CN105977460B - A kind of graphene composite material, preparation method and application - Google Patents
A kind of graphene composite material, preparation method and application Download PDFInfo
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- CN105977460B CN105977460B CN201610341146.1A CN201610341146A CN105977460B CN 105977460 B CN105977460 B CN 105977460B CN 201610341146 A CN201610341146 A CN 201610341146A CN 105977460 B CN105977460 B CN 105977460B
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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 kind of graphene composite material, preparation method and applications, wherein the graphene composite material is by graphene and is distributed in the titanium dioxide granule of graphene surface and forms.Due to the barrier of graphene surface titanium dioxide granule, the reunion of graphene can be prevented；After lithium ion battery being assembled into using the graphene composite material of the present invention, in charge and discharge process, it is possible to reduce the distance of ion transmission is shortened in the generation of graphene surface SEI films during electrochemical reaction, electron mobility is improved, to promote its chemical property.
Description
Technical field
The present invention relates to field of lithium ion battery, more particularly to a kind of graphene composite material, preparation method and application.
Background technology
Lithium ion battery has many advantages, such as that bigger than energy, operating voltage is high, memory-less effect and environmentally friendly, not only exists
It is widely used in the compact electric apparatus such as mobile phone, camera, notebook, and in the large-scale electricity such as electric vehicle, satellite, fighter plane
Application in dynamic equipment also receives favor.The promotion of performance of lithium ion battery and widening for application range are largely depended on
In the raising of negative material performance and the decline of cost.Therefore, the negative material for developing electrochemical performance be current lithium from
The hot spot of sub- battery research.
Graphene is the two-dimentional carbon film of atomic thickness there are one a kind of, and the chemical bond between carbon atom is by sp2 hydridization rails
Road forms, studies have shown that graphene has excellent electric conductivity and high theoretical specific surface area (2630m2g-1), and which dictates that
, in the great potential of field of lithium ion battery, the prior art has been reported using graphene as lithium ion battery negative material for it.
But graphene is particularly easy to reunite, and affects its capacity and cycle performance.Therefore, search out it is a kind of solution graphene reunite
Method is just very crucial.
Invention content
The embodiment of the invention discloses a kind of graphene composite material, preparation method and applications, for solving graphene
Agglomeration traits when as lithium ion battery negative material.Technical solution is as follows：
Present invention firstly provides a kind of graphene composite materials, by graphene and are distributed in the dioxy of graphene surface
Change titanium particle composition.
In the preferred embodiment of the present invention, the grain size 5-7nm of the titanium dioxide granule.
The present invention also provides the preparation methods of above-mentioned graphene composite material, including：
Graphene oxide and titanium source are added in the first nonpolar solvent, stirring to graphene oxide is uniformly dispersed, so
After centrifuge, and wash centrifugation gained solid content；
Solid content after washing is scattered in the second nonpolar solvent, and hydro-thermal reaction 4-8 is small at 140-200 DEG C
When, after reaction, reaction product is subjected to centrifugal treating, by the solid product drying of centrifugation gained and in an inert atmosphere
Calcining is to get the graphene composite material.
In the preferred embodiment of the present invention, first nonpolar solvent and the second nonpolar solvent are selected from
At least one of pentane, pentamethylene, n-hexane and hexamethylene；The titanium source is selected from four isopropyl of butyl titanate or metatitanic acid
Ester.
In the preferred embodiment of the present invention, graphene oxide and the mass ratio of titanium source are 1:20-40, preferably
It is 1:25-35.
In the preferred embodiment of the present invention, calcination temperature is 400-500 DEG C, and calcination time is 120-240 points
Clock, heating rate are 1-5 DEG C/min.
The present invention also provides a kind of negative electrode of lithium ion battery, using above-mentioned graphene composite material as negative electrode active material
Matter.
In the preferred embodiment of the present invention, above-mentioned negative electrode of lithium ion battery further includes adhesive, the bonding
The weight of agent is the 1%-3% of the graphene composite material weight.
The present invention also provides a kind of lithium ion batteries, including above-mentioned negative electrode of lithium ion battery.
In the preferred embodiment of the present invention, above-mentioned lithium ion battery further includes anode, diaphragm and electrolyte.
