CN105390676B - A kind of fast preparation method of the graphene-based metal of sandwich structure or metal oxide - Google Patents

A kind of fast preparation method of the graphene-based metal of sandwich structure or metal oxide Download PDF

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CN105390676B
CN105390676B CN201510725322.7A CN201510725322A CN105390676B CN 105390676 B CN105390676 B CN 105390676B CN 201510725322 A CN201510725322 A CN 201510725322A CN 105390676 B CN105390676 B CN 105390676B
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graphene
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sandwich structure
oxide
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岳文博
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Beijing Normal University
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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
    • Y02E60/13—Energy storage using capacitors

Abstract

The present invention relates to the fast preparation methods of a kind of graphene-based metal of sandwich structure or metal oxide.The preparation method of the graphene-based metal of the sandwich structure or metal oxide includes the following steps：Graphene oxide and metal amino complex solution are prepared respectively；Metal amino complex solution is added drop-wise in graphene solution, generates precipitation；Precipitation is collected, is heated at high temperature under inert gas shielding；Obtain the graphene-based metal or metal oxide with sandwich structure.Graphene-based metal or metal oxide compounds prepared by this method has the advantage that：Preparation method is simple and quick, can largely prepare graphene-based metal or metal oxide compounds, and compound has sandwich structure, and metal or metal oxide particle have nano-scale, and metal or metal oxide particle are highly dispersed between graphene layer.Therefore, which has excellent chemical property, can be used as the electrode material of lithium battery and ultracapacitor.

