CN105977460A - Graphene composite material, preparation method and application thereof - Google Patents
Graphene composite material, preparation method and application thereof Download PDFInfo
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- CN105977460A CN105977460A CN201610341146.1A CN201610341146A CN105977460A CN 105977460 A CN105977460 A CN 105977460A CN 201610341146 A CN201610341146 A CN 201610341146A CN 105977460 A CN105977460 A CN 105977460A
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- 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
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- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- Y02E60/10—Energy storage using batteries
Abstract
The embodiment of the invention discloses a graphene composite material, a preparation method and an application thereof. The graphene composite material is prepared from graphene and titanium dioxide particles distributed on the surface of the graphene. Due to blocking of the titanium dioxide particles on the surface of the graphene, agglomeration of the graphene can be prevented. After the graphene composite material disclosed by the invention is assembled into a lithium-ion battery, in the charge-discharge process, generation of an SEI film on the surface of the graphene in an electrochemical reaction process can be reduced; the ion transmission distance is shortened; and the electronic mobility is improved, so that the electrochemical properties of the graphene composite material are improved.
Description
Technical field
The present invention relates to field of lithium ion battery, particularly to a kind of graphene composite material, its preparation method
And application.
Background technology
Lithium ion battery has that specific energy is big, running voltage is high, memory-less effect and the advantage such as environmentally friendly,
Not only be widely used in the compact electric apparatus such as mobile phone, camera, notebook, and electric motor car,
Application in the Large Electric equipment such as satellite, fighter plane also enjoys favor.The lifting of performance of lithium ion battery and
The decline widening raising and the cost depending greatly on negative material performance of range of application.Therefore,
The negative material of exploitation electrochemical performance is the focus of current Study on Li-ion batteries.
Graphene is the two-dimentional carbon film of a kind of only one of which atomic thickness, and the chemical bond between carbon atom is by sp2
Hybrid orbital forms, and research shows, Graphene has excellent electric conductivity and high theoretical specific surface area (2630
m2g-1), and which dictates that its great potential in field of lithium ion battery, prior art has been reported graphite
Alkene is as lithium ion battery negative material.But Graphene is particularly easy to reunite, and have impact on its capacity and circulation
Performance.Therefore, search out a kind of solve Graphene reunite way the most crucial.
Summary of the invention
The embodiment of the invention discloses a kind of graphene composite material, its preparation method and application, be used for solving
Graphene is as agglomeration traits during lithium ion battery negative material.Technical scheme is as follows:
Present invention firstly provides a kind of graphene composite material, it is by Graphene and is distributed in graphenic surface
Titanium dioxide granule forms.
In the preferred embodiment of the present invention, the particle diameter 5-7nm of described titanium dioxide granule.
Present invention also offers the preparation method of above-mentioned graphene composite material, including:
Graphene oxide and titanium source are joined in the first non-polar solven, stirs to graphene oxide dispersion all
Even, it is then centrifuged for, and washs the solid content of centrifugal gained；
Solid content after washing is scattered in the second non-polar solven, and hydro-thermal reaction 4-8 at 140-200 DEG C
Hour, after reaction terminates, it is centrifuged product processing, the solid product of centrifugal gained is dried,
And calcine in an inert atmosphere, obtain described graphene composite material.
In the preferred embodiment of the present invention, described first non-polar solven and the second non-polar solven
Selected from least one in pentane, Pentamethylene., normal hexane and hexamethylene；Described titanium source is selected from metatitanic acid
Four butyl esters or tetraisopropyl titanate.
In the preferred embodiment of the present invention, graphene oxide is 1:20-40 with the mass ratio in titanium source,
It is preferably 1:25-35.
In the preferred embodiment of the present invention, calcining heat is 400-500 DEG C, and calcination time is
120-240 minute, heating rate was 1-5 DEG C/min.
Present invention also offers a kind of lithium ion battery negative, live as negative pole using above-mentioned graphene composite material
Property material.
In the preferred embodiment of the present invention, above-mentioned lithium ion battery negative also includes binding agent, institute
State the 1%-3% that weight is described graphene composite material weight of binding agent.
Present invention also offers a kind of lithium ion battery, comprise above-mentioned lithium ion battery negative.
In the preferred embodiment of the present invention, above-mentioned lithium ion battery also includes positive pole, barrier film and electricity
Solve liquid.
