CN104701490A - Preparing method and application of sandwich-structure graphene-based carbon cladding metal oxide - Google Patents
Preparing method and application of sandwich-structure graphene-based carbon cladding metal oxide Download PDFInfo
- Publication number
- CN104701490A CN104701490A CN201510153412.3A CN201510153412A CN104701490A CN 104701490 A CN104701490 A CN 104701490A CN 201510153412 A CN201510153412 A CN 201510153412A CN 104701490 A CN104701490 A CN 104701490A
- Authority
- CN
- China
- Prior art keywords
- metal oxide
- graphene
- oxide
- preparation
- scope
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 87
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 73
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 73
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000005253 cladding Methods 0.000 title abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 239000007772 electrode material Substances 0.000 claims abstract description 10
- 229920002521 macromolecule Polymers 0.000 claims abstract description 10
- 239000002105 nanoparticle Substances 0.000 claims abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 20
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims description 13
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001338 self-assembly Methods 0.000 claims description 4
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 claims description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 claims 1
- 238000005576 amination reaction Methods 0.000 claims 1
- 239000001768 carboxy methyl cellulose Substances 0.000 claims 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims 1
- 229910000428 cobalt oxide Inorganic materials 0.000 claims 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims 1
- 229960004643 cupric oxide Drugs 0.000 claims 1
- 150000001991 dicarboxylic acids Chemical class 0.000 claims 1
- 238000001027 hydrothermal synthesis Methods 0.000 claims 1
- 238000000593 microemulsion method Methods 0.000 claims 1
- 229910000480 nickel oxide Inorganic materials 0.000 claims 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 238000005979 thermal decomposition reaction Methods 0.000 claims 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims 1
- 229910001887 tin oxide Inorganic materials 0.000 claims 1
- 239000011787 zinc oxide Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract 1
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical compound [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000003763 carbonization Methods 0.000 abstract 1
- 229910052744 lithium Inorganic materials 0.000 abstract 1
- 239000002135 nanosheet Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 229910002804 graphite Inorganic materials 0.000 description 13
- 239000010439 graphite Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000004408 titanium dioxide Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 238000010790 dilution Methods 0.000 description 6
- 239000012895 dilution Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 125000002769 thiazolinyl group Chemical group 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000012702 metal oxide precursor Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- 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
- 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
-
- 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
-
- 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
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparing method and application of a sandwich-structure graphene-based carbon cladding metal oxide. The preparing method comprises the steps of preparing oxidized graphene nano-sheets and metal oxide nano-particles, wherein macromolecules with carboxyl are adsorbed on the surface of the metal oxide, and macromolecules with amidogen are adsorbed on the surface of the oxidized graphene; adjusting the pH value of a solution to enable the surface of the metal oxide and the surface of the oxidized graphene to have opposite charges, and obtaining a sandwich-structure oxidized-graphene-based metal oxide through electrostatic adsorption; conducting high-temperature carbonization under the protection of inert gas to obtain the sandwich-structure graphene-based carbon cladding metal oxide. The graphene-based metal oxide composite material obtained with the method has the advantages that nanoscale metal oxide particles are obtained, the surfaces of the metal oxide particles are coated with carbon layers, and the composite material is of a sandwich structure. In this way, the composite material has excellent electrochemical property and can serve as the electrode material of a lithium cell and a supercapacitor.
Description
Technical field
The present invention relates to a kind of preparation of novel battery electrode material, specifically, relate to a kind of preparation method and the application with the graphene-based carbon-clad metal oxide of sandwich structure.
