CN103490040A - Preparation method of lithium titanate-graphene composite material - Google Patents
Preparation method of lithium titanate-graphene composite material Download PDFInfo
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
A preparation method of a lithium titanate-graphene composite material comprises following steps: providing a lithium source and a titanium source, preparing graphene; dissolving the lithium source and the titanium source in a solvent, adding deionized water and acetic acid into the solvent, then adding the graphene so as to obtain a mixed solution containing the lithium source, the titanium source, and the graphene; subjecting the mixed solution containing the lithium source, the titanium source, and the graphene to a centrifugal treatment so as to obtain a solid product, drying the solid product, and then processing the dried solid product for 5 to 10 minutes at the temperature of 800 to 900 DEG C in vacuum so as to obtain the lithium titanate-graphene composite material. Through mixing the precursor of lithium titanate, namely the lithium source and the titanium source, with graphene, and then subjecting the mixture to a heat treatment, the method obtains the lithium titanate-graphene composite material by an in-situ composite method, the in-situ composite method makes the lithium titanate to disperse more evenly in the graphene, and to have a stronger adhesive force, and thus if the lithium titanate-graphene composite material prepared by the method is taken as the negative electrode material of a lithium battery, the rate performance and circulation performance of the lithium battery are prominently improved.
Description
Technical field
The present invention relates to the lithium ion battery negative material preparation field, particularly relate to a kind of preparation method of lithium titanate-graphene composite material.
Background technology
Lithium ion battery is as a kind of novel energy-storing device, and lot of domestic and international scientific research institution and enterprise fall over each other research.It mainly is comprised of positive pole, negative pole, barrier film and electrolyte four major parts.Current lithium ion battery faces stored energy capacitance and hangs down and the large topmost problem of fail safe not high two, and wherein fail safe is not high mainly causes because lithium ion easily forms Li dendrite on the negative material surface.Can pierce through barrier film when Li dendrite produces when a certain amount of, make both positive and negative polarity be short-circuited, short circuit produces a large amount of heats, thereby makes whole battery spontaneous combustion or blast.Forming Li dendrite in negative terminal surface is mainly due to the charging potential of negative material low causing, when current potential approaches 0V vs Li/Li+, due to the existence of overpotential, is easy to cause lithium ion to be reduced fully, forms Li dendrite.The negative material that commercial lithium-ion batteries is used at present is generally graphite, because its theoretical capacity has 372mAh/g, but its energy storage current potential platform is lower, and between 0 ~ 0.25V vs Li/Li+, this tends to cause the generation of Li dendrite.Adopt lithium titanate as negative material, its energy storage current potential platform is 1.55V vs Li/Li+, can avoid the generation of Li dendrite fully.But lithium titanate is as the negative material of lithium battery, and multiplying power property and the cycle performance of lithium battery are poor, these 2 weak points have seriously restricted lithium titanate and have carried out commercial applications.
Graphene is a kind of two-dimentional monolayer material, there is higher conductance, mix a certain amount of Graphene in lithium titanate, form a conductive network, this conductive network is very beneficial for improving high rate performance and the cycle performance of lithium titanate as lithium ion battery negative material.At present, lithium titanate is directly mixed with Graphene by certain method with lithium titanate with the compound great majority of Graphene, this simple mechanical mixture, lithium titanate mixes even not with Graphene, and adhesive force a little less than, can not give full play to the conductivity advantages of higher of Graphene, thereby multiplying power property and the cycle performance of the lithium battery of use lithium titanate-graphene composite material are not high, still can not meet the commercialization demand of lithium titanate-graphene composite material.
Summary of the invention
Based on this, be necessary to provide a kind of preparation method of lithium titanate-graphene composite material of the adhesive force that can improve lithium titanate and Graphene.