By above-mentioned technical scheme, the invention provides a kind of graphene composite material, by Graphene
And the titanium dioxide granule being distributed in graphenic surface forms, due to the resistance of graphenic surface titanium dioxide granule
Every, it is possible to prevent the reunion of Graphene；The lithium ion graphene composite material of the application present invention is assembled into battery
After, in charge and discharge process, it is possible to reduce graphenic surface is SEI film (solid electricity during electrochemical reaction
Solve matter interfacial film) generation, shorten ion transmission distance, improve electron mobility, thus promote its electrification
Learn performance.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to enforcement
In example or description of the prior art, the required accompanying drawing used is briefly described, it should be apparent that, describe below
In accompanying drawing be only some embodiments of the present invention, for those of ordinary skill in the art, do not paying
On the premise of going out creative work, it is also possible to obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is the TEM figure of the graphene composite material of preparation in embodiment 1；
Fig. 2 is the Graphene of preparation in the graphene composite material and embodiment 4 prepared in embodiment 1
XRD figure, the Graphene XRD figure of preparation during wherein A is embodiment 4 in Fig. 2；In Fig. 2, B is for implementing
The XRD figure of the graphene composite material of preparation in example 1；
Fig. 3 A is the test result that No. 1 battery is tested on LAND battery test system；
Fig. 3 B is the test result that No. 2 batteries are tested on LAND battery test system；
Fig. 3 C is the test result that No. 3 batteries are tested on LAND battery test system.
Detailed description of the invention
The invention provides a kind of graphene composite material, by Graphene and the dioxy that is distributed in graphenic surface
Changing titanium granule composition, the particle diameter of described titanium dioxide granule is 5-7nm.This graphene composite material can by with
Lower section method prepares:
Graphene oxide and titanium source are joined in the first non-polar solven, stirs to graphene oxide dispersion all
Even, it is then centrifuged for, and washs the solid content of centrifugal gained；
Solid content after washing is scattered in the second non-polar solven, and hydro-thermal reaction 4-8 at 140-200 DEG C
Hour, after reaction terminates, it is centrifuged product processing, the solid product of centrifugal gained is dried,
And calcine in an inert atmosphere, obtain described graphene composite material.Wherein, described first nonpolar molten
Agent and the second non-polar solven are preferably chosen from least in pentane, Pentamethylene., normal hexane and hexamethylene
Kind, the first non-polar solven can be identical with the second non-polar solven, it is also possible to different.For the first non-pole
Property solvent and the consumption of the second non-polar solven, do not have particular/special requirement, as long as the first non-polar solven ensures it
Graphene oxide can be disperseed, it is preferable that the first non-polar solven with the ratio of graphene oxide is
200-400:1mL/g；Similarly, as long as the second non-polar solven ensures that the solid content after washing can be divided by it
Dissipate, it is preferable that the second non-polar solven is 300-500:1mL/g with the ratio of graphene oxide；；This
Titanium source used by invention can be selected from the compound being capable of the object of the invention titanium elements, preferably metatitanic acid
At least one in four butyl esters and tetraisopropyl titanate, graphene oxide is 1:20-40 with the mass ratio in titanium source,
It is preferably 1:25-35.Described noble gas can be the gas that argon, nitrogen etc. are conventional, preferably nitrogen；
Owing to calcine technology is technology commonly used in the art, the present invention is not described in detail at this, only limits its work
Skill parameter, as calcining heat is 400-500 DEG C, calcination time is 120-240 minute, heating rate is 1-5 DEG C/
Minute.Those skilled in the art can realize calcination process according to parameter disclosed in this invention.
Present invention also offers this graphene composite material of a kind of application lithium-ion electric as negative electrode active material
Pond negative pole, also includes binding agent, but does not include conductive agent and negative current collector in this lithium ion battery negative；
The weight of described binding agent is negative electrode active material (graphene composite material that the present invention provides) weight
1%-3%.Described binding agent can use the binding agent that in prior art, lithium ion battery negative is conventional, such as
Can be selected from Kynoar, politef, POLYPROPYLENE GLYCOL, epoxy resin, polymethylacrylic acid,
At least one in polymethyl methacrylate and polyvinylpyrrolidone.The lithium ion battery that the present invention provides
Negative pole can be lamellar or other shape, when being in lamellar, can be called anode plate for lithium ionic cell.