Background technology
Lithium ion battery owing to having high storage power density, the advantage such as capacity is large, memory-less effect, rated voltage are high, self-discharge rate is low, lightweight, long service life, high/low temperature strong adaptability, environmental protection, be widely applied in daily life, as the battery of mobile phone and notebook computer.Some metal oxides have higher theoretical capacity, and rich reserves, easily prepare, be expected to the electrode material as lithium ion battery, such as Co
3o
4, NiO, Fe
3o
4, the theoretical specific capacity of the metal oxides such as ZnO is at 700 ~ 1000mAh/g.But the poorly conductive of metal oxide own, electron transfer rate is slow, has larger volume deformation simultaneously, cause breaking of battery material in charge and discharge process, therefore cycle performance and high rate performance poor.The impact that the volume deformation that can effectively reduce metal oxide by the particle size or appearance structure (as loose structure and hollow structure) that control metal oxide brings, improve the chemical property (P.G.Bruce of metal oxide particle, B.Scrosati, J-M.Tarascon, Angew.Chem.Int.Ed.2008,47,2930-2946).It is prepare carbon composite that another kind is improved one's methods, and carbon carrier both can suppress the volume deformation of metal oxide, can improve again the conductivity of compound, thus improves the chemical property of compound.Graphene is a kind of monolayer carbon atomic plane material separated from graphite material, has larger specific area, higher mechanical strength and good heat-conductivity conducting performance.Therefore, compare other carbon carrier, graphene-supported metal oxide has more outstanding chemical property (H.L.Wang, L.F.Cui, Y.Yang, H.S.Casalongue, J.T.Robinson, Y.Y.Liang, Y.Cui, H.J.Dai, J.Am.Chem.Soc.2010,132,13978-13980).But; metal oxide is not easy to control in the growth course of graphenic surface, causes the distribution of sizes of metal oxide particle wider, simultaneously when the load capacity of metal oxide improves; metal oxide particle can be reunited at graphenic surface, all can affect the chemical property of compound.Therefore, wish a kind of novel graphene-based metal oxide of design and synthesis, both particle size and the load capacity of metal oxide can have been controlled, the reunion of metal oxide particle can be suppressed again while high capacity amount, thus improve the chemical property of graphene-based metal oxide, be expected to the electrode material as high performance lithium ion battery or ultracapacitor.
Summary of the invention
The object of the present invention is to provide the preparation method of the graphene-based carbon-clad metal oxide of a kind of sandwich structure, for the electrode material of existing lithium ion battery and ultracapacitor adds a class new product.
The graphene-based carbon-clad metal oxide of sandwich structure disclosed in this invention, it is characterized in that: this composite material has sandwich structure, the length of composite material is within the scope of 1 ~ 5 μm, wide within the scope of 1 ~ 5 μm, high within the scope of 0.5 ~ 1 μm, metal oxide particle diameter is within the scope of 1 ~ 20nm, metal oxide particle surface is coated by carbon-coating, carbon layers having thicknesses is in 0.5 ~ 2nm nanometer range, metal oxide particle is fixed between the graphene layer of self assembly, and the load capacity of metal oxide is within the scope of 50 ~ 90wt%.
The preparation method of the graphene-based carbon-clad metal oxide of above-mentioned sandwich structure, comprises the following steps:
(1) adsorption is prepared containing amino high molecular graphene oxide
By the concentrated sulfuric acid and sodium nitrate mixing, ice bath is cooled to 0 DEG C, adds graphite; Mix after 4 ~ 5 hours, slowly add potassium permanganate; 35 DEG C are reacted 2 hours, add deionized water dilution, and 98 DEG C are stirred 15 minutes, add deionized water dilution, and add hydrogen peroxide; Filter, with the watery hydrochloric acid washing of 5%, then spend deionized water to neutral, obtain graphite oxide; Graphite oxide is ultrasonic in water, obtain graphene oxide solution; Graphene oxide solution is joined, ultrasonic disperse by containing amino macromolecule and NaOH; Centrifugal, wash, be re-dispersed in the aqueous solution for subsequent use.
(2) the carboxylic high molecular metal oxide of adsorption is prepared
Metal oxide precursor, carboxylic surfactant are mixed with alcohols solvent, and pass into nitrogen, stirring and dissolving at 100 DEG C; Temperature rises to 260 DEG C, reacts 30 minutes; Be cooled to room temperature, dialyse four times with sodium citrate solution, then use distill water dialysis twice.
(3) graphene oxide metal oxides is prepared
Carboxylic for adsorption high molecular metal oxide suspension and adsorption are diluted to 100mL respectively containing amino high molecular graphene oxide; With diluted alkaline, the pH value of metal oxide suspension is adjusted to 7 ~ 10, with diluted acid, the pH value of graphene oxide solution is adjusted to 4 ~ 7; Metal oxide suspension is added drop-wise in graphene oxide solution, stirs 1 ~ 3 hour; Centrifugal, washing, drying obtains graphene oxide metal oxides.
(4) graphene-based carbon-clad metal oxide is prepared
Under inert gas shielding, by graphene oxide metal oxides 500 ~ 1000 DEG C of heating 0.1 ~ 2 hour; Be down to room temperature, obtain graphene-based carbon-clad metal oxide.