A kind of preparation method of lithium titanate-graphene composite material, comprise the steps:
,Tai source, lithium source is provided, and prepares Graphene;
He Tai source, described lithium source is dissolved in same solvent successively, adds deionized water and acetic acid, then add described Graphene, obtain the mixed liquor that contains ,Tai source, lithium source and Graphene;
The described mixed liquor that contains ,Tai source, lithium source and Graphene is carried out centrifugal, obtain solid product, described solid product drying is placed under vacuum condition, process under 800 ~ 900 ℃ 5 ~ 10 minutes, obtain lithium titanate-graphene composite material.
In embodiment, described lithium source is lithium acetate therein, and described titanium source is butyl titanate.
In embodiment, prepared by described Graphene as follows therein:
Graphite is provided;
Described graphite is added in the mixed acid of the concentrated sulfuric acid and red fuming nitric acid (RFNA), add potassium permanganate stir 10 ~ 30 minutes in the frozen water mixing is bathed after, then the mixed solution of described graphite, mixed acid and potassium permanganate is heated to 80 ~ 90 ℃, and keep 15 ~ 30 minutes, finally add hydrogen peroxide to stir 10 ~ 30 minutes, suction filtration, washing, drying, obtain graphite oxide;
Described graphite oxide is placed in to atmosphere of inert gases, is warming up to 300 ~ 500 ℃, keep obtaining in 0.5 ~ 2 hour Graphene.
In embodiment, the ratio of described graphite, the concentrated sulfuric acid, red fuming nitric acid (RFNA) and potassium permanganate is 1g:85 ~ 95ml:24 ~ 25ml:4 ~ 6g therein; The ratio of described potassium permanganate and hydrogen peroxide is 1g:1 ~ 3ml.
In embodiment, described washing step is to adopt respectively watery hydrochloric acid and deionized water to be washed therein, and described drying steps is 60 ~ 100 ℃ of lower vacuumizes 12 ~ 24 hours.
Therein in embodiment, the described heating rate that is warming up to the step of 300 ~ 500 ℃ be 20 ~ 30 ℃/per minute.
In embodiment, described solvent is isopropyl alcohol therein.
In embodiment, the mol ratio in He Li source, described titanium source is 1 ~ 6:2 ~ 8 therein.
In embodiment, the volume ratio of described solvent, deionized water and acetic acid is 40 ~ 100:10 ~ 30:6 ~ 20 therein, and the mass ratio in described Graphene, He Tai source, lithium source is 3 ~ 5:132 ~ 528:340 ~ 2040.
Therein in embodiment, it is that centrifugal force with 75000 ~ 80000g carries out centrifugal 3 ~ 10 minutes that ,Tai source, described lithium source and Graphene mixed liquor carry out centrifugal step.
The preparation method of above-mentioned lithium titanate-graphene composite material, by the presoma by lithium titanate, be He Tai source, lithium source and heat-treat after Graphene is mixed, compound lithium titanate-the graphene composite material that obtains of original position, the compound method of this original position makes lithium titanate disperse more evenly in Graphene, adhesive force is stronger, thereby lithium titanate-graphene composite material prepared by the method can significantly improve high rate performance and the cycle performance of lithium battery as the negative material of lithium battery.
The accompanying drawing explanation
The preparation method's of lithium titanate-graphene composite material that Fig. 1 is an execution mode process chart.
Embodiment
Below by embodiment and accompanying drawing, the preparation method to above-mentioned lithium titanate-graphene composite material further sets forth.
Refer to Fig. 1, the preparation method of the lithium titanate-graphene composite material of an execution mode, comprise the steps:
Step S110: ,Tai source, lithium source is provided, and prepares Graphene.
The lithium source is lithium acetate.The titanium source is butyl titanate.He Tai source, lithium source is as the presoma of lithium titanate.The mol ratio in He Tai source, lithium source is 1 ~ 6:2 ~ 8.
Prepared by the following method by Graphene:
(1) provide graphite.The graphite that preferably purity is 99.%.