Those skilled in the art all know, in existing lithium ion battery, for ensureing that battery has good charge and discharge electrical
Can, lithium ion battery negative is required for adding conductive agent and negative current collector.And in the present invention, inventor
Having been surprisingly found that, the graphene composite material using the present invention to provide prepares lithium-ion electric as negative electrode active material
During the negative pole of pond, it is not necessary to add conductive agent and negative current collector, and at conductive agent and negative current collector the most not
In the presence of, it is possible to ensure that the charge-discharge performance of lithium ion battery does not declines.Application is the present invention provide
Lithium ion battery negative, assembles with positive pole, barrier film and electrolyte etc., it is possible to obtain the present invention provides
Lithium ion battery；It should be noted that when assembling the lithium ion battery that the present invention provides, just used
Pole, barrier film and electrolyte etc. all can use and assemble the material that lithium ion battery is commonly used in prior art, this
Invention is not defined at this.Similarly, the method assembling lithium ion battery is also prior art, the present invention
It is not defined at this.Lithium ion battery provided by the present invention is specifically as follows 2032 button cells etc..
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clearly
Chu, be fully described by, it is clear that described embodiment be only a part of embodiment of the present invention rather than
Whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not making creation
The every other embodiment obtained under property work premise, broadly falls into the scope of protection of the invention.
First, the preparation method of graphene oxide is illustrated.Graphene oxide employed in the present invention
Can be prepared by the Hummer method improved, detailed process includes: by natural flake graphite (5g), dense
Sulphuric acid (230mL, 98%) and sodium nitrate (NaNO3, 5g) and mixing, cool down under condition of ice bath and do not disable glass
Glass rod stirs, and after mix homogeneously, is slowly added to potassium permanganate (KMnO4, 30g), control temperature of reaction system.
Then reaction vessel is placed in the water bath with thermostatic control of about 35 DEG C, after stirring 30 minutes, adds deionized water
(460mL), oil bath, control reacting liquid temperature at about 98 DEG C.Continue stirring 15 minutes, be subsequently adding big
Deionized water (1.4L) washing of amount, is simultaneously introduced hydrogen peroxide (30%H2O2, 25mL), at this moment solution from
Brownish black becomes vivid yellow.Filter after still aging, and with dilute hydrochloric acid (1:10 volume ratio, 2L) to product
Thing washs.Fully wash until without SO in filtrate with deionized water4 2-(BaCl2Solution detects).65 DEG C of skies
Air dry is dry, airtight preservation.
Embodiment 1
0.1g GO (graphene oxide) is dispersed in 30mL hexamethylene, adds 3mL metatitanic acid four fourth
Ester (C16H36O4Ti), 15 days are stirred until GO is uniformly dispersed.Then by dispersion liquid centrifugation (15000
R/ minute), remove supernatant, by the solid content thiacyclohexane repeated washing 3 times of centrifugal gained, then will wash
Solid content after washing is dispersed in 40mL hexamethylene again, is then transferred in 100mL reactor,
180 DEG C of hydro-thermals 6 hours, are cooled to after room temperature centrifugal (15000 revs/min), go after supernatant liquid 30 DEG C
It is dried, tube furnace is calcined under 450 DEG C of nitrogen atmospheres 180 minutes (heating rate is 2 DEG C/min) and obtains
Graphene composite material 0.18g.
Embodiment 2
0.1g GO (graphene oxide) is dispersed in 30mL hexamethylene, adds 3.5mL metatitanic acid four
Butyl ester (C16H36O4Ti), 15 days are stirred until GO is uniformly dispersed.Then by dispersion liquid centrifugation (15000
Rev/min), remove supernatant, by the solid content thiacyclohexane repeated washing 3 times of centrifugal gained, then will wash
Solid content after washing is dispersed in 40mL hexamethylene again, is then transferred in 100mL reactor,
200 DEG C of hydro-thermals 4 hours, are cooled to after room temperature centrifugal (15000 revs/min), go after supernatant liquid 30 DEG C
It is dried, tube furnace is calcined under 500 DEG C of nitrogen atmospheres 120 minutes (heating rate is 5 DEG C/min) and obtains
Graphene composite material 0.20g.
Embodiment 3
0.1g GO (graphene oxide) is dispersed in 30mL hexamethylene, adds 2.5mL metatitanic acid four
Isopropyl ester, stirs 15 days until GO is uniformly dispersed.Then by dispersion liquid centrifugation (15000 revs/min),
Remove supernatant, by the solid content thiacyclohexane repeated washing 3 times of centrifugal gained, then will consolidating after washing
Shape thing is dispersed in 40mL hexamethylene again, is then transferred in 100mL reactor, 140 DEG C of hydro-thermals 8
Hour, it is cooled to after room temperature centrifugal (15000 revs/min), after removing supernatant liquid, 30 DEG C are dried, at pipe
Formula stove is calcined under 400 DEG C of nitrogen atmospheres 240 minutes (heating rate is 1 DEG C/min) obtain Graphene and be combined
Material 0.17g.
