CN107017094A - A kind of graphene@NiMn LDH combination electrode materials of polyaniline-coated and preparation method thereof - Google Patents
A kind of graphene@NiMn LDH combination electrode materials of polyaniline-coated and preparation method thereof Download PDFInfo
- Publication number
- CN107017094A CN107017094A CN201710405475.2A CN201710405475A CN107017094A CN 107017094 A CN107017094 A CN 107017094A CN 201710405475 A CN201710405475 A CN 201710405475A CN 107017094 A CN107017094 A CN 107017094A
- Authority
- CN
- China
- Prior art keywords
- polyaniline
- graphene
- graphene oxide
- aniline
- nimn
- 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.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 75
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 60
- 239000007772 electrode material Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910003289 NiMn Inorganic materials 0.000 title abstract description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 86
- 238000002604 ultrasonography Methods 0.000 claims abstract description 25
- 239000012043 crude product Substances 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 239000002270 dispersing agent Substances 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 19
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 18
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 18
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 17
- -1 polytetrafluoroethylene Polymers 0.000 claims description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- 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 11
- 239000003999 initiator Substances 0.000 claims description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 8
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 18
- 239000002131 composite material Substances 0.000 abstract description 10
- 229910052759 nickel Inorganic materials 0.000 abstract description 9
- 230000005611 electricity Effects 0.000 abstract description 8
- 238000001914 filtration Methods 0.000 abstract description 8
- 238000005406 washing Methods 0.000 abstract description 8
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000003750 conditioning effect Effects 0.000 abstract 1
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 239000011572 manganese Substances 0.000 abstract 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000003990 capacitor Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical class [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 239000006260 foam Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000000643 oven drying Methods 0.000 description 7
- 239000000178 monomer Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 description 4
- 239000002322 conducting polymer Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 229910002518 CoFe2O4 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- BYOBIQOEWYNTMM-UHFFFAOYSA-N manganese;nitric acid Chemical compound [Mn].O[N+]([O-])=O BYOBIQOEWYNTMM-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 210000002700 urine Anatomy 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
- H01G11/30—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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- 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
-
- 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
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention belongs to electrode material technical field, the graphene@NiMn LDH combination electrode materials of specially a kind of polyaniline-coated and preparation method thereof.Preparation process of the present invention includes：Graphene oxide is dissolved in deionized water and carries out ultrasound；Aniline is added to dispersant for ultrasonic and prepares aniline dispersion liquid；Graphene oxide solution mixes ultrasound with aniline dispersion liquid；Graphene oxide/aniline mixed liquor carries out polymerisation and obtains graphene oxide/polyaniline crude product；Nickel source, manganese source and conditioning agent are added into graphene oxide/polyaniline crude product and carries out hydro-thermal reaction；Filtration washing and drying, that is, obtain the graphene NiMn LDH composites of polyaniline-coated.The composite has played the electrochemistry feature of polyaniline, graphene and nickel manganese layered double hydroxide, big with specific surface area, conducts electricity very well, the features such as specific capacitance is high.
Description
Technical field
Present invention relates particularly to a kind of graphene@NiMn-LDH combination electrode materials of polyaniline-coated and its preparation side
Method, belongs to electrode composite material technical field.
Background technology
Ultracapacitor, the electrochemistry advantage with better than traditional capacitor and secondary cell, with than traditional capacitor
High energy density, the power density higher than secondary cell and long cycle life.Electrode material as ultracapacitor core
Center portion part, decides the quality of ultracapacitor chemical property.The focus electrode material studied at present mainly includes graphene
Deng carbon material, transition metal oxide, conducting polymer materials.
Polyaniline has conjugated system as a kind of intrinsic conducting polymer on its main chain, can be conductive by doping.
The features such as polyaniline is by low cost, green non-pollution, ability of adulterating by force, high porosity, wide potential range, good reversibility,
There is preferably application, theoretical specific capacitance is up to 2000Fg in terms of preparing electrode of super capacitor-1, as in super capacitor electrode
One of conducting polymer of greatest concern in the material of pole.Polyaniline is by occurring Faraday pseudo-capacitance effect storage energy, in electricity
Redox reaction storage electric charge occurs in the intrinsic material of pole.High-energy-density and high specific capacitance that transition metal oxide has
Also received much concern in ultracapacitor field.Such as MnO2、Co3O4、Fe3O4、CoFe2O4Deng transition metal oxide, but its compared with
Low conductance and not high power density limit the further raising of its chemical property.