(2) graphite is added in the mixed acid of the concentrated sulfuric acid and red fuming nitric acid (RFNA), add potassium permanganate stir 10 ~ 30 minutes in the frozen water mixing is bathed after, then the mixed solution of graphite, mixed acid and potassium permanganate is heated to 80-90 ℃, and keep 15 ~ 30 minutes, finally add the hydrogen peroxide stirring reaction 10 ~ 30 minutes, suction filtration, washing, drying, obtain graphite oxide.
The concentrated sulfuric acid adopts the sulfuric acid that mass fraction is 98%, and red fuming nitric acid (RFNA) adopts the nitric acid that mass fraction is 65%, and it is 30% hydrogen peroxide that hydrogen peroxide adopts mass fraction.The ratio of graphite, the concentrated sulfuric acid, red fuming nitric acid (RFNA) and potassium permanganate is 1g:85 ~ 95ml:24 ~ 25ml:4 ~ 6g; The ratio of potassium permanganate and hydrogen peroxide is 1g:1 ~ 3ml.
After the mixed solution of graphite, mixed acid and potassium permanganate keeps 15 ~ 30 minutes under 80 ~ 90 ℃, add hydrogen peroxide, stir 10 ~ 30 minutes to remove potassium permanganate, carry out suction filtration and obtain solids, advance to wash solids with watery hydrochloric acid and deionized water successively again, wash altogether three times, then this solids is obtained to graphite oxide in 12 ~ 24 hours 60 ~ 100 ℃ of lower vacuumizes.
(3) graphite oxide is placed in to atmosphere of inert gases, is warming up to 300 ~ 500 ℃, keep obtaining in 0.5 ~ 2 hour Graphene.
Inert gas can be argon gas, helium etc., and the flow velocity of inert gas is 200 ~ 400mL/ minute.
Heating rate be preferably 20 ~ 30 ℃/per minute.Graphite oxide keeps carrying out the oxygen-containing functional group that the graphite oxide interlayer is removed in pyrolysis in 0.5 ~ 2 hour under 300 ~ 500 ℃, obtains Graphene.
Step S120: He Tai source, lithium source is dissolved in same solvent successively, adds deionized water and acetic acid, then add Graphene, obtain the mixed liquor that contains ,Tai source, lithium source and Graphene.
Solvent is isopropyl alcohol.Lithium acetate and butyl titanate are soluble in isopropyl alcohol.The volume ratio of solvent, deionized water and acetic acid is 40 ~ 100:10 ~ 30:6 ~ 20.The mass ratio in Graphene, He Tai source, lithium source is 3 ~ 5:132 ~ 528:340 ~ 2040.
Step S130: the mixed liquor that will contain ,Tai source, lithium source and Graphene carries out centrifugal, obtains solid product, and the solid product drying is placed under vacuum condition, under 800 ~ 900 ℃, processes 5 ~ 10 minutes, obtains lithium titanate-graphene composite material.
The mixed liquor that preferably, will contain ,Tai source, lithium source and Graphene carries out centrifugal 3 ~ 10 minutes at the centrifugal force of 75000 ~ 80000g.Carry out ultrahigh speed at the centrifugal force at 75000 ~ 80000g centrifugal, ,Tai source, lithium source and Graphene is tightly compacted, be conducive to improve the tack of follow-up lithium titanate and Graphene.
Obtain solid product after centrifugal, this solid product is obtained to dry solid product in 60 ℃ of lower vacuumizes after 15 ~ 24 hours.Dry solid product is placed under vacuum condition, processes under 800 ~ 900 ℃ 5 ~ 10 minutes, the precursor in situ reaction of lithium titanate obtains lithium titanate, the compound lithium titanate-graphene composite material that obtains of lithium titanate and Graphene.
The preparation method of this lithium titanate-graphene composite material passes through the presoma of lithium titanate, be He Tai source, lithium source and heat-treat after Graphene is mixed, compound lithium titanate-the graphene composite material that obtains of original position, the compound method of this original position makes lithium titanate disperse more evenly in Graphene, adhesive force is stronger, thereby lithium titanate-graphene composite material prepared by the method can significantly improve high rate performance and the cycle performance of lithium battery as the negative material of lithium battery.