Embodiment 4
The preparation of Graphene
0.5308gGO (graphene oxide) ultrasonic disperse is in 60mL deionized water and the mixing of dehydrated alcohol
In solution, (water is 1:5 with the volume ratio of ethanol), magnetic agitation 1 hour, after being uniformly dispersed, will mix molten
Liquid transfers in 80mL politef reactor 180 DEG C of hydro-thermal reactions 8 hours, after being cooled to room temperature,
After deionized water wash, 60 DEG C of vacuum drying, obtain 0.2145g Graphene.
Performance and test
1, transmission electron microscope (TEM) is analyzed
Use transmission electron microscope (JEOL JEM-2010) to the Graphene composite wood of preparation in embodiment 1
Material is scanned analyzing, and result is as it is shown in figure 1, can find out titanium dioxide granule in FIG clearly
Lattice structure, spacing of lattice is aboutMatch with the diffraction maximum of titanium dioxide in XRD, titanium dioxide
The particle diameter of granule is about at 5-7nm.
2, X-ray diffraction (XRD) is analyzed
The x-ray powder diffraction instrument (model: X Pert PRO MPD) using PANalytical company of Holland to produce is right
The Graphene prepared in the graphene composite material prepared in the embodiment of the present invention 1 and embodiment 4 carries out X and penetrates
Line diffraction analysis, analysis result is as shown in Figure 2；Radioactive source during analysis is Cu-Ka, measures step-length and is
0.017 °, sweep time is 10 seconds/step, and in Fig. 2, A is the XRD figure of Graphene, and in Fig. 2, B is stone
The XRD figure of ink alkene composite.
From Fig. 2 in the contrast of A Yu B it can be seen that graphene composite material after calcination processing with
Simple Graphene is compared, it will be apparent that have more a lot of diffraction maximum, and the diffraction maximum having more and standard PDF card
The base peak of middle titanium dioxide very matching, it was demonstrated that the most successfully load titanium dioxide at graphenic surface
Little granule.
Embodiment 5
Preparation is without conductive agent and the anode plate for lithium ionic cell of negative current collector
Kynoar (PVDF) 0.6730g is dissolved in N-Methyl pyrrolidone (NMP) 10.5437g
In, forming mass fraction is the solution of 6%；Graphene composite material (0.0634g) prepared by embodiment 1 with
In this solution, PVDF is according to the ratio mixing that mass ratio is 80:20, and the quality of the PVDF solution weighed is about
For 0.2642g, it is fully ground uniformly.Thick mixed slurry after grinding, is transferred to use ethanol
On the glass surface crossed, then the height of regulation automatic coating machine scraper is 25 microns, and automatic coating is at glass
Surface, be then placed within infrared lamp irradiate within 40 minutes, vapor away to NMP after, be transferred to vacuum
In drying baker.Place 12 hours at 110 DEG C.Then tweezers are used the battery membranes completed to be separated with glass,
With sanction film machine, battery membranes is cut into the circular negative plate of a diameter of 14 millimeters, after weighing quality, is placed on glove box
In standby.
Embodiment 6
2032 button cells are assembled with the anode plate for lithium ionic cell of embodiment 5 preparation
Battery assembling is carried out in the glove box of full high-purity argon.Detailed process is: lithium sheet is put into negative electrode casing
In, spread barrier film (PE film), (solute of electrolyte is LiPF to add 110 μ L electrolyte6, solvent is body
Ethylene carbonate/diethyl carbonate/dimethyl carbonate (EC/DEC/DMC) that long-pending ratio is 1:1:1 mixes,
LiPF6Molar concentration be 1mol/L).The lithium of embodiment 5 preparation is added after liquid uniform wet barrier film to be electrolysed
Ion battery negative plate, adds steel disc and shell fragment afterwards, finally buckles anode cover, loads in valve bag, envelope
Mouthful.After taking out from glove box, immediately by cell sealing on sealing machine, stand 12 hours.This battery claims
It it is No. 1 battery.
