CN104701490B - A kind of preparation method and application of the graphene-based carbon-clad metal oxide of sandwich structure - Google Patents
A kind of preparation method and application of the graphene-based carbon-clad metal oxide of sandwich structure Download PDFInfo
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- H01M4/00—Electrodes
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention relates to a kind of preparation method and application of the graphene-based carbon-clad metal oxide of sandwich structure.The preparation method of the graphene-based carbon-clad metal oxide of sandwich structure comprises the following steps：Stannic oxide/graphene nano piece and metal oxide nanoparticles, macromolecule of the metal oxide surface absorption with carboxyl, macromolecule of the surface of graphene oxide absorption with amino are prepared respectively；Solution ph is adjusted, makes metal oxide and surface of graphene oxide oppositely charged, the graphene oxide metal oxides with sandwich structure is obtained by Electrostatic Absorption；High temperature cabonization under inert gas shielding, obtains the graphene-based carbon-clad metal oxide with sandwich structure.Graphene-based metal oxide composite prepared by this method has the advantage that：Metal oxide particle has nano-scale, and metal oxide particle surface is coated by carbon-coating, and composite has sandwich structure.Therefore, the composite has excellent chemical property, can be used as the electrode material of lithium battery and ultracapacitor.
Description
Technical field
It is to be related to one kind there is sandwich specifically the present invention relates to a kind of preparation of new battery electrode material
The preparation method and application of the graphene-based carbon-clad metal oxide of structure.
Background technology
Lithium ion battery is because with height storage energy density, capacity is big, memory-less effect, rated voltage are high, self discharge
Rate is low, lightweight, service life length, high/low temperature strong adaptability, environmental protection the advantages of, be widely applied to the daily life of people
In work, such as battery of mobile phone and notebook computer.Some metal oxides have higher theoretical capacity, and rich reserves, hold
Easily prepare, be expected to the electrode material as lithium ion battery, such as Co3O4, NiO, Fe3O4, the theory of the metal oxide such as ZnO
Specific capacity is in 700~1000mAh/g.But metal oxide poorly conductive, electron transfer rate itself is slow, while in discharge and recharge
Larger volume deformation is had in journey, causes the rupture of battery material, therefore cycle performance and high rate performance are poor.Pass through control
The particle size or appearance structure (such as loose structure and hollow structure) of metal oxide can effectively reduce metal oxide
The influence that brings of volume deformation, improve chemical property (P.G.Bruce, B.Scrosati, the J- of metal oxide particle
M.Tarascon, Angew.Chem.Int.Ed.2008,47,2930-2946).Another improved method is to prepare carbon composite wood
Material, carbon carrier can both suppress the volume deformation of metal oxide, the electric conductivity of compound can be improved again, so as to improve compound
The chemical property of thing.Graphene is a kind of single layer of carbon atom facestock material separated from graphite material, with larger ratio
Surface area, higher mechanical strength and good thermal conductivity.Therefore, it is graphene-supported compared to other carbon carriers
Metal oxide have more excellent 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).So
And, metal oxide is not easily controlled in the growth course of graphenic surface, cause the Size Distribution of metal oxide particle compared with
Width, while when the load capacity of metal oxide is improved, metal oxide particle can reunite in graphenic surface, can all influence multiple
The chemical property of compound.Therefore, it is intended that a kind of new graphene-based metal oxide of design synthesis, can both control metal
The particle size and load capacity of oxide, can suppress the reunion of metal oxide particle while high capacity amount again, so that
The chemical property of graphene-based metal oxide is improved, the electricity as high performance lithium ion battery or ultracapacitor is expected to
Pole material.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the graphene-based carbon-clad metal oxide of sandwich structure,
A class new product is added for the electrode material of existing lithium ion battery and ultracapacitor.
The graphene-based carbon-clad metal oxide of sandwich structure disclosed in this invention, it is characterised in that：The composite wood
Material has sandwich structure, and the length of composite is wide in 1~5 μ m in 1~5 μ m, and height is in 0.5~1 μ m
Interior, metal oxide particle diameter is in the range of 1~20nm, and metal oxide particle surface is coated by carbon-coating, and carbon layers having thicknesses exist
In 0.5~2nm nanometer ranges, metal oxide particle is fixed between the graphene layer of self assembly, the load capacity of metal oxide
In the range of 50~90wt%.
The preparation method of the above-mentioned graphene-based carbon-clad metal oxide of sandwich structure, comprises the following steps：
(1) high molecular graphene oxide of the adsorption containing amino is prepared
The concentrated sulfuric acid and sodium nitrate are mixed, ice bath is cooled to 0 DEG C, add graphite；After mixing 4~5 hours, height is slowly added into
Potassium manganate；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；Filtering, is washed with 5% watery hydrochloric acid, then is washed with deionized to neutrality, obtains graphite oxide；By graphite oxide
It is ultrasonic in water, obtain graphene oxide solution；Macromolecule and sodium hydroxide containing amino are added to graphene oxide solution,
Ultrasonic disperse；Centrifuge, wash, be re-dispersed into it is standby in the aqueous solution.
