur and nitrogen co-doped graphene is made in secondary doping process.Then it is mixed with sulfur and nitrogen co-doped graphene with cobalt, manganese presoma, ammonia is added
Water washs drying after hydro-thermal reaction.The present invention is described further with attached drawing combined with specific embodiments below.
Embodiment 1
Take at room temperature graphite oxide powder, thioacetic acid, neopelex, hexamethylenetetramine (mass ratio 1:
1:0.5:2) the ultrasonic disperse 0.5h in 50ml deionized water, later 60 DEG C of reaction 5h in reaction kettle, filtered, dry (60 DEG C,
Sulphur nitrogen just doped graphene is obtained after 12h).Doped graphene at the beginning of sulphur nitrogen is mixed with melamine 1:2 in mass ratio, is being connected with
400 DEG C of reaction 2h obtain sulfur and nitrogen co-doped graphene (S, N- graphene) in the tube furnace of nitrogen.Take cobalt-manganese salt mixture (Co
(NO 3)2、MnSO4Mass ratio 1:1 mixing) 0.01mol, S, N- graphene 3g are dissolved in 50ml deionized water, are mixed evenly
After add 10g ammonium hydroxide, mixed solution reacts at 200 DEG C in hydrothermal reaction kettle is dried to obtain final product cobalt through filtering after 2h
Manganese alloy oxide nano-slice/sulfur and nitrogen co-doped graphene nanocomposite material.
Embodiment 2
Take at room temperature graphite oxide powder, 2 mercapto ethanol, lauryl sodium sulfate, ammonium hydroxide (mass ratio 1:5:2:10) in
Ultrasonic disperse 2h in 50ml deionized water, later 100 DEG C of reaction 10h of reaction kettle, filtered, dry (80 DEG C, 12h) after obtain sulphur
The first doped graphene of nitrogen.Doped graphene at the beginning of sulphur nitrogen is mixed with hexamethylenetetramine 1:5 in mass ratio, in the pipe for being connected with nitrogen
300 DEG C of reaction 5h obtain sulfur and nitrogen co-doped graphene (S, N- graphene) in formula furnace.Take cobalt-manganese salt mixture (CoSO4、MnCl2Matter
Amount is mixed than 1:1) 0.05mol, S, N- graphene 5g dissolve in 80ml deionized water, and 16g ammonia is added after being mixed evenly
Water, mixed solution are dried to obtain final product cobalt manganese alloy oxide through filtering after reaction 5h at 230 DEG C in hydrothermal reaction kettle
Nanometer sheet/sulfur and nitrogen co-doped graphene nanocomposite material.
Embodiment 3
Take at room temperature graphite oxide powder, 2 mercapto ethanol, dodecyl sodium sulfate, melamine (mass ratio 1:8:5:
15) the ultrasonic disperse 5h in 50ml deionized water reacts for 24 hours, after being filtered, drying (60 DEG C, 12h) for 200 DEG C of reaction kettle later
Obtain sulphur nitrogen just doped graphene.Doped graphene at the beginning of sulphur nitrogen is mixed with urea 1:15 in mass ratio, in the pipe for being connected with nitrogen
500 DEG C of reaction 10h obtain sulfur and nitrogen co-doped graphene (S, N- graphene) in formula furnace.Take cobalt-manganese salt mixture (CoCl2、MnC2O4
Mass ratio 1:1 mixing) 0.02mol, S, N- graphene 2g dissolve in 80ml deionized water, adds 20g after being mixed evenly
Ammonium hydroxide, mixed solution is filtered after reaction 3h at 250 DEG C in hydrothermal reaction kettle is dried to obtain the oxidation of final product cobalt manganese alloy
Object nanometer sheet/sulfur and nitrogen co-doped graphene nanocomposite material.
Application example 1
Cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material obtained in embodiment 1 is configured to
The solution of 8mg/mL is applied in electrode of super capacitor.Wherein electrolyte is 0.5molL-1H2SO4, diaphragm is
Celgard3501, binder nafion ratio are 5%, deionized water and isopropanol ratios 1:4.By solution drop coating in graphitic carbon
Button capacitor is assembled into using two electrode slices identical in quality as cathode and anode as electrode slice on paper.Measurement is different
The specific capacity of capacitor under current density, the results are shown in Table 1, and when current density is in 2A/g, specific capacity reaches 1510Fg-1.When current density increases to 30Ag-1, still remain in 990Fg-1.Pure cobalt manganese alloy oxide nano-slice is used simultaneously
Crystalline electrode and cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene mixture as a control group, capacitor under different discharge currents
Comparison as shown in figure 3, cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material prepared by the present invention capacitor
Amount is significantly higher than control group.