Comparative example 1
Preparation has the anode plate for lithium ionic cell of conductive agent and negative current collector
Kynoar (PVDF) 0.6730g is dissolved in N-Methyl pyrrolidone (NMP) 10.5437g
In, forming mass fraction is the solution of 6%；Graphene composite material (0.1075g) prepared by embodiment 1,
Acetylene black (0.0235) (conductive agent) and PVDF (claiming solution, 0.3588g) are 70:15:15's according to mass ratio
Ratio mixes, and is fully ground uniformly, and the thick material obtained is transferred to the Copper Foil crossed with ethanol
On (negative current collector), the height then regulating automatic coating machine scraper is 25 microns.Just may be used after coating
To obtain battery membranes.The battery membranes completed is irradiated under infrared lamp after a period of time vapors away to NMP,
It is transferred in vacuum drying oven.Place 12 hours at 110 DEG C.Then it is cut into circular negative plate with sanction film machine,
Weigh, be placed in glove box standby.
Comparative example 2
With embodiment 4 preparation Graphene as negative electrode active material, prepare anode plate for lithium ionic cell
The preparation process of comparative example 2 is only that the negative electrode active material in comparative example 1 with the difference of comparative example 1
Matter (graphene composite material of embodiment 1 preparation) replaces to Graphene, and other is identical with comparative example 1.
Comparative example 3
With the anode plate for lithium ionic cell composition lithium ion battery of comparative example 1 preparation, its assembling process and enforcement
Example 6 is identical, simply uses the lithium ion battery negative of comparative example 1 preparation.This battery is referred to as No. 2 batteries.
Comparative example 4
With the anode plate for lithium ionic cell composition lithium ion battery of comparative example 2 preparation, its assembling process and contrast
Example 3 is identical, simply uses the lithium ion battery negative of comparative example 2 preparation.This battery is referred to as No. 3 batteries.
Performance of lithium ion battery is tested
No. 1 battery, No. 2 batteries and No. 3 batteries are tested respectively on LAND battery test system, surveys
Test result is respectively as shown in Fig. 3 A, Fig. 3 B and Fig. 3 C, and this experiment is to carry out discharge and recharge under constant current,
Electric current density is 0.5C (1C=200mA/g), and voltage range is 0-3.0V.
Fig. 3 A is the test result of No. 1 battery, it can be seen that after carrying out 100 discharge and recharges, fill
Specific discharge capacity is about stable at 635mAh/g；Fig. 3 B is the test result of No. 2 batteries, can from figure
Going out, after No. 2 batteries carry out 100 discharge and recharges, charging and discharging capacity is about stable at 467mAh/g；Fig. 3 C
Being the test result of No. 3 batteries, after carrying out 100 discharge and recharges, charging and discharging capacity is about stable at 246mAh/g；
Visible, No. 1 battery and the performance of No. 2 batteries, compared with No. 3 batteries, all it is greatly improved.And 1
Number battery there has also been bigger lifting compared with the performance of No. 2 batteries, and No. 1 battery eliminates making battery cathode
Required conductive agent acetylene black and required copper foil of affluxion body, reduce the cost of lithium battery.
The electricity utilizing lithium ion battery negative provided by the present invention to make is can be seen that by above-mentioned test
Pond, its performance is compared with the battery utilizing Graphene to make, and charge-discharge performance is greatly improved, and utilizes this
The battery that the lithium ion battery negative that invention is provided makes, in the case of saving conductive agent and collector,
The charging and discharging capabilities of battery does not the most decline, and also has on the contrary and promotes.
Above a kind of graphene composite material provided by the present invention, its preparation method and application are carried out in detail
Thin introduction.Principle and the embodiment of the present invention are set forth by specific embodiment used herein, with
The explanation of upper embodiment is only intended to help to understand method and the central idea thereof of the present invention.It is right to it should be pointed out that,
For those of ordinary skill in the art, under the premise without departing from the principles of the invention, it is also possible to this
Bright carrying out some improvement and modification, these improve and modify the protection also falling into the claims in the present invention.
Claims (10)
1. a graphene composite material, it is characterised in that by Graphene and be distributed in the two of graphenic surface
Titan oxide particles forms.
2. the method for claim 1, it is characterised in that the particle diameter of described titanium dioxide granule is
5-7nm。
3. the preparation method of graphene composite material described in claim 1 or 2, it is characterised in that including:
Graphene oxide and titanium source are joined in the first non-polar solven, stirs to graphene oxide dispersion all
Even, it is then centrifuged for, and washs the solid content of centrifugal gained；
Solid content after washing is scattered in the second non-polar solven, and hydro-thermal reaction 4-8 at 140-200 DEG C
Hour, after reaction terminates, it is centrifuged product processing, the solid product of centrifugal gained is dried,
And calcine in an inert atmosphere, obtain described graphene composite material.