Description

A kind of fast preparation method of the graphene-based metal of sandwich structure or metal oxide
Technical field
The present invention relates to a kind of fast preparation method of novel battery electrode material, specifically, being to be related to a kind of tool There are fast preparation method and the application of the graphene-based metal or metal oxide of sandwich structure.
Background technology
Lithium ion battery have storage energy density is high, capacity is big, memory-less effect, rated voltage are high, self-discharge rate is low, It light-weight, the advantages that service life is long, high/low temperature is adaptable, environmentally protective, is widely applied in daily life, Such as mobile phone and the battery of laptop.Some metal oxides, such as Co3O4, NiO, Fe3O4, ZnO etc., there is higher theory Capacity (700~1000mAh/g), and rich reserves easily prepare, are expected to the electrode material as lithium ion battery.It is however, golden Belong to oxide poorly conductive itself, electron transfer rate is slow, while larger volume deformation is had in charge and discharge process, causes The rupture of battery material, therefore its cycle performance and high rate performance are poor.By preparing carbon composite, inhibited using carbon carrier The volume deformation of metal oxide, while the electric conductivity of compound is improved, the chemical property of compound can be improved.Graphene It is a kind of single layer of carbon atom plane materiel material separated from graphite material, there is larger specific surface area, higher mechanical strength With good thermal conductivity.Therefore, compared to other carbon carriers, graphene-supported metal oxide has more excellent Chemical property.And the graphene-based metal oxide with sandwich structure, since nano particle is evenly distributed in graphite The interlayer of alkene, while compound high conductivity is kept, graphene layer can inhibit the volume deformation of metal oxide, and protect Metal oxide particle is protected, it is prevented to be lost in and rupture, is conducive to the promotion of compound chemical property (J.Mater.Chem.A2013,1,6928-6933；ACS Appl.Mater.Interfaces 2015,7,9709-9715). However, the preparation method of the graphene-based metal oxide of sandwich structure usually requires first to obtain metal oxide nano at present Grain, then the method by surface modification, make itself and stannic oxide/graphene nano piece self assembly, obtain sandwich structure.Preparation method It is cumbersome, and metal oxide nanoparticles are not easy to prepare and preserve and (easily reunite).Therefore, it is intended that a kind of new preparation side of design Method can quickly and largely prepare the graphene-based metal of sandwich structure or metal oxide compounds, be expected to as high property The lithium ion battery of energy or the electrode material of ultracapacitor.
Invention content
The purpose of the present invention is to provide the quick preparations of a kind of graphene-based metal of sandwich structure or metal oxide Method can be used as the electrode material of lithium ion battery and ultracapacitor.
The graphene-based metal of sandwich structure disclosed in this invention or metal oxide compounds, feature include：It is multiple Closing object has sandwich structure, and compound is grown in 2~10 μ ms, wide in 2~10 μ ms, and height is in 1~5 μ m Interior, in the range of 2~50nm, metal or metal oxide particle are fixed on self assembly for metal or metal oxide particle diameter Between graphene layer, the load capacity of metal or metal oxide is in the range of 5~90wt%.
The preparation method of the graphene-based metal of above-mentioned sandwich structure or metal oxide, includes the following steps：
(1) graphene oxide is prepared
The concentrated sulfuric acid and sodium nitrate are mixed, ice bath is cooled to 0 DEG C, adds in graphite；After mixing 4~5 hours, it is slowly added into height Potassium manganate；35 DEG C are reacted 2 hours, add in deionized water dilution, and 98 DEG C are stirred 15 minutes, add in deionized water dilution, and add in Hydrogen peroxide；Filtering, is washed, then be washed with deionized to neutrality with 5% dilute hydrochloric acid, obtains graphite oxide；By graphite oxide It is ultrasonic in water, obtain graphene oxide solution.
(2) metal amino complex solution is prepared
The metal chloride of 0.01~0.1mol is weighed, is dissolved in the deionized water of 100mL, adds in the ammonia of 10~50mL Water is made into corresponding metal amino complex solution.
(3) the graphene oxide Base Metal amido complex compound of sandwich structure is prepared
5~20mL metal amino complex solutions are slowly dropped into the graphene oxide solution of 100mL, stirring 1~3 is small When；The solution that precipitation is precipitated is centrifuged, washed and dried, obtains the graphene oxide Base Metal amino complexing of sandwich structure Object.
(4) the graphene-based metal or metal oxide of sandwich structure are prepared
Under inert gas shielding, graphene oxide Base Metal amido complex compound is heated 0.1~2 at 500~1000 DEG C Hour, heating rate is 1~10 DEG C/min；Room temperature is down to, obtains the graphene-based metal or metal oxide of sandwich structure.
The graphene-based metal or metal oxide of sandwich structure provided by the invention have outstanding chemical property, It can be used as the electrode material of lithium ion battery and ultracapacitor.
The effect of the present invention：
The present invention is first respectively synthesized graphene oxide and metal amino complex solution, then adjust the pH value of solution, makes oxygen Graphite alkene surface is negatively charged, surface of graphene oxide is made to adsorb positively charged metal amino complex compound by self assembly, Sandwich structure is formed, then is heated under inert gas shielding, metal amino complex compound is made to be decomposed into metal or metal oxide, Redox graphene simultaneously, obtains the graphene-based metal or metal oxide of sandwich structure.The composite material is shown Higher charge/discharge capacity, outstanding cycle performance and high rate performance, can be as lithium ion battery or the electricity of ultracapacitor Pole material.
Description of the drawings
Fig. 1 is X-ray diffraction (XRD) figure of graphene-based zinc oxide prepared by the present invention；
Fig. 2 is scanning electron microscope (SEM) figure of graphene-based zinc oxide prepared by the present invention；
Fig. 3 is transmission electron microscope (TEM) figure of graphene-based zinc oxide prepared by the present invention；
Fig. 4 is the cycle performance of battery figure of graphene-based zinc oxide prepared by the present invention.
Specific embodiment
The preparation method of graphene oxide involved in the present invention includes all methods for preparing graphene oxide, is related to The preparation method of metal amino complex solution includes all methods for preparing metal amino complex compound, can also use other in addition Ligand substituting amino.
It is making further detailed, clear and complete description of how realizing to the present invention with reference to specific embodiment, institute Row embodiment is only further described the present invention, not thereby limiting the invention：
Embodiment 1：
(1) graphene oxide 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, it is added with stirring and is changed to 5g graphite；After mixing 4~5 hours, it is slowly added into 30g Gao Meng Sour potassium (KMnO4)；35 DEG C are reacted 2 hours, add in the dilution of 460mL deionized waters, and 98 DEG C are stirred 15 minutes, and it is dilute to add in deionized water It releases, and adds in 100mL hydrogen peroxide (30%, H2O2)；Filtering, is washed, then be washed with deionized into the dilute hydrochloric acid of 2L 5% Property is to get graphite oxide.
(2) four ammino zinc solution of dichloride is prepared
Weigh the ZnCl of 0.03mol2, dissolve in the deionized water of 100mL, add the ammonium hydroxide of 20mL, obtain dichloride Four ammino zinc solutions.
(3) four ammino zinc complexes of graphite oxide alkenyl dichloride are prepared
Four ammino zinc solution of 5mL dichlorides is measured, is slowly dropped into 100mL in the graphene oxide solution of ultrasonic disperse； After stirring 1~3 hour, the solution that precipitation is precipitated is centrifuged, washed and dried, obtains four ammino zinc of graphite oxide alkenyl dichloride Compound.
(4) graphene-based zinc oxide is prepared
Under nitrogen protection, four ammino zinc complexes of graphite oxide alkenyl dichloride are heated 0.2 hour at 500 DEG C, 10 DEG C/min of heating rate；Room temperature is down to, obtains the graphene-based zinc oxide of sandwich structure.
The XRD spectra of sample is shown in Fig. 1, it was demonstrated that the sample of preparation contains carbon and zinc oxide；The SEM photograph of sample is shown in Fig. 2, card Bright sample has sandwich structure, and Zinc oxide particles are fixed in the graphene layer of superposition；The TEM photos of sample are shown in Fig. 3, it was demonstrated that Zinc oxide particles have nano-scale, and are dispersed between graphene layer.
(5) electrochemical properties are tested
The graphene-based zinc oxide of zinc oxide and sandwich structure is subjected to electrochemical properties test respectively, finds graphene Base zinc oxide has higher charge/discharge capacity, better cycle performance and high rate performance (see Fig. 4).
Embodiment 2：
(1) 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；It is cooled to room temperature, uses 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 in (30%, H2O2)；Filtering, is washed with the dilute hydrochloric acid of 1: 10 (volume ratio), then is washed with deionized to neutrality to get oxidation stone Ink；By graphite oxide, ultrasound can obtain graphene oxide solution in 0.5~1 hour in water.
(2) four ammino copper solution of dichloride is prepared
Weigh the CuCl of 0.05mol2, dissolve in the deionized water of 100mL, add the ammonium hydroxide of 30mL, obtain dichloride Four ammino copper solutions.
(3) four ammino copper composition of graphite oxide alkenyl dichloride is prepared
Four ammino copper solution of 10mL dichlorides is measured, is slowly dropped into 100mL in the graphene oxide solution of ultrasonic disperse； After stirring 1~3 hour, the solution that precipitation is precipitated is centrifuged, washed and dried, obtains four ammino copper of graphite oxide alkenyl dichloride Compound.
(4) graphene-based copper is prepared
Under nitrogen protection, four ammino copper composition of graphite oxide alkenyl dichloride is heated 0.5 hour at 600 DEG C, 5 DEG C/min of heating rate；Room temperature is down to, obtains the graphene-based copper of sandwich structure.
The sample that the XRD spectra of sample proves to prepare contains carbon and copper；The SEM photograph of sample proves that sample has sandwich Structure, copper particle are fixed in the graphene layer of superposition；The TEM photos of sample prove that copper particle has nano-scale, and uniformly It is dispersed between graphene layer.
The more than 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, variation 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 (6)