1 cobalt manganese alloy oxide of table-sulfur and nitrogen co-doped graphene nanocomposite material capacitance
Application example 2
Cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material obtained in embodiment 1 is configured to
The solution of 10mg/mL, in 0.5molL-1H2SO4As carrying out electro-chemical test, Ag/AgCl in the three-electrode system of electrolyte
For reference electrode, platinum electrode is auxiliary electrode.Binder nafion mass accounts for the 5% of active material, deionized water and isopropyl
Alcohol ratio 1:4 is used as working electrode after dry by solution drop coating on vitreous carbon.CV is carried out under voltage 0-1.1V range to follow
Ring volt-ampere is tested, calculated cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material under different scanning rates
The specific capacitor of electrode, test result are shown in Table 2, Fig. 4.
Cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material capacitor under 2 different scanning rates of table
Application example 3
Cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material obtained in embodiment 2 is configured to
The solution of 10mg/mL is applied in electrode of super capacitor.In 2molL-1Li2SO4For in the three-electrode system of electrolyte into
The test of row electrochemical cycle stability, wherein Ag/AgCl is reference electrode, and platinum electrode is auxiliary electrode.Binder PVDF
(polyvinylidene fluoride) ratio is 5%, deionized water and isopropanol ratios 1:4, by solution drop coating in vitreous carbon
On, working electrode is used as after dry.Fig. 5 is cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanometer composite electrode electricity
Chemical cycle stability curve, the capacitor of electrode is gradually increased due to activation when starting as the result is shown, and
It is not deteriorated significantly in 10000 circulations.
The foregoing is merely the detailed descriptions of specific embodiments of the present invention, do not limit the present invention with this, all at this
Made any modifications, equivalent replacements, and improvements etc. in the mentality of designing of invention, should be included in protection scope of the present invention it
It is interior.
Claims (7)
1. a kind of preparation method of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material, it is characterised in that packet
Include following steps:
(1) graphite oxide powder, sulfur-containing compound, anionic surfactant, the nitrogenous compound A for taking certain mass, are dissolved in
In deionized water, after ultrasonic disperse dissolves, then doped graphene at the beginning of by being dried to obtain sulphur nitrogen through suction filtration after hydro-thermal reaction；
(2) the first doped graphene of the resulting sulphur nitrogen of step (1) is mixed with nitrogenous compound B, obtains sulphur after tube furnace is calcined
Nitrogen co-doped graphene；
(3) cobalt salt and manganese salt mixed configuration cobalt-manganese salt mixture are taken, then by itself and the resulting sulfur and nitrogen co-doped graphene of step (2)
It is dissolved in deionized water, is mixed evenly to obtain mixed liquor；
(4) ammonium hydroxide is added into step (3) resulting mixed liquor, in hydrothermal reaction kettle after heating reaction, dry through suction filtration
To cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material；
Sulfur-containing compound described in step (1) is the reducing agent of sulfur-bearing, is selected from one of thioacetic acid, 2 mercapto ethanol or two
Kind, anionic surfactant be selected from neopelex, dodecyl sodium sulfate, lauryl sodium sulfate one kind or
It is a variety of；
Nitrogenous compound A described in step (1) is selected from one of hexamethylenetetramine, urea, melamine or a variety of；
Hydrothermal temperature is 60 ~ 100 DEG C in the step (1), 5 ~ 72h of reaction time.
2. the preparation side of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material according to claim 1
Method, it is characterised in that: graphite oxide powder described in step (1), sulfur-containing compound, anionic surfactant, nitrogenous chemical combination
The mass ratio of object A is 1:(1 ~ 10): (0.5 ~ 5): (2 ~ 15).
3. the preparation side of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material according to claim 1
Method, it is characterised in that: 0.5 ~ 5h of ultrasonic time in the step (1), drying condition are as follows: 60-80 DEG C of temperature, time 1-12 h.
4. the preparation side of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material according to claim 1
Method, it is characterised in that: nitrogenous compound B is selected from one of hexamethylenetetramine, urea, melamine in the step (2)
Or a variety of, the mass ratio (1 ~ 20) of nitrogenous compound B and the first doped graphene of sulphur nitrogen: 1.
5. the preparation of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material according to claim 1 or 4
Method, it is characterised in that: the step (2) reaction temperature in tube furnace is 150 ~ 750 DEG C, and the reaction time is 0.5 ~ 10 h.
6. the preparation side of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material according to claim 1
Method, it is characterised in that: sulfur and nitrogen co-doped graphene concentration is 1 ~ 100mg/ml in the mixed liquor of the step (3), and cobalt salt is nitre
One of sour cobalt, cobaltous sulfate, cobalt chloride, cobalt oxalate, manganese salt be one of manganese nitrate, manganese sulfate, manganese chloride, manganese oxalate,
The cobalt salt and manganese salt 1:1 in mass ratio mixing.
7. the preparation side of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material according to claim 6
Method, it is characterised in that: in the step (4), the ratio of sulfur and nitrogen co-doped graphene, ammonium hydroxide and cobalt-manganese salt mixture is (1 ~ 5)
G:(10 ~ 18) g:(0.01 ~ 0.05) mol, reaction temperature is 150 ~ 250 DEG C in hydrothermal reaction kettle, and the reaction time is 2 ~ 5 h.
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