Through the above technical solution it is found that the present invention provides a kind of graphene composite material, by graphene and distribution
It is formed in the titanium dioxide granule of graphene surface, due to the barrier of graphene surface titanium dioxide granule, graphite can be prevented
The reunion of alkene；After being assembled into battery using the lithium ion graphene composite material of the present invention, in charge and discharge process, it is possible to reduce
The generation of graphene surface SEI films (solid electrolyte interface film) during electrochemical reaction, shorten ion transmission away from
From raising electron mobility, to promote its chemical property.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
Obtain other attached drawings according to these attached drawings.
Fig. 1 is the TEM figures of the graphene composite material prepared in embodiment 1；
Fig. 2 is the XRD diagram of the graphene composite material prepared in embodiment 1 and the graphene prepared in embodiment 4, wherein
A is the graphene XRD diagram prepared in embodiment 4 in Fig. 2；B is the XRD of the graphene composite material prepared in embodiment 1 in Fig. 2
Figure；
Fig. 3 A are the test results that No. 1 battery is tested on LAND battery test systems；
Fig. 3 B are the test results that No. 2 batteries are tested on LAND battery test systems；
Fig. 3 C are the test results that No. 3 batteries are tested on LAND battery test systems.
Specific implementation mode
The present invention provides a kind of graphene composite materials, by graphene and are distributed in the titanium dioxide of graphene surface
The grain size of grain composition, the titanium dioxide granule is 5-7nm.The graphene composite material can be made by following methods：
Graphene oxide and titanium source are added in the first nonpolar solvent, stirring to graphene oxide is uniformly dispersed, so
After centrifuge, and wash centrifugation gained solid content；
Solid content after washing is scattered in the second nonpolar solvent, and hydro-thermal reaction 4-8 is small at 140-200 DEG C
When, after reaction, reaction product is subjected to centrifugal treating, by the solid product drying of centrifugation gained and in an inert atmosphere
Calcining is to get the graphene composite material.Wherein, the first described nonpolar solvent and the second nonpolar solvent are preferably selected from
In at least one of pentane, pentamethylene, n-hexane and hexamethylene, the first nonpolar solvent can be with the second nonpolar solvent
It is identical, it can also be different.It is non-without particular/special requirement, first for the dosage of the first nonpolar solvent and the second nonpolar solvent
As long as polar solvent ensures that it can disperse graphene oxide, it is preferable that the first nonpolar solvent and graphene oxide
Ratio be 200-400:1mL/g；Similarly, as long as the second nonpolar solvent ensures that it can disperse the solid content after washing
, it is preferable that the ratio of the second nonpolar solvent and graphene oxide is 300-500:1mL/g；；Titanium source used in the present invention
It can be selected from the compound that can realize the object of the invention titanium elements, preferably in butyl titanate and tetraisopropyl titanate
The mass ratio of at least one, graphene oxide and titanium source is 1:20-40, preferably 1:25-35.Described inert gas can be with
For the common gas such as argon gas, nitrogen, preferably nitrogen；Since calcine technology is technology commonly used in the art, the present invention is herein
Without detailed description, its technological parameter is only limited, if calcination temperature is 400-500 DEG C, calcination time is 120-240 minutes,
Heating rate is 1-5 DEG C/min.Those skilled in the art can realize calcination process according to parameter disclosed in this invention.
It is negative as the lithium ion battery of negative electrode active material that the present invention also provides a kind of application graphene composite materials
Pole further includes adhesive in the negative electrode of lithium ion battery, but does not include conductive agent and negative current collector；The weight of described adhesive
For the 1%-3% of negative electrode active material (graphene composite material provided by the invention) weight.Described adhesive may be used existing
There is the common adhesive of negative electrode of lithium ion battery in technology, such as Kynoar, polytetrafluoroethylene (PTFE), polypropylene can be selected from
At least one of alcohol, epoxy resin, polymethylacrylic acid, polymethyl methacrylate and polyvinylpyrrolidone.The present invention
The negative electrode of lithium ion battery of offer can be sheet or other shapes, and when in sheet, it is negative can be called lithium ion battery
Pole piece.Those skilled in the art know, in existing lithium ion battery, to ensure that battery has good charge-discharge performance, lithium
Ion battery cathode is required for that conductive agent and negative current collector is added.And in the present invention, inventors be surprised to learn that, using this hair
When the graphene composite material of bright offer prepares negative electrode of lithium ion battery as negative electrode active material, need not be added conductive agent and
Negative current collector, and in the case where conductive agent and negative current collector are not present, can ensure the charge and discharge of lithium ion battery
Electrical property does not decline.Using negative electrode of lithium ion battery provided by the invention, assembled with anode, diaphragm and electrolyte etc., it can
To obtain lithium ion battery provided by the invention；It should be noted that when assembling lithium ion battery provided by the invention, adopted
The common material of assembling lithium ion battery institute in the prior art, the present invention may be used in anode, diaphragm and electrolyte etc.