Sandwich structure provided by the invention graphene-based carbon-clad metal oxide has outstanding chemical property, can be used as the electrode material of lithium ion battery and ultracapacitor.
Effect of the present invention:
The present invention first distinguishes the metal oxide of the amidized graphene oxide of synthetic surface and surface carboxyl groups; the pH value of solution is regulated to make surface of graphene oxide positively charged again; metal oxide surface is electronegative; surface of graphene oxide adsorbing metal oxide particle is made by self assembly; heat under inert gas shielding again; make the macromolecule carbon on metal oxide particle surface change into carbon-coating, redox graphene, obtains the graphene-based carbon-clad metal oxide of sandwich structure simultaneously.This composite material shows higher charge/discharge capacity, outstanding cycle performance and high rate performance, can as the electrode material of lithium ion battery or ultracapacitor.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) figure of graphene-based carbon coated ferriferrous oxide prepared by the present invention;
Fig. 2 is scanning electron microscopy (SEM) figure of graphene-based carbon coated ferriferrous oxide prepared by the present invention;
Fig. 3 is transmission electron microscope (TEM) figure of graphene-based carbon coated ferriferrous oxide prepared by the present invention;
Fig. 4 is the cycle performance of battery figure of graphene-based carbon coated ferriferrous oxide prepared by the present invention.
Embodiment
The preparation method of the graphene oxide related in the present invention comprises the method for the ownership for graphene oxide, the preparation method of the metal oxide related to comprises the method for the ownership for metal oxide nanoparticles, the macromolecule related to comprises all containing macromolecule that is amino or carboxyl, the metal oxide related to comprise all can as the metal oxide of battery electrode material.
Be making further detailed, clear and complete description of how realizing below in conjunction with specific embodiment to the present invention, listed embodiment is only further described the present invention, not thereby limiting the invention:
embodiment 1:
(1) graphene oxide of adsorption PDDA is prepared
Adopt Hummers legal system for graphene oxide, by 230mL sulfuric acid (98%, H
2sO
4) and 5g sodium nitrate (NaNO
3) after mixing, ice bath cools; When temperature is 0 DEG C, under stirring, add 5g graphite; Mix after 4 ~ 5 hours, slowly add 30g potassium permanganate (KMnO
4); 35 DEG C are reacted 2 hours, add the dilution of 460mL deionized water, and 98 DEG C are stirred 15 minutes, add deionized water dilution, and add 100mL hydrogen peroxide (30%, H
2o
2); Filter, wash with the watery hydrochloric acid of 2L 5%, then spend deionized water to neutral, obtain graphite oxide; By graphite oxide in water ultrasonic 0.5 ~ 1 hour graphene oxide solution; By the PDDA (PDDA) of the graphene oxide of 0.03g and 1.3g respectively ultrasonic disperse in the distilled water of 100mL, after ultrasonic 30 minutes, the NaOH of 0.4g is joined PDDA solution for continuous ultrasonic half an hour; Graphene oxide solution is dropwise added drop-wise in PDDA solution under ultrasound condition, ultrasonic 2 hours; Centrifugal, to wash, obtain adsorption PDDA graphene oxide, ultrasonic disperse is for subsequent use in distilled water.
(2) tri-iron tetroxide of poly-(ethene glycol) two (carboxymethyl) ether of adsorption is prepared
The ferric acetyl acetonade of 7.5mmol and poly-(ethene glycol) two (carboxymethyl) ether (PEG) of 30g are joined in 100mL triethylene glycol, passes into nitrogen, at 100 DEG C, be stirred to reagent dissolve completely; Temperature is risen to 260 DEG C, constant temperature 30 minutes; Be cooled to room temperature, dialyse four times with the sodium citrate solution of 0.1mol/L, then use distill water dialysis twice.
(3) graphite oxide thiazolinyl tri-iron tetroxide is prepared
Graphene oxide solution and tri-iron tetroxide suspension are diluted to 100mL respectively; With NaOH, the pH value of graphene oxide solution is adjusted to 8.0, with HCl, the pH value of tri-iron tetroxide suspension is adjusted to 5.5; Tri-iron tetroxide suspension is dropwise joined in the solution of graphene oxide, stirs 2 hours; Centrifugal, washing, 60 DEG C of dryings, obtain graphite oxide thiazolinyl tri-iron tetroxide.