Graphene is as the two-dimensional material of ultra-thin and ultra-light, specific surface area and high-strength electrical conductivity by superelevation, as super
Favorite in level capacitor material.Conjugation group on polyaniline backbone can interact with graphene, and such as π-π are common
Yoke, electrostatic interaction, are adsorbed in graphenic surface, can regulate and control the functional group's number and species of graphenic surface, improve electrode material
The specific capacitance of material；Polyaniline can also be by wrapping up the specific capacitance of the further composite of transition metal oxide.
The content of the invention
In order to improve the chemical property of electrode material for super capacitor, it is an object of the invention to provide a kind of polyaniline bag
Graphene@NiMn-LDH combination electrode materials covered and preparation method thereof.The present invention can solve existing laminated type bimetal hydroxide
The problem of thing electrode material specific capacitance is not high enough, and strengthen its cycle performance.
A kind of preparation method of the graphene@NiMn-LDH combination electrode materials of polyaniline-coated provided by the present invention,
Its preparing raw material includes：Graphene oxide, aniline, neopelex, ammonium persulfate, concentrated hydrochloric acid, nickel nitrate, nitric acid
Manganese, urea and ammonium fluoride.
The present invention provides a kind of preparation method of the graphene@NiMn-LDH combination electrode materials of polyaniline-coated, specifically
Step is as follows：
(1) initiator and inorganic acid are added in graphene oxide/aniline mixed liquor, polymerisation is carried out, after reaction terminates,
Centrifugation, filter cake is washed with deionized to the pH of efflux untill neutral, obtains graphene oxide/polyaniline crude product；
(2) nickel nitrate, manganese nitrate, ammonium fluoride and urea or hexa-methylene are added into graphene oxide/polyaniline crude product
Tetramine, carries out ultrasound；
(3) mixed liquor after ultrasound is transferred to polytetrafluoroethylene (PTFE) stainless steel cauldron and carries out hydro-thermal reaction, reaction terminates
Afterwards, filter, wash, being dried to obtain the graphene@NiMn-LDH combination electrode materials of polyaniline-coated.
In above-mentioned steps (1), graphene oxide/aniline mixed liquor is mixed by graphene oxide water solution and aniline dispersion liquid
Obtain；In graphene oxide water solution, the mass ratio of graphene oxide and deionized water is 1:2~3:2；Aniline dispersion liquid is by benzene
Amine and dispersant are 1 in mass ratio:5~10:1 is mixed to get, and dispersant is neopelex.
In above-mentioned steps (1), the mass ratio of graphene oxide and aniline in graphene oxide/aniline mixed liquor is 1:10
~5:1；Initiator is ammonium persulfate；Hydrochloric acid is concentrated hydrochloric acid.
In above-mentioned steps (2), the mass ratio of graphene oxide/polyaniline crude product and nickel nitrate is 1:2~1:10；Nickel nitrate
Mass ratio with manganese nitrate is 2:1~6:1；The mass ratio of nickel nitrate and urea or hexa is 1:1~5:1；Nitric acid
The mass ratio of nickel and ammonium fluoride is 10:1~20:1；Ultrasonic time is 1~2h.
In above-mentioned steps (3), hydrothermal temperature is 160~180 DEG C；The hydro-thermal reaction time is 12~24h.
In above-mentioned steps (3), drying temperature is 30~60 DEG C；Drying time is 12~18h.
The present invention also provides a kind of graphene@NiMn-LDH combination electrodes of polyaniline-coated made from above-mentioned preparation method
Material.
Compared to the prior art, the beneficial effects of the present invention are：
The graphene@NiMn-LDH composites of polyaniline-coated prepared by the present invention, polyaniline successfully wraps up graphene@
NiMn, parcel is uniform, with higher specific surface area.
The graphene@NiMn-LDH composites of polyaniline-coated prepared by the present invention, are used as electrode of super capacitor material
Material, shows excellent chemical property.
Brief description of the drawings
Fig. 1 be the graphene@NiMn-LDH composites of the polyaniline-coated of the gained of embodiment 1 at 10000 times and
Scanning electron microscope (SEM) photograph under 1000000 times.
Fig. 2 is graphene@NiMn-LDH composites the sweeping under 10000 times of the polyaniline-coated of the gained of embodiment 2
Retouch electron microscope.
Fig. 3 is the XRD diffraction patterns of the graphene@NiMn-LDH composites of the polyaniline-coated of the gained of embodiment 3.
Fig. 4 is that the graphene@NiMn-LDH composites of the polyaniline-coated of the gained of embodiment 4 pass through electro-chemical test institute
The cyclic voltammogram obtained.
Embodiment
In order to more specifically illustrate the present invention, the present invention is further explained below by specific embodiment and with reference to accompanying drawing
State, but do not limit the scope of the invention.