Herein without limiting.Similarly, the method for assembling lithium ion battery is also the prior art, and the present invention is herein without limiting.
Lithium ion battery provided by the present invention is specifically as follows 2032 button cells etc..
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation describes, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other without creative efforts
Embodiment shall fall within the protection scope of the present invention.
First, the preparation method of graphene oxide is illustrated.Graphene oxide employed in the present invention can be by
Prepared by improved Hummer methods, detailed process includes：By natural flake graphite (5g), the concentrated sulfuric acid (230mL, 98%) and nitre
Sour sodium (NaNO3, 5g) and mixing, it is cooling under condition of ice bath not deactivate glass bar stirring, after mixing, it is slowly added to Gao Meng
Sour potassium (KMnO4, 30g), control temperature of reaction system.Then reaction vessel is placed in 35 DEG C or so of water bath with thermostatic control, is stirred
After 30 minutes, deionized water (460mL) is added, oil bath, control reacting liquid temperature is at 98 DEG C or so.Continue stirring 15 minutes, so
After a large amount of deionized water (1.4L) washing is added, while hydrogen peroxide (30%H is added2O2, 25mL), at this moment solution is from brownish black
Become vivid yellow.Filtering, is used in combination dilute hydrochloric acid (1 after still aging：10 volume ratios, 2L) product is washed.Spend from
Sub- water fully washs until without SO in filtrate4 2-(BaCl2Solution detects).65 DEG C are air-dried, closed preservation.
Embodiment 1
0.1g GO (graphene oxide) are dispersed in 30mL hexamethylenes, 3mL butyl titanates are added
(C16H36O4Ti), stir 15 days until GO is uniformly dispersed.Then dispersion liquid is centrifuged into (15000r/ minutes), removes supernatant
The solid content thiacyclohexane of centrifugation gained is washed repeatedly 3 times, the solid content after washing is then dispersed in 40mL rings again by liquid
In hexane, it is then transferred into 100mL reaction kettles, 180 DEG C of hydro-thermals 6 hours centrifuge (15000 revs/min) after being cooled to room temperature,
30 DEG C of dryings after supernatant liquid are gone, under 450 DEG C of nitrogen atmospheres calcining 180 minutes in tube furnace, (heating rate is 2 DEG C/minute
Clock) obtain graphene composite material 0.18g.
Embodiment 2
0.1g GO (graphene oxide) are dispersed in 30mL hexamethylenes, 3.5mL butyl titanates are added
(C16H36O4Ti), stir 15 days until GO is uniformly dispersed.Then dispersion liquid is centrifuged into (15000 revs/min), removes supernatant
The solid content thiacyclohexane of centrifugation gained is washed repeatedly 3 times, the solid content after washing is then dispersed in 40mL rings again by liquid
In hexane, it is then transferred into 100mL reaction kettles, 200 DEG C of hydro-thermals 4 hours centrifuge (15000 revs/min) after being cooled to room temperature,
30 DEG C of dryings after supernatant liquid are gone, under 500 DEG C of nitrogen atmospheres calcining 120 minutes in tube furnace, (heating rate is 5 DEG C/minute
Clock) obtain graphene composite material 0.20g.