(2) the carboxylic high molecular metal oxide of adsorption is prepared
Metal oxide precursor, carboxylic surfactant are mixed with alcohols solvent, and are passed through nitrogen, 100
Stirring and dissolving at DEG C；Temperature rises to 260 DEG C, reacts 30 minutes；Room temperature is cooled to, is dialysed four times with sodium citrate solution, then
With distilled water dialysis twice.
(3) graphene oxide metal oxides are prepared
By adsorption carboxylic high molecular metal oxide suspension and adsorption containing the high molecular of amino
Graphene oxide is diluted to 100mL respectively；The pH value of metal oxide suspension is adjusted to 7~10 with diluted alkaline, will 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, stirring 1
~3 hours；Centrifugation, washing, is dried to obtain graphene oxide metal oxides.
(4) graphene-based carbon-clad metal oxide is prepared
Under inert gas shielding, graphene oxide metal oxides are heated 0.1~2 hour at 500~1000 DEG C；Drop
To room temperature, graphene-based carbon-clad metal oxide is obtained.
The graphene-based carbon-clad metal oxide of sandwich structure that the present invention is provided has outstanding chemical property, can
It is used as the electrode material of lithium ion battery and ultracapacitor.
The effect of the present invention：
The present invention is first respectively synthesized the graphene oxide of surface amination and the metal oxide of surface carboxyl groups, then adjusts
The pH value of solution makes surface of graphene oxide positively charged, and metal oxide surface is negatively charged, makes oxidation stone by self assembly
Black alkene adsorption metal oxide particle, then heated under inert gas shielding, make the high score on metal oxide particle surface
Son is carbonized into carbon-coating, while redox graphene, obtains the graphene-based carbon-clad metal oxide of sandwich structure.This is combined
Material shows higher charge/discharge capacity, outstanding cycle performance and high rate performance, can be used as lithium ion battery or super
The electrode material of capacitor.
Brief description of the drawings
Fig. 1 is X-ray diffraction (XRD) figure of graphene-based carbon coated ferriferrous oxide prepared by the present invention；
Fig. 2 is SEM (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 for the graphene oxide being related in the present invention includes all methods for preparing graphene oxide, is related to
The preparation method of metal oxide includes all methods for preparing metal oxide nanoparticles, and the macromolecule being related to includes all
Macromolecule containing amino or carboxyl, the metal oxide being related to include it is all can as battery electrode material metal oxide.
It is making further detailed, clear and complete description of how realizing, institute to the present invention with reference to specific embodiment
Row embodiment is only further described to the present invention, not thereby limiting the invention：
Embodiment 1：
(1) graphene oxide of adsorption PDDA is prepared
Graphene oxide is prepared using Hummers methods, by 230mL sulfuric acid (98%, H2SO4) and 5g sodium nitrate (NaNO3) mixed
After conjunction, ice bath cooling；When temperature is 0 DEG C, stirring is lower to add 5g graphite；After mixing 4~5 hours, 30g potassium permanganate is slowly added into
(KMnO4)；35 DEG C are reacted 2 hours, add the dilution of 460mL deionized waters, and 98 DEG C are stirred 15 minutes, add deionized water dilution,
And add 100mL hydrogen peroxide (30%, H2O2)；Filtering, is washed with 2L 5% watery hydrochloric acid, then is washed with deionized to neutrality,
Produce graphite oxide；By graphite oxide, ultrasound can obtain graphene oxide solution in 0.5~1 hour in water；By 0.03g oxidation
Ultrasonic disperse is in 100mL distilled water respectively for graphene and 1.3g PDDA (PDDA), ultrasound
After 30 minutes, 0.4g NaOH is added in PDDA solution and continues ultrasonic half an hour；By graphene oxide solution in ultrasonic bar
It is added drop-wise to dropwise in PDDA solution under part, ultrasound 2 hours；Adsorption PDDA graphene oxide is centrifuged, washed, obtaining, is surpassed
Sound is scattered in standby in distilled water.
(2) ferroso-ferric oxide of adsorption poly- (ethene glycol) double (carboxymethyl) ether is prepared
7.5mmol ferric acetyl acetonade and 30g poly- (ethene glycol) double (carboxymethyl) ether (PEG) are added to 100mL
In triethylene glycol, nitrogen is passed through, stirs to reagent and is completely dissolved at 100 DEG C；Temperature is risen into 260 DEG C, constant temperature 30 minutes；Cooling
To room temperature, dialysed four times with 0.1mol/L sodium citrate solution, then with distilled water dialysis twice.