(4) graphene-based carbon coated ferriferrous oxide is prepared
Graphite oxide thiazolinyl tri-iron tetroxide is transferred in tube furnace, under nitrogen protection, rises to 500 DEG C by room temperature, constant temperature 10 minutes, heating rate 5 DEG C/min; Be down to room temperature, obtain graphene-based carbon coated ferriferrous oxide.
The XRD spectra of sample is shown in Fig. 1, proves that the sample prepared contains carbon and tri-iron tetroxide; Fig. 2 is shown in by the SEM photo of sample, proves that sample has sandwich structure, and ferriferrous oxide particles is fixed in the graphene layer of superposition; Fig. 3 is shown in by the TEM photo of sample, proves that ferriferrous oxide particles is nano level, and is dispersed in graphenic surface.
(5) electrochemical properties test
Ferriferrous oxide particles and graphene-based carbon coated ferriferrous oxide compound are carried out electrochemical properties test respectively, finds that graphene-based carbon coated ferriferrous oxide has higher charge/discharge capacity, better cycle performance and high rate performance (see Fig. 4).
embodiment 2:
(1) graphene oxide of adsorption PDDA is prepared
Adopt and improve Hummers legal system for graphene oxide, by 12mL sulfuric acid (98%, H
2sO
4), 2.5g potassium peroxydisulfate (K
2s
2o
8) and 2.5g phosphorus pentoxide (P
2o
5) mixing, add 3g graphite at 80 DEG C, stir 4 ~ 5 hours; Be cooled to room temperature, with deionized water dilution, hold over night; The graphite of pre-oxidation is slowly joined in the 120mL concentrated sulfuric acid of 0 DEG C, more slowly adds 15g potassium permanganate (KMnO
4), 35 DEG C are stirred 2 ~ 4 hours; After the dilution of 480ml deionized water, add 20mL hydrogen peroxide (30%, H
2o
2); Filter, wash with the watery hydrochloric acid of 1: 10 (volume ratio), then spend deionized water to neutral, obtain graphite oxide; By graphite oxide in water ultrasonic 0.5 ~ 1 hour graphene oxide solution; By the PDDA of the graphene oxide of 0.03g and 1.3g respectively ultrasonic disperse in the distilled water of 100mL, after ultrasonic 30 minutes, the NaOH of 0.4g is joined PDDA solution for continuous ultrasonic half an hour; Graphene oxide solution is dropwise added drop-wise in PDDA solution under ultrasound condition, ultrasonic 2 hours; Centrifugal, to wash, obtain adsorption PDDA graphene oxide, ultrasonic disperse is for subsequent use in distilled water.
(2) titanium dioxide of adsorption PEG is prepared
The titanium tetrachloride solution of 1.5ml is slowly added drop-wise in 10ml absolute ethyl alcohol, ultrasonic 0.5 hour, obtains transparent yellow solution; By this solution left standstill certain hour, obtain vitreosol; 80 DEG C of heating, except desolventizing, form flaxen xerogel; 400 DEG C of heat treatments, constant temperature 1 hour, obtains nano-titanium dioxide powder; The PEG of 0.01g is dispersed in 100mL containing in the deionized water of a small amount of hydrochloric acid, add the nano titanium oxide of 1g, ultrasonic emulsification is disperseed for 4 hours; Add aniline hydrochloric acid again, continue stirring after 30 minutes, slowly drip the hydrochloric acid solution of ammonium persulfate, react 3.5 hours; Filtration, washing, 60 DEG C of dryings, obtain the titania nanoparticles that PEG is coated.
(3) graphene oxide based titanium dioxide is prepared
Graphene oxide solution and tio_2 suspension are diluted to 100mL respectively; With NaOH, the pH value of graphene oxide solution is adjusted to 8.0, with HCl, the pH value of tio_2 suspension is adjusted to 5.0; Tio_2 suspension is dropwise joined in the solution of graphene oxide, stirs 2 hours; Centrifugal, washing, 60 DEG C of dryings, obtain graphene oxide based titanium dioxide.
(4) graphene-based carbon cladding titanium dioxide is prepared
Graphene oxide based titanium dioxide is transferred in tube furnace, under nitrogen protection, rises to 600 DEG C by room temperature, constant temperature 30 minutes, heating rate 10 DEG C/min; Be down to room temperature, obtain graphene-based carbon cladding titanium dioxide.
The XRD spectra of sample proves that the sample of preparation contains carbon and titanium dioxide; The TEM photo of sample and SEM photo prove that nano titanium oxide is dispersed in the surface of Graphene uniformly, and are fixed in the graphene layer of accumulation; The electrochemical properties of contrast titanium dioxide granule and graphene-based carbon cladding titanium dioxide, finds that graphene-based carbon cladding titanium dioxide has better electrochemical properties.