Than the general method that prepared by lithium titanate and Graphene mechanical mixture to lithium titanate-graphene composite material, the preparation method's of this lithium titanate-graphene composite material lithium titanate mixes more even with Graphene, can give full play to advantage and the high advantage of Graphene conductivity that lithium titanate energy storage current potential platform is high, can greatly improve specific capacity and the conductive capability of lithium titanate-graphene composite material, lithium titanate-graphene composite material prepared by the method, as the negative material of lithium battery, can improve the performance of lithium battery greatly.
And equipment, technique that this preparation method requires are simple, easily realize large-scale production.
Lithium titanate-graphene composite material prepared by this preparation method can significantly improve the performance of lithium ion battery for lithium ion battery.Concrete application process is as follows:
At first, according to mass ratio 85:5:10, lithium titanate-graphene composite material, Kynoar binding agent and conductive agent acetylene black are mixed, obtain cathode size;
Secondly, cathode size is coated on Copper Foil, drying, slicing treatment, make the lithium ion cell electrode negative plate;
Finally, using the lithium sheet as to the electrode anode sheet, by lithium sheet, barrier film, lithium titanate-graphene composite material electrode negative plate in order stack of laminations dress up battery core, use again battery housing seal battery core, inject electrolyte toward the liquid injection port be arranged on battery container in battery container subsequently, the sealing liquid injection port, obtain lithium ion battery.
Electrolyte in electrolyte adopts lithium ion battery electrolyte lithium hexafluoro phosphate (LiPF commonly used
6), LiBF4 (LiBF
4), two (trifluoromethane sulfonic acid acyl) imine lithium (LiTFSI or LiN (SO
2cF
3)
2), two (fluorine sulphonyl) imine lithium (LiFSI or LiN (SO
2f)
2) etc., solvent adopts one or more mixing in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate, acetonitrile, and electrolytical concentration is generally 1mol/L.
It is below specific embodiment.
Embodiment 1
Technological process by graphite → graphite oxide → Graphene → lithium titanate-graphene composite material prepares lithium titanate-graphene composite material.
(1) provide the graphite that purity is 99.5%;
(2) prepare graphite oxide: take the graphite 1g that (1) moderate purity is 99.5% and add in the mixed acid formed by the 90mL concentrated sulfuric acid (mass fraction is 98%) and 25mL red fuming nitric acid (RFNA) (mass fraction is 65%), graphite and the mixture of mixed acid are placed in to frozen water to be mixed to bathe under environment and is stirred 20 minutes, add 6g potassium permanganate at leisure in mixture again, stir 1 hour, then mixture is heated to 85 ℃ and keep 30 minutes, add afterwards the 92mL deionized water to continue to keep 20 minutes under 85 ℃, finally add 10mL hydrogenperoxide steam generator (mass fraction 30%), stir 10 minutes, mixture is carried out to suction filtration, with 100mL watery hydrochloric acid and 150mL deionized water, solids is washed respectively successively again, wash altogether three times, last solid matter is the dry graphite oxide that obtains in 24 hours in 60 ℃ of vacuum drying ovens,
(3) prepare Graphene: the graphite oxide obtained in (2) is placed in to argon gas (flow velocity: 400mL/ minute) under atmosphere, with the heating rates of 25 ℃/minute, the temperature around graphite oxide is risen to 500 ℃, keep 1 hour, then at argon gas, (flow velocity: 400mL/ minute) atmosphere drops to room temperature, obtains Graphene;
(4) prepare lithium titanate-graphene composite material: 4mol butyl titanate, 5mol lithium acetate are added in the 50mL isopropyl alcohol successively, add again 10mL deionized water and 10mL acetic acid, and then the Graphene (5g) of preparation in (3) is added in above-mentioned mixed solution, mixed solution is carried out to 75000g centrifugal, after centrifugal 10 minutes, remove supernatant, solid product is placed in to 60 ℃ of vacuum drying ovens to be dried 15 hours, afterwards solid matter is placed in to vacuum environment, process 10 minutes under 900 ℃, obtain lithium titanate-graphene composite material.