1. the fast preparation method of a kind of graphene-based metal of sandwich structure or metal oxide, it is characterised in that using following Step：
(1) graphene oxide is prepared；
(2) metal amino complex solution is prepared；
(3) the graphene oxide Base Metal amido complex compound of sandwich structure is prepared by self assembly；
Specifically：The graphene oxide of 0.01~0.1g is added in 100mL water, it is molten that ultrasonic disperse is made into graphene oxide Liquid；The metal amino complex compound of 0.01~0.1mol is added in 100mL water, it is molten that ultrasonic disperse is made into metal amino complex compound Liquid；Metal amino complex solution is added drop-wise in graphene oxide solution, is stirred 1~3 hour；Centrifugation, washing, drying；
(4) complex precipitate is collected, is heated at high temperature under inert gas shielding；
(5) the graphene-based metal or metal oxide of sandwich structure are obtained.
2. preparation method according to claim 1, which is characterized in that the surface functional group quantity of the graphene oxide can It is adjusted by controlling degree of oxidation.
3. preparation method according to claim 1, which is characterized in that the surface of the graphene oxide can pass through modification Other functional groups increase number of functional groups：Amino, imino group, secondary amino.
4. preparation method according to claim 1, which is characterized in that the metal amino complex compound includes：Zinc ammonia complexing Object, cobalt ammonia complex, nickel ammine, cupric ammine complex, chromium ammino-complex, magnesium ammino-complex, manganese ammino-complex, platinum ammonia complexing Object, palladium ammino-complex, silver ammonia complex.
5. preparation method according to claim 1, which is characterized in that the self assembling process metal amino complex compound Load capacity is related with the surface functional group quantity of graphene oxide.
6. preparation method according to claim 1, which is characterized in that heating temperature in the step (4) 500~ In the range of 1000 DEG C, the residence time, heating rate was in the range of 1~10 DEG C/min, product species in the range of 0.1~2 hour It is related with reaction temperature and time.
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