Embodiment 3
0.1g GO (graphene oxide) are dispersed in 30mL hexamethylenes, 2.5mL tetraisopropyl titanates are added, are stirred
15 days until GO is uniformly dispersed.Then dispersion liquid is centrifuged into (15000 revs/min), removes supernatant, by centrifugation gained
Solid content is washed repeatedly 3 times with thiacyclohexane, and then the solid content after washing is dispersed in again in 40mL hexamethylenes, is then shifted
Into 100mL reaction kettles, 140 DEG C of hydro-thermals 8 hours centrifuge (15000 revs/min), after removing supernatant liquid after being cooled to room temperature
30 DEG C of dryings, calcining 240 minutes (heating rate is 1 DEG C/min) under 400 DEG C of nitrogen atmospheres in tube furnace, to obtain graphene multiple
Condensation material 0.17g.
Embodiment 4
The preparation of graphene
0.5308gGO (graphene oxide) ultrasonic disperses (water in the mixed solution of 60mL deionized waters and absolute ethyl alcohol
Volume ratio with ethyl alcohol is 1:5) mixed solution after being uniformly dispersed, is transferred to 80mL polytetrafluoroethylene (PTFE) by, magnetic agitation 1 hour
180 DEG C of hydro-thermal reactions 8 hours in reaction kettle, after being cooled to room temperature, after deionized water washing, 60 DEG C of vacuum drying obtain
0.2145g graphenes.
Performance and test
1, transmission electron microscope (TEM) is analyzed
The graphene composite material prepared in embodiment 1 is carried out using transmission electron microscope (JEOL JEM-2010)
Scanning analysis, the results are shown in Figure 1, can clearly find out the lattice structure of titanium dioxide granule in Fig. 1, spacing of lattice is about
ForIt matches with the diffraction maximum of titanium dioxide in XRD, the grain size of titanium dioxide granule is about in 5-7nm.
2, X-ray diffraction (XRD) is analyzed
X-ray powder diffraction instrument (the model produced using Dutch Panaco company：X Pert PRO MPD) to the present invention
The graphene prepared in the graphene composite material and embodiment 4 that are prepared in embodiment 1 carries out X-ray diffraction analysis, analysis knot
Fruit is as shown in Figure 2；Radioactive source in analytic process is Cu-Ka, and it is 0.017 ° to measure step-length, and sweep time is 10 seconds/step, Fig. 2
Middle A is the XRD diagram of graphene, and B is the XRD diagram of graphene composite material in Fig. 2.
Graphene composite material from the comparison of A in Fig. 2 and B as can be seen that after calcination processing and simple stone
Black alkene is compared, it will be apparent that the diffraction maximum for having more many diffraction maximums, and having more and the base peak of titanium dioxide in standard PDF cards are non-
Often fitting, it was demonstrated that successfully load upper titanium dioxide little particle on the surface of graphene.
Embodiment 5
Prepare the anode plate for lithium ionic cell without conductive agent and negative current collector
Kynoar (PVDF) 0.6730g is dissolved in N-Methyl pyrrolidone (NMP) 10.5437g, quality is formed
Score is 6% solution；Graphene composite material (0.0634g) prepared by embodiment 1 is with PVDF in the solution according to quality
Than being 80:20 ratio mixing, the quality of the PVDF solution weighed is about 0.2642g, is fully ground uniformly.It will be viscous after grinding
The mixed slurry of thick shape is transferred on the glass surface crossed with ethanol, and the height for then adjusting automatic coating machine scraper is
25 microns, automatic coating is then placed on the surface of glass after irradiating 40 minutes under infrared lamp and being vapored away to NMP, is turned
It moves in vacuum drying chamber.It is placed 12 hours at 110 DEG C.Then the battery membranes completed are detached using tweezers with glass, is used
The round negative plate that battery membranes are cut into a diameter of 14 millimeters by film machine is cut out, after weighing quality, is placed on spare in glove box.
Embodiment 6
2032 button cells are assembled with anode plate for lithium ionic cell prepared by embodiment 5
Battery assembling is carried out in the glove box full of high-purity argon.Detailed process is：Lithium piece is put into negative electrode casing, is spread
Diaphragm (PE films), 110 μ L electrolyte are added, and (solute of electrolyte is LiPF6, solvent is that volume ratio is 1:1:1 ethylene carbonate
Ester/diethyl carbonate/dimethyl carbonate (EC/DEC/DMC) mixes, LiPF6Molar concentration be 1mol/L).It is to be electrolysed
Anode plate for lithium ionic cell prepared by embodiment 5 is added after liquid uniform wet diaphragm, steel disc and shrapnel are added later, finally buckles
Anode cover is fitted into valve bag, sealing.After being taken out in glove box, it is small to be stood 12 for cell sealing on sealing machine immediately
When.The battery is known as No. 1 battery.