(3) graphite oxide alkenyl ferroso-ferric oxide is prepared
Graphene oxide solution and ferroso-ferric oxide suspension are diluted to 100mL respectively；With NaOH by graphene oxide
The pH value of solution is adjusted to 8.0, is adjusted the pH value of ferroso-ferric oxide suspension to 5.5 with HCl；By ferroso-ferric oxide suspension
It is added dropwise in the solution of graphene oxide, stirs 2 hours；Centrifugation, washing, 60 DEG C of dryings, obtain graphite oxide alkenyl four
Fe 3 O.
(4) graphene-based carbon coated ferriferrous oxide is prepared
Graphite oxide alkenyl ferroso-ferric oxide is transferred in tube furnace, under nitrogen protection, 500 DEG C, perseverance are risen to by room temperature
Temperature 10 minutes, 5 DEG C/min of heating rate；Room temperature is down to, graphene-based carbon coated ferriferrous oxide is obtained.
The XRD spectra of sample is shown in Fig. 1, it was demonstrated that the sample of preparation contains carbon and ferroso-ferric oxide；The SEM photograph of sample is shown in figure
2, it was demonstrated that sample has sandwich structure, ferriferrous oxide particles are fixed in the graphene layer of superposition；The TEM photos of sample are shown in
Fig. 3, it was demonstrated that ferriferrous oxide particles are nano level, and are dispersed in graphenic surface.
(5) electrochemical properties are tested
Ferriferrous oxide particles and graphene-based carbon coated ferriferrous oxide compound are subjected to electrochemical properties survey respectively
Examination, it is found that graphene-based carbon coated ferriferrous oxide has higher charge/discharge capacity, more preferable cycle performance and high rate performance
(see Fig. 4).
Embodiment 2：
(1) adsorption PDDA graphene oxide is prepared
Graphene oxide is prepared using Hummers methods are improved, by 12mL sulfuric acid (98%, H2SO4), 2.5g potassium peroxydisulfates
(K2S2O8) and 2.5g phosphorus pentoxides (P2O5) mix, 3g graphite is added at 80 DEG C, is stirred 4~5 hours；Room temperature is cooled to, is used
Deionized water dilutes, and stands overnight；The graphite of pre-oxidation is slowly added into 0 DEG C of the 120mL concentrated sulfuric acids, is slow added into
15g potassium permanganate (KMnO4), 35 DEG C are stirred 2~4 hours；After being diluted with 480ml deionized waters, 20mL hydrogen peroxide is added
(30%, H2O2)；Filtering, is washed with the watery hydrochloric acid of 1: 10 (volume ratio), then is washed with deionized to neutrality, produces oxidation stone
Ink；By graphite oxide, ultrasound can obtain graphene oxide solution in 0.5~1 hour in water；By 0.03g graphene oxide and
1.3g PDDA distinguishes ultrasonic disperse in 100mL distilled water, and 0.4g NaOH is added to PDDA molten by ultrasound after 30 minutes
Continue ultrasonic half an hour in liquid；Graphene oxide solution is added drop-wise in PDDA solution dropwise under ultrasound condition, ultrasound 2 is small
When；Adsorption PDDA graphene oxide is centrifuged, washs, obtaining, ultrasonic disperse is standby in distilled water.
(2) adsorption PEG titanium dioxide is prepared
1.5ml titanium tetrachloride solution is slowly dropped in 10ml absolute ethyl alcohols, ultrasound 0.5 hour obtains transparent
Yellow solution；By the solution left standstill certain time, vitreosol is obtained；80 DEG C of heating remove solvent, form flaxen dry
Gel；In 400 DEG C of heat treatments, constant temperature 1 hour obtains nano-titanium dioxide powder；0.01g PEG is dispersed in 100mL containing few
In the deionized water for measuring hydrochloric acid, 1g nano titanium oxide is added, ultrasonic emulsification is disperseed for 4 hours；Aniline hydrochloric acid is added,
Continue after stirring 30 minutes, the hydrochloric acid solution of ammonium persulfate is slowly added dropwise, react 3.5 hours；Filtering, washing, 60 DEG C of dryings, are obtained
The titania nanoparticles coated to PEG.
(3) graphene oxide based titanium dioxide is prepared
Graphene oxide solution and tio_2 suspension are diluted to 100mL respectively；It is with NaOH that graphene oxide is molten
The pH value of liquid is adjusted to 8.0, is adjusted the pH value of tio_2 suspension to 5.0 with HCl；Tio_2 suspension is added dropwise
Enter into the solution of graphene oxide, stir 2 hours；Centrifugation, washing, 60 DEG C of dryings, obtain graphene oxide based titanium dioxide.