Embodiment 2
Technological process by graphite → graphite oxide → Graphene → lithium titanate-graphene composite material prepares lithium titanate-graphene composite material.
(1) provide the graphite that purity is 99.5%;
(2) prepare graphite oxide: take the graphite 1g that (1) moderate purity is 99.5% and add in the mixed solution formed by the 95mL concentrated sulfuric acid (mass fraction is 98%) and 24mL red fuming nitric acid (RFNA) (mass fraction is 65%), mixture is placed under frozen water mixing bath environment and is stirred 30 minutes, add 4g potassium permanganate at leisure in mixture again, stir 1 hour, then mixture is heated to 85 ℃ and keep 30 minutes, add afterwards the 92mL deionized water to continue to keep 10 minutes under 90 ℃, finally add 6mL hydrogenperoxide steam generator (mass fraction 30%), stir 20 minutes, mixture is carried out to suction filtration, with 100mL watery hydrochloric acid and 150mL deionized water, solids is washed respectively successively again, wash altogether three times, last solid matter is the dry graphite oxide that obtains in 12 hours in 100 ℃ of vacuum drying ovens,
(3) prepare Graphene: the graphite oxide obtained in (2) is placed in to argon gas (flow velocity: 200mL/ minute) under atmosphere, with the heating rates of 30 ℃/minute, the temperature around graphite oxide is risen to 400 ℃, keep 2 hours, then at argon gas, (flow velocity: 200mL/ minute) atmosphere drops to room temperature, obtains Graphene;
(4) prepare lithium titanate-graphene composite material: 6mol butyl titanate, 8mol lithium acetate are added in the 80mL isopropyl alcohol successively, add again 20mL deionized water and 15mL acetic acid, and then the Graphene (5g) of preparation in (3) is added in above-mentioned mixed solution, mixed solution is carried out to 80000g centrifugal, after centrifugal 5 minutes, remove supernatant, solid product is placed in to 60 ℃ of vacuum drying ovens to be dried 24 hours, afterwards solid matter is placed in to vacuum environment, process 20 minutes under 800 ℃, obtain lithium titanate-graphene composite material.
Embodiment 3
Technological process by graphite → graphite oxide → Graphene → lithium titanate-graphene composite material prepares lithium titanate-graphene composite material.
(1) provide the graphite that purity is 99.5%;
(2) prepare graphite oxide: take the graphite 1g that (1) moderate purity is 99.5% and add in the mixed solution formed by the 85mL concentrated sulfuric acid (mass fraction is 98%) and 24mL red fuming nitric acid (RFNA) (mass fraction is 65%), mixture is placed under frozen water mixing bath environment and is stirred 20 minutes, add 6g potassium permanganate at leisure in mixture again, stir 1 hour, then mixture is heated to 85 ℃ and keep 30 minutes, add afterwards the 92mL deionized water to continue to keep 30 minutes under 80 ℃, finally add 8mL hydrogenperoxide steam generator (mass fraction 30%), stir 30 minutes, mixture is carried out to suction filtration, with 100mL watery hydrochloric acid and 150mL deionized water, solids is washed respectively successively again, wash altogether three times, last solid matter is the dry graphite oxide that obtains in 18 hours in 80 ℃ of vacuum drying ovens,
(3) prepare Graphene: the graphite oxide obtained in (2) is placed in to argon gas (flow velocity: 400mL/ minute) under atmosphere, with the heating rates of 20 ℃/minute, the temperature around graphite oxide is risen to 300 ℃, keep 1 hour, then at argon gas, (flow velocity: 400mL/ minute) atmosphere drops to room temperature, obtains Graphene;
(4) prepare lithium titanate-graphene composite material: 2mol butyl titanate, 4mol lithium acetate are added in the 40mL isopropyl alcohol successively, add again 10mL deionized water and 6mL acetic acid, and then the Graphene (6g) of preparation in (3) is added in above-mentioned mixed solution, mixed solution is carried out to 75000g centrifugal, after centrifugal 8min, remove supernatant, solid product is placed in to 60 ℃ of vacuum drying ovens to be dried 15 hours, afterwards solid matter is placed in to vacuum environment, process 30 minutes under 800 ℃, obtain lithium titanate-graphene composite material.