Embodiment 1
(1) 10mg graphene oxides are added in 20mg deionized waters, and carry out ultrasonic mixing 1h；
(2) 100mg aniline monomers are weighed to be added in 100mg dispersant neopelexes, aniline is obtained and disperses
Liquid；
(3) graphene dispersing solution for obtaining step (1) mixes ultrasound 1h with the aniline dispersion liquid that step (2) is obtained；
(4) initiator ammonium persulfate 50mg is sequentially added in the graphene oxide obtained to step (3)/aniline mixed liquor,
Concentrated hydrochloric acid 90mg, then at 0 DEG C, rotating speed is that 300r/min stirring 12h progress polymerisations obtain mixed liquor, is centrifuged, gained
The pH to efflux is washed with deionized untill neutrality in filter cake, obtains graphene oxide/polyaniline crude product；
(5) 20mg graphene oxides/polyaniline crude product is taken, 180mg nickel nitrates, 90mg manganese nitrates, 60mg urine is sequentially added
Plain (or hexa), 18mg ammonium fluorides carry out ultrasound 1h；
(6) mixed liquor after ultrasound is transferred to polytetrafluoroethylene (PTFE) stainless steel cauldron, in carrying out hydro-thermal reaction at 160 DEG C
24h；
(7) graphite that oven drying 12h at filtration washing, 40 DEG C obtains polyaniline-coated is carried out with ethanol and deionized water
Alkene@NiMn-LDH composites.
According to the graphene@NiMn-LDH composites of the polyaniline-coated obtained by this embodiment method, it is 10000
See Fig. 1 with the ESEM under 1000000 times again, product performance multi-layer flower laminated structure, polyaniline-graphite alkene is wrapped up
NiMn-LDH surface.Electrode of super capacitor is prepared into, with 2molL-1KOH solution is used as ginseng as electrolyte, Ag electrodes
Than electrode, nickel foam is as reference electrode, and specimen material determines its chemical property, be in current density as working electrode
0.5Ag-1When, its specific capacitance is 1699.3F g-1, obvious redox peaks are showed in cyclic voltammetry, counterfeit electricity is represented
Hold effect；Specific capacitance after the circle of circulation 2000 is 1609.23F g-1, cycle efficieny is up to 94.7%.
Embodiment 2
(1) 20mg graphene oxides are added in 20mg deionized waters, and carry out ultrasonic mixing 2h；
(2) 140mg aniline monomers are weighed to be added in 500mg dispersant neopelexes, aniline is obtained and disperses
Liquid；
(3) graphene dispersing solution for obtaining step (1) mixes ultrasound 2h with the aniline dispersion liquid that step (2) is obtained；
(4) initiator ammonium persulfate 50mg is sequentially added in the graphene oxide obtained to step (3)/aniline mixed liquor,
Concentrated hydrochloric acid 100mg, then at 0 DEG C, rotating speed is that 200r/min stirring 24h progress polymerisations obtain mixed liquor, is centrifuged, gained
The pH to efflux is washed with deionized untill neutrality in filter cake, obtains graphene oxide/polyaniline crude product；
(5) 150mg graphene oxides/polyaniline crude product is taken, 260mg nickel nitrates, 130mg manganese nitrates, 100mg is sequentially added
Urea (or hexa), 30mg ammonium fluorides carry out ultrasound 1h；
(6) mixed liquor after ultrasound is transferred to polytetrafluoroethylene (PTFE) stainless steel cauldron, in carrying out hydro-thermal reaction at 180 DEG C
18h；
(7) graphite that oven drying 16h at filtration washing, 40 DEG C obtains polyaniline-coated is carried out with ethanol and deionized water
Alkene@NiMn-LDH composites.
According to the graphene@NiMn-LDH composites of the polyaniline-coated obtained by this embodiment method, it is 10000
ESEM under times is shown in Fig. 2, and graphene-polyaniline has wrapped up NiMn-LDH.Electrode of super capacitor is prepared into, with 2mol
L-1KOH solution is as electrolyte, and Ag electrodes are as reference electrode, and nickel foam is used as work electricity as reference electrode, specimen material
Pole, determines its chemical property, is 0.5A g in current density-1When, its specific capacitance is 1257.8F g-1；After the circle of circulation 2000
Specific capacitance be 1142.1F g-1, cycle efficieny is 90.8%.