The above description of this invention is illustrative; and it is nonrestrictive; it will be understood by those skilled in the art that claim limit spirit and scope within can carry out many amendments, change or equivalence to it, but they all will fall within the scope of protection of the present invention.
Claims (12)
1. a preparation method for the graphene-based carbon-clad metal oxide of sandwich structure, is characterized in that comprising the following steps:
(1) graphene oxide is prepared;
(2) metal oxide nanoparticles is prepared;
(3) surface of graphene oxide absorption is containing amino macromolecule;
(4) metal oxide surface adsorbs carboxylic macromolecule;
(5) graphene oxide metal oxides is prepared by self assembly;
(6) high temperature cabonization under inert gas shielding;
(7) graphene-based carbon-clad metal oxide composite is obtained.
2. preparation method according to claim 1, is characterized in that, the preparation method of described graphene oxide comprises: Hummers method, Brodie method, Staudenmaier method.
3. preparation method according to claim 1, is characterized in that, the preparation method of described metal oxide nanoparticles comprises: template, hydro thermal method, thermal decomposition method, sol-gal process, microemulsion method, Hydrolyze method.
4. preparation method according to claim 1, is characterized in that, described metal oxide comprises: iron oxide, cobalt oxide, nickel oxide, cupric oxide, manganese oxide, tin oxide, zinc oxide, titanium oxide.
5. preparation method according to claim 1, is characterized in that, the described macromolecule containing amino comprises: PDDA, polydiallyldimethyl ammonium chloride, poly-Hydroxypropyldimonium Chloride.
6. preparation method according to claim 1, is characterized in that, described carboxylic macromolecule comprises: poly-(ethene glycol) two (carboxymethyl) ether, polyethylene glycol dicarboxylic acids, carboxymethyl cellulose.
7. preparation method according to claim 1, is characterized in that, in described step (3), Graphene and the high molecular mass ratio containing amino are in 1: 1 ~ 10: 1 scope.
8. preparation method according to claim 1, is characterized in that, in described step (4), metal oxide and carboxylic high molecular mass ratio are in 10: 1 ~ 20: 1 scope.
9. preparation method according to claim 1, is characterized in that, the self assembling process in described step (5) comprises the following steps:
(1) joined in 100mL water by the graphene oxide of 0.01 ~ 0.1g surface amination, ultrasonic disperse is made into graphene oxide solution;
(2) joined in 100mL water by the metal oxide of 0.1 ~ 1g surface carboxyl groups, ultrasonic disperse is made into metal oxide suspension;
(3) regulate the pH value of graphene oxide solution in 7 ~ 10 scopes with diluted alkaline, regulate the pH value of metal oxide suspension in 4 ~ 7 scopes with diluted acid;
(4) be added drop-wise in graphene oxide solution by metal oxide suspension, stir 1 ~ 3 hour, the mass ratio of graphene oxide and metal oxide is in 1: 1 ~ 1: 10 scopes;
(5) centrifugal, washing, dry.
10. preparation method according to claim 1, is characterized in that, the heating-up temperature in described step (6) is within the scope of 500 ~ 1000 DEG C, and the time of staying, the rate of heat addition was within the scope of 1 ~ 10 DEG C/min in 0.1 ~ 2 hours window.
11. graphene-based carbon-clad metal oxide composites according to claim 1, its feature comprises: composite material has sandwich structure, the length of composite material is within the scope of 1 ~ 5 μm, wide within the scope of 1 ~ 5 μm, high within the scope of 0.5 ~ 1 μm, metal oxide particle diameter is within the scope of 1 ~ 20nm, metal oxide particle surface is coated by carbon-coating, carbon layers having thicknesses is in 0.5 ~ 2nm nanometer range, metal oxide particle is fixed between the graphene layer of self assembly, and the load capacity of metal oxide is within the scope of 50 ~ 90wt%.