4. method as claimed in claim 3, it is characterised in that described first non-polar solven and second non-
Polar solvent is selected from least one in pentane, Pentamethylene., normal hexane and hexamethylene；Described titanium source is selected
From in butyl titanate or tetraisopropyl titanate.
5. method as claimed in claim 3, it is characterised in that graphene oxide and the mass ratio in titanium source
For 1:20-40, preferably 1:25-35.
6. method as claimed in claim 3, it is characterised in that calcining heat is 400-500 DEG C, during calcining
Between be 120-240 minute, heating rate is 1-5 DEG C/min.
7. a lithium ion battery negative, it is characterised in that be combined with the Graphene described in claim 1 or 2
Material is as negative electrode active material.
8. lithium ion battery negative as claimed in claim 7, it is characterised in that also include binding agent, institute
State the 1%-3% that weight is described graphene composite material weight of binding agent.
9. a lithium ion battery, it is characterised in that comprise the lithium ion battery described in claim 7 or 8 and bear
Pole.
10. lithium ion battery as claimed in claim 9, it is characterised in that also include positive pole, barrier film and electricity
Solve liquid.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108172804A (en) * | 2017-12-31 | 2018-06-15 | 中南大学 | A kind of graphene/coated by titanium dioxide positive electrode and its preparation and application |
| CN109182821A (en) * | 2018-09-17 | 2019-01-11 | 南昌大学 | A kind of pressure casting method of graphene enhancing ADC12 aluminium alloy |
| CN109182822A (en) * | 2018-09-17 | 2019-01-11 | 南昌大学 | A kind of die forging method of 7075 aluminium alloy of high-performance |
| CN109385551A (en) * | 2018-09-17 | 2019-02-26 | 南昌大学 | A kind of coated with titanium oxide/graphene oxide enhancing preparation method for material of substrate containing magnalium |
| CN110611964A (en) * | 2018-06-14 | 2019-12-24 | 苏州汉纳材料科技有限公司 | Heating film material with PTC effect and preparation method thereof |
| CN111446429A (en) * | 2020-03-27 | 2020-07-24 | 珠海冠宇电池股份有限公司 | Poly-polyanion cathode material and preparation method and application thereof |
| CN113964315A (en) * | 2021-10-14 | 2022-01-21 | 北京师范大学 | Preparation method and application of large-size two-dimensional lithium titanate nanosheet |
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| CN108172804A (en) * | 2017-12-31 | 2018-06-15 | 中南大学 | A kind of graphene/coated by titanium dioxide positive electrode and its preparation and application |
| CN108172804B (en) * | 2017-12-31 | 2020-09-08 | 中南大学 | Graphene/titanium dioxide coated positive electrode material and preparation and application thereof |
| CN110611964A (en) * | 2018-06-14 | 2019-12-24 | 苏州汉纳材料科技有限公司 | Heating film material with PTC effect and preparation method thereof |
| CN109182821A (en) * | 2018-09-17 | 2019-01-11 | 南昌大学 | A kind of pressure casting method of graphene enhancing ADC12 aluminium alloy |
| CN109182822A (en) * | 2018-09-17 | 2019-01-11 | 南昌大学 | A kind of die forging method of 7075 aluminium alloy of high-performance |
| CN109385551A (en) * | 2018-09-17 | 2019-02-26 | 南昌大学 | A kind of coated with titanium oxide/graphene oxide enhancing preparation method for material of substrate containing magnalium |
| CN109385551B (en) * | 2018-09-17 | 2020-07-14 | 南昌大学 | Preparation method of titanium oxide/graphene oxide coated enhanced aluminum-magnesium-containing base material |
| CN111446429A (en) * | 2020-03-27 | 2020-07-24 | 珠海冠宇电池股份有限公司 | Poly-polyanion cathode material and preparation method and application thereof |
| CN113964315A (en) * | 2021-10-14 | 2022-01-21 | 北京师范大学 | Preparation method and application of large-size two-dimensional lithium titanate nanosheet |
| CN114029009A (en) * | 2021-11-22 | 2022-02-11 | 哈尔滨工业大学 | Preparation method of high-efficiency and environment-friendly graphene-paraffin phase-change microcapsule material |
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