CN104064735A - Lithium titanate-graphene-carbon nanotube composite material and preparation method and application thereof - Google Patents
Lithium titanate-graphene-carbon nanotube composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of a lithium titanate-graphene-carbon nanotube composite material. The preparation method is low in equipment requirement, simple in process, and easy to realize large-scale production. A suspension is obtained by ultrasonic mixing of graphene oxide, lithium titanate nanoparticles and carbon nanotubes; graphene oxide is reduced to graphene under the action of a reducing agent to obtain the lithium titanate-graphene-carbon nanotube composite material. The lithium titanate nanoparticles and carbon nanotubes are uniformly distributed in the lamellar structure of graphene; since graphene and carbon nanotubes have high conductivity and carbon nanotubes are long in long diameter, problems of poor cycle performance and rate capability of pure lithium titanate nanoparticles used as an electrode material are overcome effectively; meanwhile, lithium titanate is high in energy storage potential, is not liable to generate lithium dendrites when used as an electrode material; and lithium ion batteries prepared by the composite material has good cycle performance and stability.
Description
Technical field
The present invention relates to electrode material field, especially relate to a kind of lithium titanate-graphene-carbon nano tube composite material and its preparation method and application.
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 is mainly made up of positive pole, negative pole, barrier film and electrolyte four major parts.The two large topmost problems that tradition lithium ion battery faces are that stored energy capacitance is low and fail safe is not high, wherein fail safe is not high is mainly because lithium ion easily forms Li dendrite on negative material surface, when producing when a certain amount of, Li dendrite can pierce through barrier film, both positive and negative polarity is short-circuited, produce a large amount of heats, thereby make whole battery spontaneous combustion or blast.Forming Li dendrite in negative terminal surface is mainly lower the causing of charging potential due to negative material, when current potential approaches 0V vs Li/Li
+time, due to the existence of overpotential, be easy to cause lithium ion to be reduced completely, form Li dendrite.The negative material that tradition lithium ion battery uses is generally graphite.The theoretical capacity of graphite can reach 372mAh/g, but the energy storage current potential platform of graphite is lower, at 0～0.25V vs Li/Li
+between, thereby can cause the generation of Li dendrite, affect the performance of lithium ion battery.
Summary of the invention
Based on this, be necessary to provide a kind of and can effectively prevent lithium titanate-graphene-carbon nano tube composite material that Li dendrite produces and preparation method thereof while applying as lithium ion battery electrode material.
A preparation method for lithium titanate-graphene-carbon nano tube composite material, comprises the steps:
Graphite oxide is added in the mixed solvent of water and ethanol, after ultrasonic dispersion, make graphene oxide suspension;
In described graphene oxide suspension, add lithium titanate nano particle, after ultrasonic mixing, add again the carbon nano tube suspension of ultrasonic processing, obtain lithium titanate-graphene oxide-carbon nano tube suspension, wherein, the mass ratio of graphene oxide, lithium titanate and carbon nano-tube is 15～120:120:5～60;
In described lithium titanate-graphene oxide-carbon nano tube suspension, add reducing agent, and be heated to 90～130 DEG C, stirring reaction makes graphene oxide be reduced to Graphene, filters and wash the solid product obtaining, and obtains described lithium titanate-graphene-carbon nano tube composite material after oven dry.
In an embodiment, described graphite oxide prepares as follows therein:
Purity being not less than to 99.5% graphite is added in the mixed solution of the concentrated sulfuric acid and red fuming nitric acid (RFNA), at 0 DEG C, be uniformly mixed, in mixed solution, add potassium permanganate again, stirring reaction is tentatively oxidized graphite, reaction system is heated to 85 DEG C again and makes graphite complete oxidation, in the most backward reaction system, add hydrogenperoxide steam generator to remove excessive potassium permanganate, suction filtration, with watery hydrochloric acid and deionized water, the solids obtaining is washed successively, after being dried, obtain described graphite oxide.
Therein in an embodiment, the mass concentration of the described concentrated sulfuric acid is 98%, the mass concentration of described red fuming nitric acid (RFNA) is 65%, the mass fraction of described hydrogenperoxide steam generator is 30%, every gram of described graphite correspondence 85～95mL concentrated sulfuric acid, 24～25mL red fuming nitric acid (RFNA), 4～6g potassium permanganate and 6～10mL hydrogen peroxide.
In an embodiment, in described mixed solvent, the volume ratio of water and ethanol is 1～3:1 therein, and in described graphene oxide suspension, the concentration of graphene oxide is 0.5～1mg/mL.
Therein in an embodiment, the carbon nano tube suspension of described ultrasonic processing is the ultrasonic 4 hours concentration after treatment suspension of carbon nano-tube in water that is 1～20mg/mL.
In an embodiment, described reducing agent is sodium borohydride or hydrazine hydrate therein, and the mass ratio of described reducing agent and described graphene oxide is 9～48:15～120.
Therein in an embodiment, it is 200～300 revs/min that described stirring reaction makes graphene oxide be reduced to stir speed (S.S.) in the process of Graphene, and the stirring reaction time is 2 hours.