Embodiment 3
(1) 20mg graphene oxides are added in 20mg deionized waters, and carry out ultrasonic mixing 2h；
(2) 160mg aniline monomers are weighed to be added in 200mg dispersant neopelexes, aniline is obtained and disperses
Liquid；
(3) graphene dispersing solution for obtaining step (1) mixes ultrasound 2h with the aniline dispersion liquid that step (2) is obtained；
(4) initiator ammonium persulfate 30mg is sequentially added in the graphene oxide obtained to step (3)/aniline mixed liquor,
Concentrated hydrochloric acid 60mg, then at 0 DEG C, rotating speed is that 300r/min stirring 15h progress polymerisations obtain mixed liquor, is centrifuged, gained
The pH to efflux is washed with deionized untill neutrality in filter cake, obtains graphene oxide/polyaniline crude product；
(5) 100mg graphene oxides/polyaniline crude product is taken, 350mg nickel nitrates, 180mg manganese nitrates, 150mg is sequentially added
Urea (or hexa), 60mg ammonium fluorides carry out ultrasound 1h；
(6) mixed liquor after ultrasound is transferred to polytetrafluoroethylene (PTFE) stainless steel cauldron, in carrying out hydro-thermal reaction at 180 DEG C
18h；
(7) graphite that oven drying 16h at filtration washing, 40 DEG C obtains polyaniline-coated is carried out with ethanol and deionized water
Alkene@NiMn-LDH composites.
According to the graphene@NiMn-LDH composites of the polyaniline-coated obtained by this embodiment method, its XRD diffraction
Figure is shown in Fig. 3, the angle of diffraction 11.07 °, 19.25 °, 23.64 °, 32.72 °, 33.71 °, 36.49 °, 37.37 °, 43.16 °,
46.94 °, 51.87 °, 53.22 °, 59.00 °, 60.82 ° respectively correspond to crystal face (110), (211), (221), (322), (330),
(421), (332), (440), (530), (621), (533), (640), (113), show NiMn-LDH successful synthesis；It is prepared into
Electrode of super capacitor, with 2molL-1KOH solution is as electrolyte, and Ag electrodes are used as control as reference electrode, nickel foam
Electrode, specimen material determines its chemical property as working electrode, is 0.5A g in current density-1When, its specific capacitance is
1096.3F g-1, obvious faraday's redox peaks are showed in cyclic voltammetry；Circulating the specific capacitance after 2000 circles is
972.4F g-1, cycle efficieny is 88.7%.
Embodiment 4
(1) 20mg graphene oxides are added in 20mg deionized waters, and carry out ultrasonic mixing 2h；
(2) 220mg aniline monomers are weighed to be added in 500mg dispersant neopelexes, aniline is obtained and disperses
Liquid；
(3) graphene dispersing solution for obtaining step (1) mixes ultrasound 1.5h with the aniline dispersion liquid that step (2) is obtained；
(4) initiator ammonium persulfate 30mg is sequentially added in the graphene oxide obtained to step (3)/aniline mixed liquor,
Concentrated hydrochloric acid 100mg, then at 0 DEG C, rotating speed is that 200r/min stirring 12h progress polymerisations obtain mixed liquor, is centrifuged, gained
The pH to efflux is washed with deionized untill neutrality in filter cake, obtains graphene oxide/polyaniline crude product；
(5) 100mg graphene oxides/polyaniline crude product is taken, 500mg nickel nitrates, 300mg manganese nitrates, 200mg is sequentially added
Urea (or hexa), 80mg ammonium fluorides carry out ultrasound 1h；
(6) mixed liquor after ultrasound is transferred to polytetrafluoroethylene (PTFE) stainless steel cauldron, in carrying out hydro-thermal reaction at 160 DEG C
12h；
(7) graphite that oven drying 16h at filtration washing, 40 DEG C obtains polyaniline-coated is carried out with ethanol and deionized water
Alkene@NiMn-LDH composites.
According to the graphene@NiMn-LDH composites of the polyaniline-coated obtained by this embodiment method, it is prepared into super
Level electrode for capacitors, with 2molL-1KOH solution is as electrolyte, and Ag electrodes are used as control electricity as reference electrode, nickel foam
Pole, specimen material determines its chemical property as working electrode, and obvious redox is showed in cyclic voltammetry
Peak, its cyclic voltammogram is shown in Fig. 4；It is 0.5A g in current density-1When, its specific capacitance is 1381.6F g-1；After the circle of circulation 2000
Specific capacitance be 1242.1F g-1, cycle efficieny is 89.9%.