12. graphene-based carbon-clad metal oxide composites according to claim 1, its purposes comprises: the electrode material of lithium ion battery, the electrode material of ultracapacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510153412.3A CN104701490B (en) | 2015-04-02 | 2015-04-02 | A kind of preparation method and application of the graphene-based carbon-clad metal oxide of sandwich structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510153412.3A CN104701490B (en) | 2015-04-02 | 2015-04-02 | A kind of preparation method and application of the graphene-based carbon-clad metal oxide of sandwich structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104701490A true CN104701490A (en) | 2015-06-10 |
| CN104701490B CN104701490B (en) | 2017-09-29 |
Family
ID=53348397
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510153412.3A Expired - Fee Related CN104701490B (en) | 2015-04-02 | 2015-04-02 | A kind of preparation method and application of the graphene-based carbon-clad metal oxide of sandwich structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104701490B (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105140464A (en) * | 2015-08-10 | 2015-12-09 | 复旦大学 | Nano composite material of carbon-coated nickel oxide nanosheet-loaded graphene and preparation method of nano composite material |
| CN105384146A (en) * | 2015-12-09 | 2016-03-09 | 唐山建华科技发展有限责任公司 | Graphene-loaded nanometer Fe<3>O<4>/ZnO composite and preparation method thereof |
| CN105390676A (en) * | 2015-11-02 | 2016-03-09 | 北京师范大学 | Quick preparation method for graphene base metal or metal oxide with sandwich structure |
| CN105551828A (en) * | 2015-12-11 | 2016-05-04 | 郑州大学 | Nano titanium dioxide/graphene composite material and preparation method thereof |
| CN106158416A (en) * | 2016-08-22 | 2016-11-23 | 电子科技大学 | A kind of Graphene/zinc oxide composite material of core-shell structure is the preparation method of the ultracapacitor of negative pole |
| CN106450279A (en) * | 2016-10-28 | 2017-02-22 | 武汉理工大学 | Preparation method of graphene coated nickel cobalt manganese lithium ion battery cathode material |
| CN106549147A (en) * | 2016-11-02 | 2017-03-29 | 成都新柯力化工科技有限公司 | Nickle cobalt lithium manganate that a kind of two-dimension nano materials are fixed and preparation method and application |
| CN106744863A (en) * | 2017-03-23 | 2017-05-31 | 天津工业大学 | A kind of preparation method of the grapheme modified zinc oxide composites of PDDA |
| CN106935805A (en) * | 2017-04-07 | 2017-07-07 | 哈尔滨工业大学 | A kind of preparation method of di-iron trioxide/Graphene self-supporting electrode |
| CN107159259A (en) * | 2017-05-16 | 2017-09-15 | 西北师范大学 | A kind of gold/ferroso-ferric oxide/stannic oxide/graphene nano hybrid material and preparation method thereof |
| CN107565112A (en) * | 2017-08-29 | 2018-01-09 | 湖南长远锂科有限公司 | A kind of preparation method of graphene coated lithium ion secondary battery anode material |
| CN108580883A (en) * | 2018-06-21 | 2018-09-28 | 中国科学技术大学 | A kind of sandwich nanogold particle nanometer sheet of graphene and preparation method thereof |
| CN108922792A (en) * | 2018-07-13 | 2018-11-30 | 黑龙江省科学院高技术研究院 | A kind of preparation method of graphene/ZnO/NiO composite material |
| CN109273690A (en) * | 2018-09-20 | 2019-01-25 | 天津师范大学 | A kind of method of synthesizing lithium ion battery high-capacity cathode material |
| CN109809428A (en) * | 2017-11-20 | 2019-05-28 | 中国科学院大连化学物理研究所 | A kind of composite material and preparation method of inorganic carrier area load carbon-coating |
| CN111640930A (en) * | 2020-06-16 | 2020-09-08 | 陕西中丰新能源有限公司 | Efficient low-cost electrode manufacturing material and process |
| CN112366302A (en) * | 2020-11-13 | 2021-02-12 | 格林美（江苏）钴业股份有限公司 | Preparation method of coated cobaltosic oxide precursor |
| EP4310949A4 (en) * | 2022-04-18 | 2024-08-21 | Contemporary Amperex Technology Co Ltd | Electrode active material precursor and preparation method therefor, electrode active material and battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102917981A (en) * | 2010-05-14 | 2013-02-06 | 巴斯夫欧洲公司 | Method for encapsulating metals and metal oxides with graphene and use of said materials |