Comparative example 1
Prepare the anode plate for lithium ionic cell with conductive agent and negative current collector
Kynoar (PVDF) 0.6730g is dissolved in N-Methyl pyrrolidone (NMP) 10.5437g, quality is formed
Score is 6% solution；Graphene composite material (0.1075g) prepared by embodiment 1, acetylene black (0.0235) (conductive agent)
And PVDF (claiming solution, 0.3588g) is 70 according to mass ratio:15:15 ratio mixing, is fully ground uniformly, what is obtained is sticky
The substance of shape is transferred on the copper foil (negative current collector) crossed with ethanol, then regulates the height of automatic coating machine scraper
Degree is 25 microns.It can be obtained by battery membranes after coating.The battery membranes completed are irradiated under infrared lamp and are waved for a period of time to NMP
After hair falls, it is transferred in vacuum drying chamber.It is placed 12 hours at 110 DEG C.Then it is cut into round negative plate with sanction film machine, claimed
Weight, is placed on spare in glove box.
Comparative example 2
The graphene prepared using embodiment 4 prepares anode plate for lithium ionic cell as negative electrode active material
The preparation process of comparative example 2 is only that with the difference of comparative example 1 (implements the negative electrode active material in comparative example 1
Graphene composite material prepared by example 1) it is substituted for graphene, it is other identical as comparative example 1.
Comparative example 3
Lithium ion battery, assembling process and 6 phase of embodiment are formed with anode plate for lithium ionic cell prepared by comparative example 1
Together, the negative electrode of lithium ion battery for only using comparative example 1 to prepare.The battery is known as No. 2 batteries.
Comparative example 4
Lithium ion battery, assembling process and 3 phase of comparative example are formed with anode plate for lithium ionic cell prepared by comparative example 2
Together, the negative electrode of lithium ion battery for only using comparative example 2 to prepare.The battery is known as No. 3 batteries.
Performance of lithium ion battery is tested
No. 1 battery, No. 2 batteries and No. 3 batteries are tested on LAND battery test systems respectively, test result is respectively such as
Shown in Fig. 3 A, Fig. 3 B and Fig. 3 C, this experiment is that charge and discharge are carried out under constant current, and current density is 0.5C (1C=200mA/g),
Voltage range is 0-3.0V.
Fig. 3 A are the test results of No. 1 battery, it can be seen from the figure that after carrying out 100 charge and discharge, charging and discharging capacity
About stablize in 635mAh/g；Fig. 3 B are the test results of No. 2 batteries, it can be seen from the figure that No. 2 batteries carry out 100 charge and discharges
After electricity, charging and discharging capacity is about stablized in 467mAh/g；Fig. 3 C are the test results of No. 3 batteries, after carrying out 100 charge and discharge,
Charging and discharging capacity is about stablized in 246mAh/g；As it can be seen that the performance of No. 1 battery and No. 2 batteries has compared with No. 3 batteries
Prodigious promotion.And No. 1 battery compared with No. 2 batteries performance there has also been larger promotion, and No. 1 battery eliminates that make battery negative
Extremely required conductive agent acetylene black and required copper foil of affluxion body, reduce the cost of lithium battery.
By above-mentioned test it can be seen that the battery made using negative electrode of lithium ion battery provided by the present invention, property
Can be compared with the battery made using graphene, charge-discharge performance greatly improves, and utilizes lithium ion provided by the present invention
The battery that battery cathode makes, in the case where saving conductive agent and collector, the charging and discharging capabilities of battery do not decline not only,
Also have instead and is promoted.
Detailed Jie has been carried out to a kind of graphene composite material provided by the present invention, preparation method and application above
It continues.Principle and implementation of the present invention are described for specific embodiment used herein, the explanation of above example
It is merely used to help understand the method and its central idea of the present invention.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the principle of the present invention, can be with several improvements and modifications are made to the present invention, these improvement and modification
Also fall into the protection of the claims in the present invention.