Embodiment 5
(1) 20mg graphene oxides are added in 20mg deionized waters, and carry out ultrasonic mixing 2h；
(2) 200mg aniline monomers are weighed to be added in 400mg dispersant neopelexes, aniline is obtained and disperses
Liquid；
(3) graphene dispersing solution for obtaining step (1) mixes ultrasound 2h with the aniline dispersion liquid that step (2) is obtained；
(4) initiator ammonium persulfate 30mg is sequentially added in the graphene oxide obtained to step (3)/aniline mixed liquor,
Concentrated hydrochloric acid 120mg, then at 0 DEG C, rotating speed is that 300r/min stirring 12h progress polymerisations obtain mixed liquor, is centrifuged, gained
The pH to efflux is washed with deionized untill neutrality in filter cake, obtains graphene oxide/polyaniline crude product；
(5) 100mg graphene oxides/polyaniline crude product is taken, 700mg nickel nitrates, 300mg manganese nitrates, 200mg is sequentially added
Urea (or hexa), 80mg ammonium fluorides carry out ultrasound 1h；
(6) mixed liquor after ultrasound is transferred to polytetrafluoroethylene (PTFE) stainless steel cauldron, in carrying out hydro-thermal reaction at 160 DEG C
24h；
(7) graphite that oven drying 18h at filtration washing, 40 DEG C obtains polyaniline-coated is carried out with ethanol and deionized water
Alkene@NiMn-LDH composites.
According to the graphene@NiMn-LDH composites of the polyaniline-coated obtained by this embodiment method, it is prepared into super
Level electrode for capacitors, with 2molL-1KOH solution is as electrolyte, and Ag electrodes are used as control electricity as reference electrode, nickel foam
Pole, specimen material determines its chemical property as working electrode, is 0.5Ag in current density-1When, its specific capacitance is
1512.7F g-1, when current density is 10Ag-1When, its specific capacitance is 1266F g-1, with good high rate performance；In circulation
Obvious redox peaks are showed in volt-ampere test, fake capacitance effect is represented；Specific capacitance after the circle of circulation 2000 is 1408.3F
g-1, cycle efficieny is 93.1%.
Embodiment 6
(1) 20mg graphene oxides are added in 20mg deionized waters, and carry out ultrasonic mixing 2h；
(2) 500mg aniline monomers are weighed to be added in 1000mg dispersant neopelexes, aniline is obtained and disperses
Liquid；
(3) graphene dispersing solution for obtaining step (1) mixes ultrasound 2h with the aniline dispersion liquid that step (2) is obtained；
(4) initiator ammonium persulfate 80mg is sequentially added in the graphene oxide obtained to step (3)/aniline mixed liquor,
Concentrated hydrochloric acid 200mg, then at 0 DEG C, rotating speed is that 200r/min stirring 24h progress polymerisations obtain mixed liquor, is centrifuged, gained
The pH to efflux is washed with deionized untill neutrality in filter cake, obtains graphene oxide/polyaniline crude product；
(5) 200mg graphene oxides/polyaniline crude product is taken, 1000mg nickel nitrates are sequentially added, 600mg manganese nitrates,
500mg urea (or hexa), 200mg ammonium fluorides carry out ultrasound 1h；
(6) mixed liquor after ultrasound is transferred to polytetrafluoroethylene (PTFE) stainless steel cauldron, in carrying out hydro-thermal reaction at 180 DEG C
12h；
(7) graphite that oven drying 18h at filtration washing, 40 DEG C obtains polyaniline-coated is carried out with ethanol and deionized water
Alkene@NiMn-LDH composites.
According to the graphene@NiMn-LDH composites of the polyaniline-coated obtained by this embodiment method, it is prepared into super
Level electrode for capacitors, with 2molL-1KOH solution is as electrolyte, and Ag electrodes are used as control electricity as reference electrode, nickel foam
Pole, specimen material determines its chemical property as working electrode, is 0.5Ag in current density-1When, its specific capacitance is
1294.8F g-1；Specific capacitance after the circle of circulation 2000 is 1145.9F g-1, cycle efficieny is 88.5%.
Embodiment 7
This embodiment compared with Example 1, does not add graphene and polyaniline, and other steps are consistent with embodiment, system
Standby NiMn-LDH, is comprised the following steps that：
(1) 180mg nickel nitrates are taken, 90mg manganese nitrates, 60mg urea (or hexa), 18mg ammonium fluorides are surpassed
The scattered 1h of sound mixing；
(2) mixed liquor after ultrasound is transferred to polytetrafluoroethylene (PTFE) stainless steel cauldron, in carrying out hydro-thermal reaction at 160 DEG C
24h；
(3) oven drying 12h at filtration washing, 40 DEG C is carried out with ethanol and deionized water and obtains NiMn-LDH materials.