Embodiment 4
Technological process by graphite → graphite oxide → Graphene → lithium titanate-graphene composite material prepares lithium titanate-graphene composite material.
(1) provide the graphite that purity is 99.5%;
(2) prepare graphite oxide: take the graphite 1g that (1) moderate purity is 99.5% and add in the mixed solution formed by the 90mL concentrated sulfuric acid (mass fraction is 98%) and 25mL red fuming nitric acid (RFNA) (mass fraction is 65%), mixture is placed under frozen water mixing bath environment and is stirred 20 minutes, add 6g potassium permanganate at leisure in mixture again, stir 1 hour, then mixture is heated to 85 ℃ and keep 30 minutes, add afterwards the 92mL deionized water to continue to keep 30 minutes under 85 ℃, finally add 9mL hydrogenperoxide steam generator (mass fraction 30%), stir 10 minutes, mixture is carried out to suction filtration, with 100mL watery hydrochloric acid and 150mL deionized water, solids is washed respectively successively again, wash altogether three times, last solid matter is the dry graphite oxide that obtains in 20 hours in 70 ℃ of vacuum drying ovens,
(3) prepare Graphene: the graphite oxide obtained in (2) is placed in to argon gas (flow velocity: 400mL/ minute) under atmosphere, with the heating rates of 20 ℃/minute, the temperature around graphite oxide is risen to 500 ℃, keep 0.5 hour, then at argon gas, (flow velocity: 400mL/ minute) atmosphere drops to room temperature, obtains Graphene;
(4) prepare lithium titanate-graphene composite material: 10mol butyl titanate, 15mol lithium acetate are added in the 100mL isopropyl alcohol successively, add again 30mL deionized water and 20mL acetic acid, and then the Graphene (15g) of preparation in (3) is added in above-mentioned mixed solution, mixed solution is carried out to 70000g centrifugal, after centrifugal 3min, remove supernatant, solid product is placed in to 60 ℃ of vacuum drying ovens to be dried 15 hours, afterwards solid matter is placed in to vacuum environment, process 5 minutes under 900 ℃, obtain lithium titanate-graphene composite material.
Table 1 embodiment 1 ~ 4 key process parameter
Embodiment 5
The application of the lithium titanate-graphene composite material of embodiment 1 preparation
(1) be that 85:5:10 mixes lithium titanate-graphene composite material, Kynoar binding agent and the conductive agent acetylene black of embodiment 1 preparation according to mass ratio, obtain cathode size;
(2) slurry is coated on the Copper Foil paper tinsel, drying, slicing treatment, make the lithium ion cell electrode negative plate;
(3) using the lithium sheet as to the electrode anode sheet, by electrode negative plate of obtaining in lithium sheet, barrier film, (2) in order stack of laminations dress up battery core, use again battery housing seal battery core, subsequently toward being arranged on liquid injection port on battery container toward the LiPF that injects 1mol/L in battery container
6/ dimethyl carbonate electrolyte, the sealing liquid injection port, obtain lithium ion battery.