Claims (8)
1. a kind of graphene composite material, which is characterized in that by graphene and be distributed in the titanium dioxide granule of graphene surface
Composition, wherein the grain size of the titanium dioxide granule is 5-7nm；
The graphene composite material is made by following preparation method, the method includes：
Graphene oxide and titanium source are added in the first nonpolar solvent, stirring is uniformly dispersed to graphene oxide, then from
The heart, and wash the solid content of centrifugation gained；
Solid content after washing is scattered in the second nonpolar solvent, and hydro-thermal reaction 4-8 hours at 140-200 DEG C, instead
After answering, reaction product is subjected to centrifugal treating, is calcined the solid product drying of centrifugation gained and in an inert atmosphere,
Up to the graphene composite material；
First nonpolar solvent and the second nonpolar solvent are in pentane, pentamethylene, n-hexane and hexamethylene
It is at least one；The titanium source is selected from butyl titanate or tetraisopropyl titanate.
2. graphene composite material as described in claim 1, which is characterized in that graphene oxide and the mass ratio of titanium source are
1:20-40。
3. graphene composite material as claimed in claim 2, which is characterized in that graphene oxide and the mass ratio of titanium source are
1:25-35。
4. graphene composite material as described in claim 1, which is characterized in that calcination temperature is 400-500 DEG C, calcination time
It it is 120-240 minutes, heating rate is 1-5 DEG C/min.
5. a kind of negative electrode of lithium ion battery, which is characterized in that lived using graphene composite material described in claim 1 as cathode
Property substance.
6. negative electrode of lithium ion battery as claimed in claim 5, which is characterized in that further include adhesive, the weight of described adhesive
Amount is the 1%-3% of the graphene composite material weight.
7. a kind of lithium ion battery, which is characterized in that include negative electrode of lithium ion battery described in claim 5 or 6.
8. lithium ion battery as claimed in claim 7, which is characterized in that further include anode, diaphragm and electrolyte.
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| CN108172804B (en) * | 2017-12-31 | 2020-09-08 | 中南大学 | Graphene/titanium dioxide coated positive electrode material and preparation and application thereof |
| CN110611964B (en) * | 2018-06-14 | 2022-05-24 | 浙江汉纳新材料科技有限公司 | Heating film material with PTC effect and preparation method thereof |
| CN109182822B (en) * | 2018-09-17 | 2020-07-14 | 南昌大学 | Die forging method of high-performance 7075 aluminum alloy |
| CN109182821B (en) * | 2018-09-17 | 2020-07-14 | 南昌大学 | Die casting method for graphene-reinforced ADC12 aluminum alloy |
| 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 |
| CN111446429B (en) * | 2020-03-27 | 2021-12-21 | 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101153084A (en) * | 2006-09-28 | 2008-04-02 | 万向电动汽车有限公司 | Polyalcohol microporous barrier for high ratio polyalcohol lithium ion power cell |
| CN102569761A (en) * | 2010-12-08 | 2012-07-11 | 中国科学院金属研究所 | Titanium dioxide/graphene nanocomposite material and preparation method and application thereof |
| CN104157833A (en) * | 2014-08-25 | 2014-11-19 | 厦门大学 | Graphene/titanium dioxide composite porous material, preparation method and application thereof |
| CN104624220A (en) * | 2015-02-10 | 2015-05-20 | 济南大学 | Preparation method of TiO2/rGO composite |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US8557441B2 (en) * | 2010-10-09 | 2013-10-15 | Battelle Memorial Institute | Titania-graphene anode electrode paper |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101153084A (en) * | 2006-09-28 | 2008-04-02 | 万向电动汽车有限公司 | Polyalcohol microporous barrier for high ratio polyalcohol lithium ion power cell |
| CN102569761A (en) * | 2010-12-08 | 2012-07-11 | 中国科学院金属研究所 | Titanium dioxide/graphene nanocomposite material and preparation method and application thereof |
| CN104157833A (en) * | 2014-08-25 | 2014-11-19 | 厦门大学 | Graphene/titanium dioxide composite porous material, preparation method and application thereof |
| CN104624220A (en) * | 2015-02-10 | 2015-05-20 | 济南大学 | Preparation method of TiO2/rGO composite |
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