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
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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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.
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| 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 |
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