Embodiment 6
The application of the lithium titanate-graphene composite material of embodiment 2 preparations
(1) be that 85:5:10 mixes lithium titanate-graphene composite material, Kynoar binding agent and the conductive agent acetylene black of embodiment 2 preparations according to mass ratio, obtain cathode size;
(2) slurry is coated on the Copper Foil paper tinsel, drying, slicing treatment, make the lithium ion cell electrode negative plate;
(3) using the lithium sheet as to the electrode anode sheet, by electrode negative plate of obtaining in lithium sheet, barrier film, (2) in order stack of laminations dress up battery core, use again battery housing seal battery core, subsequently toward being arranged on liquid injection port on battery container toward the LiBF that injects 1mol/L in battery container
4/ diethyl carbonate electrolyte, the sealing liquid injection port, obtain lithium ion battery.
Embodiment 7
The application of the lithium titanate-graphene composite material of embodiment 3 preparations
(1) be that 85:5:10 mixes lithium titanate-graphene composite material, Kynoar binding agent and the conductive agent acetylene black of embodiment 3 preparations according to mass ratio, obtain cathode size;
(2) slurry is coated on the Copper Foil paper tinsel, drying, slicing treatment, make the lithium ion cell electrode negative plate;
(3) using the lithium sheet as to the electrode anode sheet, by electrode negative plate of obtaining in lithium sheet, barrier film, (2) in order stack of laminations dress up battery core, use again battery housing seal battery core, subsequently toward being arranged on liquid injection port on battery container toward the LiTFSI/ propene carbonate electrolyte that injects 1mol/L in battery container, the sealing liquid injection port, obtain lithium ion battery.
Embodiment 8
The application of the lithium titanate-graphene composite material of embodiment 4 preparations
(1) be that 85:5:10 mixes lithium titanate-graphene composite material, Kynoar binding agent and the conductive agent acetylene black of embodiment 4 preparations according to mass ratio, obtain cathode size;
(2) slurry is coated on the Copper Foil paper tinsel, drying, slicing treatment, make the lithium ion cell electrode negative plate;
(3) using the lithium sheet as to the electrode anode sheet, by electrode negative plate of obtaining in lithium sheet, barrier film, (2) in order stack of laminations dress up battery core, use again battery housing seal battery core, subsequently toward being arranged on liquid injection port on battery container toward the LiFSI/ ethylene carbonate that injects 1mol/L in battery container+acetonitrile electrolyte, the sealing liquid injection port, obtain lithium ion battery.
The lithium ion battery that table 2 is embodiment 5 ~ 8 carries out charge-discharge test the 2nd circle and the 301st and encloses the stored energy capacitance obtained under the 0.1C electric current
As shown in Table 2, capability retention all more than 80% after the lithium titanate that adopts this method to prepare-graphene composite material circulation 300 circles, the highlyest approach 90%, higher than lithium titanate at present as the capability retention of negative material.
The lithium ion battery that table 3 is embodiment 5 ~ 8 carries out the stored energy capacitance of charge-discharge test under 0.1C and 2C electric current
As shown in Table 3, when the lithium titanate-graphene composite material that adopts this method to prepare rises to 2C from 0.1C, capability retention all, more than 89%, is up to 92.4%, the multiplying power property higher than current lithium titanate as negative material.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. the preparation method of a lithium titanate-graphene composite material, is characterized in that, comprises the steps:
,Tai source, lithium source is provided, and prepares Graphene;
He Tai source, described lithium source is dissolved in same solvent successively, adds deionized water and acetic acid, then add described Graphene, obtain the mixed liquor that contains ,Tai source, lithium source and Graphene;
The described mixed liquor that contains ,Tai source, lithium source and Graphene is carried out centrifugal, obtain solid product, described solid product drying is placed under vacuum condition, process under 800 ~ 900 ℃ 5 ~ 10 minutes, obtain lithium titanate-graphene composite material.
2. the preparation method of lithium titanate-graphene composite material according to claim 1, is characterized in that, described lithium source is lithium acetate, and described titanium source is butyl titanate.