According to the NiMn-LDH materials obtained by this embodiment method, electrode of super capacitor is prepared into, with 2molL- 1KOH solution is as electrolyte, and Ag electrodes are as reference electrode, and nickel foam is used as work electricity as reference electrode, specimen material
Pole, determines its chemical property, is 0.5A g in current density-1When, its specific capacitance is 756.3F g-1；After the circle of circulation 2000
Specific capacitance is 677.6F g-1, cycle efficieny is up to 89.6%.
Claims (7)
1. a kind of preparation method of the graphene@NiMn-LDH combination electrode materials of polyaniline-coated, it is characterised in that specific step
It is rapid as follows：
(1) initiator and inorganic acid are added in graphene oxide/aniline mixed liquor, polymerisation is carried out, after reaction terminates, from
The heart, filter cake is washed with deionized to the pH of efflux untill neutral, obtains graphene oxide/polyaniline crude product；
(2) nickel nitrate, manganese nitrate, ammonium fluoride and urea or hexa are added into graphene oxide/polyaniline crude product,
Carry out ultrasound；
(3) mixed liquor after ultrasound is transferred to polytetrafluoroethylene (PTFE) stainless steel cauldron and carries out hydro-thermal reaction, after reaction terminates, mistake
Filter, wash, being dried to obtain the graphene@NiMn-LDH combination electrode materials of polyaniline-coated.
2. preparation method as claimed in claim 1, it is characterised in that in step (1), graphene oxide/aniline mixed liquor by
Graphene oxide water solution and aniline dispersion liquid are mixed to get；In graphene oxide water solution, graphene oxide and deionized water
Mass ratio be 1:2~3:2；Aniline dispersion liquid is 1 in mass ratio by aniline and dispersant:5~10:1 is mixed to get, dispersant
For neopelex.
3. preparation method as claimed in claim 1, it is characterised in that in step (1), in graphene oxide/aniline mixed liquor
Graphene oxide and aniline mass ratio be 1:10~5:1；Initiator is ammonium persulfate；Hydrochloric acid is concentrated hydrochloric acid.
4. preparation method as claimed in claim 1, it is characterised in that in step (2), graphene oxide/polyaniline crude product with
The mass ratio of nickel nitrate is 1:2~1:10；The mass ratio of nickel nitrate and manganese nitrate is 2:1~6:1；Nickel nitrate and urea or six are sub-
The mass ratio of tetramine is 1:1~5:1；The mass ratio of nickel nitrate and ammonium fluoride is 10:1~20:1；Ultrasonic time be 1~
2h。
5. preparation method as claimed in claim 1, it is characterised in that in step (3), hydrothermal temperature is 160~180
℃；The hydro-thermal reaction time is 12~24h.
6. preparation method as claimed in claim 1, it is characterised in that in step (3), drying temperature is 30~60 DEG C；Dry
Time is 12~18h.
7. a kind of graphene@NiMn-LDH combination electrodes of polyaniline-coated made from preparation method as described in claim 1~6
Material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710405475.2A CN107017094A (en) | 2017-06-01 | 2017-06-01 | A kind of graphene@NiMn LDH combination electrode materials of polyaniline-coated and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710405475.2A CN107017094A (en) | 2017-06-01 | 2017-06-01 | A kind of graphene@NiMn LDH combination electrode materials of polyaniline-coated and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107017094A true CN107017094A (en) | 2017-08-04 |
Family
ID=59452083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710405475.2A Pending CN107017094A (en) | 2017-06-01 | 2017-06-01 | A kind of graphene@NiMn LDH combination electrode materials of polyaniline-coated and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107017094A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108766785A (en) * | 2018-07-02 | 2018-11-06 | 桂林电子科技大学 | A kind of graphene-polypyrrole-cobalt nickel bimetal hydroxide composite material and its preparation method and application |
| CN109167074A (en) * | 2018-08-08 | 2019-01-08 | 东华大学 | The nitrogen-doped carbon nanocomposite of hollow additive Mn cobalt oxide nickel coated and preparation |
| CN110517898A (en) * | 2019-08-14 | 2019-11-29 | 上海应用技术大学 | The preparation method of the graphene@CoAl-LDH combination electrode material of polyaniline-coated |
| CN110676067A (en) * | 2019-10-24 | 2020-01-10 | 陈丰 | Polyaniline-double metal hydroxide supercapacitor material and preparation method thereof |