| CN102976314A (en) * | 2012-11-29 | 2013-03-20 | 中国科学院宁波材料技术与工程研究所 | Novel titanium dioxide-graphene nano-composite material as well as manufacturing method and application thereof |
| CN103374352A (en) * | 2012-04-17 | 2013-10-30 | 吉林师范大学 | Composite material of fluorescence magnetism composite microsphere and oxidized graphene and preparation method thereof |
| CN103647064A (en) * | 2013-12-19 | 2014-03-19 | 北京师范大学 | Graphene-coating mesoporous carbon-base metal oxide as well as preparation method thereof and application |
| CN104445155A (en) * | 2013-09-17 | 2015-03-25 | 中国科学院大连化学物理研究所 | Carboxyl functionalized graphene material and preparation method thereof |
-
2015
- 2015-04-02 CN CN201510153412.3A patent/CN104701490B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102917981A (en) * | 2010-05-14 | 2013-02-06 | 巴斯夫欧洲公司 | Method for encapsulating metals and metal oxides with graphene and use of said materials |
| CN103374352A (en) * | 2012-04-17 | 2013-10-30 | 吉林师范大学 | Composite material of fluorescence magnetism composite microsphere and oxidized graphene and preparation method thereof |
| CN102976314A (en) * | 2012-11-29 | 2013-03-20 | 中国科学院宁波材料技术与工程研究所 | Novel titanium dioxide-graphene nano-composite material as well as manufacturing method and application thereof |
| CN104445155A (en) * | 2013-09-17 | 2015-03-25 | 中国科学院大连化学物理研究所 | Carboxyl functionalized graphene material and preparation method thereof |
| CN103647064A (en) * | 2013-12-19 | 2014-03-19 | 北京师范大学 | Graphene-coating mesoporous carbon-base metal oxide as well as preparation method thereof and application |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105140464A (en) * | 2015-08-10 | 2015-12-09 | 复旦大学 | Nano composite material of carbon-coated nickel oxide nanosheet-loaded graphene and preparation method of nano composite material |
| CN105390676A (en) * | 2015-11-02 | 2016-03-09 | 北京师范大学 | Quick preparation method for graphene base metal or metal oxide with sandwich structure |
| CN105384146A (en) * | 2015-12-09 | 2016-03-09 | 唐山建华科技发展有限责任公司 | Graphene-loaded nanometer Fe<3>O<4>/ZnO composite and preparation method thereof |
| CN105551828A (en) * | 2015-12-11 | 2016-05-04 | 郑州大学 | Nano titanium dioxide/graphene composite material and preparation method thereof |
| CN106158416A (en) * | 2016-08-22 | 2016-11-23 | 电子科技大学 | A kind of Graphene/zinc oxide composite material of core-shell structure is the preparation method of the ultracapacitor of negative pole |
| CN106158416B (en) * | 2016-08-22 | 2019-01-15 | 四川英能基科技有限公司 | A kind of graphene/zinc oxide composite material of core-shell structure is the preparation method of the supercapacitor of cathode |
| CN106450279B (en) * | 2016-10-28 | 2018-12-28 | 武汉理工大学 | A kind of preparation method of graphene coated nickel cobalt manganese anode material for lithium-ion batteries |
| CN106450279A (en) * | 2016-10-28 | 2017-02-22 | 武汉理工大学 | Preparation method of graphene coated nickel cobalt manganese lithium ion battery cathode material |
| CN106549147A (en) * | 2016-11-02 | 2017-03-29 | 成都新柯力化工科技有限公司 | Nickle cobalt lithium manganate that a kind of two-dimension nano materials are fixed and preparation method and application |
| CN106744863A (en) * | 2017-03-23 | 2017-05-31 | 天津工业大学 | A kind of preparation method of the grapheme modified zinc oxide composites of PDDA |
| CN106935805A (en) * | 2017-04-07 | 2017-07-07 | 哈尔滨工业大学 | A kind of preparation method of di-iron trioxide/Graphene self-supporting electrode |
| CN107159259A (en) * | 2017-05-16 | 2017-09-15 | 西北师范大学 | A kind of gold/ferroso-ferric oxide/stannic oxide/graphene nano hybrid material and preparation method thereof |
| CN107565112A (en) * | 2017-08-29 | 2018-01-09 | 湖南长远锂科有限公司 | A kind of preparation method of graphene coated lithium ion secondary battery anode material |
| CN109809428A (en) * | 2017-11-20 | 2019-05-28 | 中国科学院大连化学物理研究所 | A kind of composite material and preparation method of inorganic carrier area load carbon-coating |
| CN108580883A (en) * | 2018-06-21 | 2018-09-28 | 中国科学技术大学 | A kind of sandwich nanogold particle nanometer sheet of graphene and preparation method thereof |