(4) graphene-based carbon coating titanium dioxide is prepared
Graphene oxide based titanium dioxide is transferred in tube furnace, under nitrogen protection, 600 DEG C, constant temperature are risen to by room temperature
30 minutes, 10 DEG C/min of heating rate；Room temperature is down to, graphene-based carbon coating titanium dioxide is obtained.
The XRD spectra of sample proves that the sample prepared contains carbon and titanium dioxide；TEM photos and the SEM photograph card of sample
Bright nano titanium oxide is uniformly dispersed in the surface of graphene, and is fixed in the graphene layer of accumulation；Contrast titanium dioxide
The electrochemical properties of titanium particle and graphene-based carbon coating titanium dioxide, it is found that graphene-based carbon coating titanium dioxide has more preferable
Electrochemical properties.
The above description of this invention is illustrative and not restrictive, it will be understood by those skilled in the art that in right
It is required that many modifications, change or equivalent can be carried out within the spirit and scope limited to it, but they fall within the present invention
Protection domain in.
Claims (12)
1. a kind of preparation method of the graphene-based carbon-clad metal oxide of sandwich structure, it is characterised in that including following step
Suddenly：
(1) graphene oxide is prepared；
(2) metal oxide nanoparticles are prepared；
(3) macromolecule of the surface of graphene oxide absorption containing amino；
(4) metal oxide surface adsorbs carboxylic macromolecule；
(5) graphene oxide metal oxides are 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, it is characterised in that the preparation method of the graphene oxide includes：
Hummers methods, Brodie methods, Staudenmaier methods.
3. preparation method according to claim 1, it is characterised in that the preparation method of the metal oxide nanoparticles
Including：Template, hydro-thermal method, thermal decomposition method, sol-gal process, microemulsion method, Hydrolyze method.
4. preparation method according to claim 1, it is characterised in that the metal oxide includes：Iron oxide, oxidation
Cobalt, nickel oxide, cupric oxide, manganese oxide, tin oxide, zinc oxide, titanium oxide.
5. preparation method according to claim 1, it is characterised in that the macromolecule containing amino includes：Poly dimethyl
Diallyl ammonium chloride, polydiallyldimethyl ammonium chloride, poly- Hydroxypropyldimonium Chloride.
6. preparation method according to claim 1, it is characterised in that the carboxylic macromolecule includes：It is poly- that (ethene is sweet
Alcohol) double (carboxymethyl) ether, polyethylene glycol dicarboxylic acids, carboxymethyl cellulose.
7. preparation method according to claim 1, it is characterised in that graphene and the height containing amino in the step (3)
The mass ratio of molecule is in the range of 1: 1~10: 1.
8. preparation method according to claim 1, it is characterised in that metal oxide is with containing carboxyl in the step (4)
High molecular mass ratio in the range of 10: 1~20: 1.
9. preparation method according to claim 1, it is characterised in that the self assembling process in the step (5) include with
Lower step：
(1) graphene oxide of 0.01~0.1g surface aminations is added in 100mL water, ultrasonic disperse is made into graphite oxide
Alkene solution；
(2) metal oxide of 0.1~1g surface carboxyl groups is added in 100mL water, ultrasonic disperse is made into metal oxide
Suspension；
(3) pH value for adjusting metal oxide suspension with diluted alkaline adjusts graphene oxide solution in the range of 7~10 with diluted acid
PH value in the range of 4~7；
(4) metal oxide suspension is added drop-wise in graphene oxide solution, stirred 1~3 hour, graphene oxide and metal
The mass ratio of oxide is in the range of 1: 1~1: 10；
(5) centrifuge, wash, dry.
10. preparation method according to claim 1, it is characterised in that heating-up temperature in the step (6) 500~
In the range of 1000 DEG C, the residence time, the rate of heat addition was in the range of 1~10 DEG C/min in the range of 0.1~2 hour.
11. graphene-based carbon-clad metal oxide composite according to claim 1, its feature includes：Composite wood
Material has sandwich structure, and the length of composite is wide in 1~5 μ m in 1~5 μ m, and height is in 0.5~1 μ m
Interior, metal oxide particle diameter is in the range of 1~20nm, and metal oxide particle surface is coated by carbon-coating, and carbon layers having thicknesses exist
In 0.5~2nm nanometer ranges, metal oxide particle is fixed between the graphene layer of self assembly, the load capacity of metal oxide
In the range of 50~90wt%.
12. graphene-based carbon-clad metal oxide composite according to claim 11, its purposes includes：Lithium ion
The electrode material of battery, the electrode material of ultracapacitor.
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| 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 |
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| 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 |
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