3. the preparation method of lithium titanate-graphene composite material according to claim 1, is characterized in that, prepared as follows by described Graphene:
Graphite is provided;
Described graphite is added in the mixed acid of the concentrated sulfuric acid and red fuming nitric acid (RFNA), add potassium permanganate stir 10 ~ 30 minutes in the frozen water mixing is bathed after, then the mixed solution of described graphite, mixed acid and potassium permanganate is heated to 80 ~ 90 ℃, and keep 15 ~ 30 minutes, finally add hydrogen peroxide to stir 10 ~ 30 minutes, suction filtration, washing, drying, obtain graphite oxide;
Described graphite oxide is placed in to atmosphere of inert gases, is warming up to 300 ~ 500 ℃, keep obtaining in 0.5 ~ 2 hour Graphene.
4. the preparation method of lithium titanate-graphene composite material according to claim 3, is characterized in that, the ratio of described graphite, the concentrated sulfuric acid, red fuming nitric acid (RFNA) and potassium permanganate is 1g:85 ~ 95ml:24 ~ 25ml:4 ~ 6g; The ratio of described potassium permanganate and hydrogen peroxide is 1g:1 ~ 3ml.
5. the preparation method of lithium titanate-graphene composite material according to claim 3, is characterized in that, described washing step is to adopt respectively watery hydrochloric acid and deionized water to be washed, and described drying steps is 60 ~ 100 ℃ of lower vacuumizes 12 ~ 24 hours.
6. the preparation method of lithium titanate-graphene composite material according to claim 3, is characterized in that, the described heating rate that is warming up to the step of 300 ~ 500 ℃ be 20 ~ 30 ℃/per minute.
7. the preparation method of lithium titanate-graphene composite material according to claim 1, is characterized in that, described solvent is isopropyl alcohol.
8. the preparation method of lithium titanate-graphene composite material according to claim 1, is characterized in that, the mol ratio in He Li source, described titanium source is 1 ~ 6:2 ~ 8.
9. the preparation method of lithium titanate-graphene composite material according to claim 1, it is characterized in that, the volume ratio of described solvent, deionized water and acetic acid is 40 ~ 100:10 ~ 30:6 ~ 20, and the mass ratio in described Graphene, He Tai source, lithium source is 3 ~ 5:132 ~ 528:340 ~ 2040.
10. the preparation method of lithium titanate-graphene composite material according to claim 1, is characterized in that, it is that centrifugal force with 75000 ~ 80000g carries out centrifugal 3 ~ 10 minutes that ,Tai source, described lithium source and Graphene mixed liquor carry out centrifugal step.
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| CN104577046A (en) * | 2014-12-31 | 2015-04-29 | 江苏江大环保科技开发有限公司 | Application of graphene/lithium titanate composite |
| CN104907018A (en) * | 2015-05-25 | 2015-09-16 | 齐鲁工业大学 | Three-dimensional titanic acid/graphene oxide composite gel, and preparation method thereof |
| CN105206810A (en) * | 2015-09-16 | 2015-12-30 | 宁波南车新能源科技有限公司 | Nanometer lithium titanate composite and preparation method thereof |
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| CN115050961A (en) * | 2022-06-17 | 2022-09-13 | 苏州易来科得科技有限公司 | Lithium battery negative coating composition, preparation method of negative pole piece and lithium battery |
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| CN104907018A (en) * | 2015-05-25 | 2015-09-16 | 齐鲁工业大学 | Three-dimensional titanic acid/graphene oxide composite gel, and preparation method thereof |
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| CN105720268A (en) * | 2016-04-08 | 2016-06-29 | 辽宁大学 | Lithium ion battery anode material and preparation method of lithium ion battery anode material |
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| CN111392766B (en) * | 2019-11-13 | 2022-11-08 | 中国人民解放军军事科学院防化研究院 | Method for preparing nano lithium titanate/graphene porous composite electrode material |
| CN115050961A (en) * | 2022-06-17 | 2022-09-13 | 苏州易来科得科技有限公司 | Lithium battery negative coating composition, preparation method of negative pole piece and lithium battery |
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