| CN110880424A (en) * | 2019-11-28 | 2020-03-13 | 朱旭烈 | Polybenzazole coated nickel-cobalt compound supercapacitor material and preparation method thereof |
| CN111118908A (en) * | 2019-12-31 | 2020-05-08 | 浙江大学 | Layered double-metal hydroxide-polyaniline modified porous conductive composite material and preparation method and application thereof |
| CN111974429A (en) * | 2019-05-21 | 2020-11-24 | 南京大学 | Preparation method of multilayer pie-shaped NiMn-LDHs catalyst |
| CN112375415A (en) * | 2020-11-12 | 2021-02-19 | 厦门大学 | Preparation method and application of graphene-based composite material anti-corrosion auxiliary agent |
| CN112542328A (en) * | 2020-12-02 | 2021-03-23 | 浙江大学 | Ternary layered metal hydroxide @ polyaniline composite electrode material and preparation method and application thereof |
| CN113345723A (en) * | 2021-04-30 | 2021-09-03 | 上海交通大学 | Porous graphene/polyaniline composite film and preparation method and application thereof |
| CN113813945A (en) * | 2021-09-30 | 2021-12-21 | 宁德师范学院 | Three-dimensional space network graphene-based polyaniline/PtAg composite catalyst and preparation method thereof |
| CN115172065A (en) * | 2022-06-16 | 2022-10-11 | 宁德师范学院 | Three-dimensional capacitance electrode material with graphene surface grafted with polyaniline/titanium dioxide |
| CN115798946A (en) * | 2023-01-30 | 2023-03-14 | 昆山美淼新材料科技有限公司 | Production process of metal graphene multi-element composite electrode |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130117607A (en) * | 2012-04-18 | 2013-10-28 | 주식회사 엘지화학 | The electrodes and the secondary battery comprising the same |
| CN105924963A (en) * | 2016-06-06 | 2016-09-07 | 上海应用技术学院 | Preparation method of graphene/ ferric oxide/ polyaniline composite material |
| CN106229163A (en) * | 2016-08-05 | 2016-12-14 | 上海应用技术学院 | A kind of Graphene coupling flower ball-shaped Ni Mn bimetallic oxide three-dimensional hierarchical structure electrode material and preparation method thereof |
-
2017
- 2017-06-01 CN CN201710405475.2A patent/CN107017094A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130117607A (en) * | 2012-04-18 | 2013-10-28 | 주식회사 엘지화학 | The electrodes and the secondary battery comprising the same |
| CN105924963A (en) * | 2016-06-06 | 2016-09-07 | 上海应用技术学院 | Preparation method of graphene/ ferric oxide/ polyaniline composite material |
| CN106229163A (en) * | 2016-08-05 | 2016-12-14 | 上海应用技术学院 | A kind of Graphene coupling flower ball-shaped Ni Mn bimetallic oxide three-dimensional hierarchical structure electrode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 付帅: "金属氢氧化物/石墨烯基复合材料的制备及其电催化性能的研究", 《中国优秀硕士学位论文全文库工程科技Ⅱ辑》 * |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108766785B (en) * | 2018-07-02 | 2020-05-22 | 桂林电子科技大学 | Graphene-polypyrrole-cobalt-nickel double-metal hydroxide composite material and preparation method and application thereof |
| CN108766785A (en) * | 2018-07-02 | 2018-11-06 | 桂林电子科技大学 | A kind of graphene-polypyrrole-cobalt nickel bimetal hydroxide composite material and its preparation method and application |
| CN109167074A (en) * | 2018-08-08 | 2019-01-08 | 东华大学 | The nitrogen-doped carbon nanocomposite of hollow additive Mn cobalt oxide nickel coated and preparation |
| CN111974429A (en) * | 2019-05-21 | 2020-11-24 | 南京大学 | Preparation method of multilayer pie-shaped NiMn-LDHs catalyst |
| CN111974429B (en) * | 2019-05-21 | 2022-04-19 | 南京大学 | Preparation method of multilayer pie-shaped NiMn-LDHs catalyst |
| CN110517898A (en) * | 2019-08-14 | 2019-11-29 | 上海应用技术大学 | The preparation method of the graphene@CoAl-LDH combination electrode material of polyaniline-coated |
| CN110676067B (en) * | 2019-10-24 | 2021-05-14 | 绍兴市梓昂新材料有限公司 | Polyaniline-double metal hydroxide supercapacitor material and preparation method thereof |
| CN110676067A (en) * | 2019-10-24 | 2020-01-10 | 陈丰 | Polyaniline-double metal hydroxide supercapacitor material and preparation method thereof |
| CN110880424A (en) * | 2019-11-28 | 2020-03-13 | 朱旭烈 | Polybenzazole coated nickel-cobalt compound supercapacitor material and preparation method thereof |
| CN111118908A (en) * | 2019-12-31 | 2020-05-08 | 浙江大学 | Layered double-metal hydroxide-polyaniline modified porous conductive composite material and preparation method and application thereof |
| CN112375415A (en) * | 2020-11-12 | 2021-02-19 | 厦门大学 | Preparation method and application of graphene-based composite material anti-corrosion auxiliary agent |