| CN108922792A (en) * | 2018-07-13 | 2018-11-30 | 黑龙江省科学院高技术研究院 | A kind of preparation method of graphene/ZnO/NiO composite material |
| CN109273690A (en) * | 2018-09-20 | 2019-01-25 | 天津师范大学 | A kind of method of synthesizing lithium ion battery high-capacity cathode material |
| CN111640930A (en) * | 2020-06-16 | 2020-09-08 | 陕西中丰新能源有限公司 | Efficient low-cost electrode manufacturing material and process |
| CN112366302A (en) * | 2020-11-13 | 2021-02-12 | 格林美（江苏）钴业股份有限公司 | Preparation method of coated cobaltosic oxide precursor |
| EP4310949A4 (en) * | 2022-04-18 | 2024-08-21 | Contemporary Amperex Technology Co Ltd | Electrode active material precursor and preparation method therefor, electrode active material and battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104701490B (en) | 2017-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104701490A (en) | Preparing method and application of sandwich-structure graphene-based carbon cladding metal oxide | |
| Yu et al. | Synthesis and application of iron-based nanomaterials as anodes of lithium-ion batteries and supercapacitors | |
| Zhang et al. | Top-down strategy to synthesize mesoporous dual carbon armored MnO nanoparticles for lithium-ion battery anodes | |
| Zeng et al. | In situ synthesis of MnO2/porous graphitic carbon composites as high-capacity anode materials for lithium-ion batteries | |
| CN102437320B (en) | Graphene-coated mesoporous metallic oxide, and preparation method and use thereof | |
| Xiao et al. | ZnO nanoparticles encapsulated in a 3D hierarchical carbon framework as anode for lithium ion battery | |
| He et al. | Graphene-doped carbon/Fe3O4 porous nanofibers with hierarchical band construction as high-performance anodes for lithium-ion batteries | |
| Xu et al. | Fluorine-doped tin oxide nanocrystal/reduced graphene oxide composites as lithium ion battery anode material with high capacity and cycling stability | |
| Zhang et al. | NiMn-layered double hydroxides chemically anchored on Ti3C2 MXene for superior lithium ion storage | |
| CN102867650A (en) | High-magnification supercapacitor composite electrode material and preparation method thereof | |
| Wang et al. | MnO2/porous carbon nanotube/MnO2 nanocomposites for high-performance supercapacitor | |
| Ju et al. | Prussian blue analogue derived low-crystalline Mn2O3/Co3O4 as high-performance supercapacitor electrode | |
| CN102842710A (en) | Preparation method of Co3O4/graphene nanocomposite material | |
| Han et al. | Preparation of PAN-based carbon fiber@ MnO2 composite as an anode material for structural lithium-ion batteries | |
| Ling et al. | Double-shelled hollow Na 2 FePO 4 F/C spheres cathode for high-performance sodium-ion batteries | |
| Cai et al. | Hierarchical micro-composite assembled from Bi spheres and expanded graphite flakes as anodes for sodium-ion half/full cells with excellent comprehensive electrochemical performance | |
| Abe et al. | Self-standing carbon nanofiber and SnO2 nanorod composite as a high-capacity and high-rate-capability anode for lithium-ion batteries | |
| Qi et al. | Covalent bonding of sulfur nanoparticles to unzipped multiwalled carbon nanotubes for high-performance lithium–sulfur batteries | |
| Wi et al. | Reduced graphene oxide/carbon double-coated 3-D porous ZnO aggregates as high-performance Li-ion anode materials | |
| CN102496481A (en) | Graphene/polypyrrole nanotube composite material, super capacitor with graphene/polypyrrole nanotube composite material as electrode, and methods for preparing graphene/polypyrrole nanotube composite material and super capacitor | |
| Zhu et al. | Review and prospect of Mn3O4‐based composite materials for supercapacitor electrodes | |
| Shi et al. | Rational design of multi-walled carbon nanotube@ hollow Fe3O4@ C coaxial nanotubes as long-cycle-life lithium ion battery anodes | |
| Ran et al. | A review on graphene-based electrode materials for supercapacitor | |
| Kang et al. | Novel aqueous rechargeable nickel//bismuth battery based on highly porous Bi2WO6 and Co0. 5Ni0. 5MoO4 microspheres | |
| Hussain et al. | Reagents assisted Mg-doped CeO2 for high-performance energy-storage applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170929 Termination date: 20190402 |