| CN112542328A (en) * | 2020-12-02 | 2021-03-23 | 浙江大学 | Ternary layered metal hydroxide @ polyaniline composite electrode material and preparation method and application thereof |
| CN113345723A (en) * | 2021-04-30 | 2021-09-03 | 上海交通大学 | Porous graphene/polyaniline composite film and preparation method and application thereof |
| CN113813945A (en) * | 2021-09-30 | 2021-12-21 | 宁德师范学院 | Three-dimensional space network graphene-based polyaniline/PtAg composite catalyst and preparation method thereof |
| CN113813945B (en) * | 2021-09-30 | 2023-08-18 | 宁德师范学院 | Three-dimensional space network graphene-based polyaniline/PtAg composite catalyst and preparation method thereof |
| CN115172065A (en) * | 2022-06-16 | 2022-10-11 | 宁德师范学院 | Three-dimensional capacitance electrode material with graphene surface grafted with polyaniline/titanium dioxide |
| CN115172065B (en) * | 2022-06-16 | 2023-04-25 | 宁德师范学院 | Three-dimensional capacitance electrode material with polyaniline/titanium dioxide grafted on graphene surface |
| CN115798946A (en) * | 2023-01-30 | 2023-03-14 | 昆山美淼新材料科技有限公司 | Production process of metal graphene multi-element composite electrode |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107017094A (en) | A kind of graphene@NiMn LDH combination electrode materials of polyaniline-coated and preparation method thereof | |
| Zhai et al. | Facile fabrication of hierarchical porous rose-like NiCo 2 O 4 nanoflake/MnCo 2 O 4 nanoparticle composites with enhanced electrochemical performance for energy storage | |
| CN105253871B (en) | Ultracapacitor nitrogenous carbon material and preparation method thereof, electrode material for super capacitor | |
| JP5322435B2 (en) | Negative electrode active material for electricity storage devices | |
| Yang et al. | A flexible and binder-free reduced graphene oxide/Na2/3 [Ni1/3Mn2/3] O2 composite electrode for high-performance sodium ion batteries | |
| CN105374571B (en) | Lithium-ion capacitor negative plate and preparation method thereof, winding type lithium ion capacitor | |
| CN104979105B (en) | A kind of nitrogen-doped porous carbon material, preparation method and applications | |
| CN104993174B (en) | A kind of preparation method of lithium ion battery negative material | |
| CN108389732A (en) | A kind of hydro-thermal method prepares the method and its composite material of manganese dioxide/carbon titanium composite material | |
| CN108147464A (en) | A kind of rice-shaped manganese dioxide/carbon titanium composite material and preparation method thereof | |
| Wu et al. | Porous Ni–Mo–Co hydroxide nanoflakes on carbon cloth for supercapacitor application | |
| CN108190962A (en) | A kind of manganese dioxide nano-plates/carbonization titanium composite material and preparation method thereof | |
| CN103247787A (en) | Composite negative pole material for lithium-ion battery and manufacturing method of negative pole material | |
| CN107394114A (en) | Anode material of lithium battery and preparation method thereof and lithium battery anode, lithium battery | |
| CN107069043A (en) | Lithium ion battery and preparation method thereof | |
| CN109428062A (en) | A kind of graphene-silicon composite cathode material and preparation method thereof | |
| Shen et al. | Versatile MnO2/CNT Putty‐Like Composites for High‐Rate Lithium‐Ion Batteries | |
| CN104300133A (en) | Carbon nanotube coated lithium titanate material and its preparation method | |
| CN108364802A (en) | A kind of manganese dioxide nanowire/titanium carbide composite material and preparation method | |
| CN109167036B (en) | TiN and conductive polymer composite modified lithium ion layered ternary positive electrode material and preparation method thereof | |
| Yang et al. | A charge-free and membrane-free hybrid capacitive mixing system for salinity gradient energy harvesting | |
| Xin et al. | Organic solvent-assisted free-standing Li 2 MnO 3· LiNi 1/3 Co 1/3 Mn 1/3 O 2 on 3D graphene as a high energy density cathode | |
| CN109148829A (en) | A kind of biomass derived Nano Carbon nickel oxide electrode and its application | |
| CN106384679B (en) | A kind of dumbbell shape CeO2The preparation method of electrode material for super capacitor | |
| CN112952099A (en) | Lithium battery composite positive electrode and preparation method 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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170804 |
|
| RJ01 | Rejection of invention patent application after publication |