A kind of lithium titanate-graphene-carbon nano tube composite material that adopts the preparation method of above-mentioned lithium titanate-graphene-carbon nano tube composite material to prepare.
The preparation method of above-mentioned lithium titanate-graphene-carbon nano tube composite material is low for equipment requirements, technique simply, easily realizes large-scale production.By by graphene oxide and lithium titanate nano particle and the ultrasonic suspension that is mixed to get of carbon nano-tube, again under the effect of reducing agent, graphene oxide is reduced to Graphene, obtain lithium titanate-graphene-carbon nano tube composite material, lithium titanate nano particle and even carbon nanotube are dispersed in the lamellar structure of Graphene, because Graphene and carbon nano-tube have higher conductivity, and carbon nano-tube major diameter is longer, cycle performance and the poor problem of high rate performance can effectively overcome simple lithium titanate nano particle and make electrode material time, and the energy storage current potential of lithium titanate is higher, during as electrode material, be difficult for generating Li dendrite, make lithium ion battery cycle performance and stablize.
In addition, be also necessary to provide a kind of lithium ion battery that can effectively prevent Li dendrite generation and stable performance and preparation method thereof.
A kind of lithium ion battery, be included in positive plate, barrier film and the negative plate arranging in housing and be filled in the electrolyte in described housing, described barrier film is between described positive plate and described negative plate, described negative plate comprises collector and is coated in the electrode slurry on described collector, and described electrode slurry comprises the binding agent, conductive agent and the above-mentioned lithium titanate-graphene-carbon nano tube composite material that mix.
A preparation method for lithium ion battery, comprises the steps:
Above-mentioned lithium titanate-graphene-carbon nano tube composite material, binding agent are mixed with conductive agent, obtain electrode slurry;
Described electrode slurry is coated on collector, and dry rear section obtains negative plate;
Negative plate, barrier film and the setting of positive plate lamination are assembled into battery core, and described barrier film, between two described electrode slices, then is used battery core described in packaging shell, injects electrolyte, obtains described lithium ion battery.
Above-mentioned lithium ion battery is by using the lithium titanate-graphene-carbon nano tube composite material of multiplying power property and good cycle as electrode material, because the energy storage current potential of lithium titanate is higher, during as electrode material, be difficult for generating Li dendrite, make lithium ion battery cycle performance and stablize, and Graphene and carbon nano-tube have higher conductivity, carbon nano-tube major diameter is longer, cycle performance and the poor problem of high rate performance can also effectively overcome simple lithium titanate nano particle and make electrode material time, thereby the stable performance of lithium ion battery really.
Brief description of the drawings
Fig. 1 is preparation method's flow chart of the lithium titanate-graphene-carbon nano tube composite material of an execution mode;
Fig. 2 is preparation method's flow chart of the lithium ion battery of an execution mode.
Embodiment
Mainly in conjunction with the drawings and the specific embodiments lithium titanate-graphene-carbon nano tube composite material and preparation method thereof, lithium ion battery and preparation method thereof are described in further detail below.
As shown in Figure 1, the preparation method of the lithium titanate-graphene-carbon nano tube composite material of an execution mode, comprises the steps:
Step S110: graphite oxide is added in the mixed solvent of water and ethanol, make graphene oxide suspension after ultrasonic dispersion.
Graphite oxide used in present embodiment prepares as follows:
Purity being not less than to 99.5% graphite is added in the mixed solution of the concentrated sulfuric acid and red fuming nitric acid (RFNA), at 0 DEG C, be uniformly mixed, in mixed solution, add potassium permanganate again, stirring reaction is tentatively oxidized graphite, reaction system is heated to 85 DEG C again and makes graphite complete oxidation, in the most backward reaction system, add hydrogenperoxide steam generator to remove excessive potassium permanganate, suction filtration, with watery hydrochloric acid and deionized water, the solids obtaining is washed successively, after being dried, obtain graphite oxide.Further, in the present embodiment, the mass concentration of the concentrated sulfuric acid is 98%, and the mass concentration of red fuming nitric acid (RFNA) is 65%, the mass fraction of hydrogenperoxide steam generator is 30%, every gram of graphite correspondence 85～95mL concentrated sulfuric acid, 24～25mL red fuming nitric acid (RFNA), 4～6g potassium permanganate and 6～10mL hydrogen peroxide.
In mixed solvent, the volume ratio of water and ethanol is 1～3:1.In graphene oxide suspension, the concentration of graphene oxide is 0.5～1mg/mL.
Step S120: add lithium titanate nano particle in graphene oxide suspension, after ultrasonic mixing, add again the carbon nano tube suspension of ultrasonic processing, obtain lithium titanate-graphene oxide-carbon nano tube suspension, wherein, the mass ratio of graphene oxide, lithium titanate and carbon nano-tube is 15～120:120:5～60.
In the present embodiment, the particle diameter of lithium titanate nano particle is 20～50nm.In ultrasonic mixed process, ultrasonic power is 500～1000W, and ultrasonic time is 1 hour.The concentration of carbon nano tube suspension is 1～20mg/mL, and carbon nano tube suspension needed pre-ultrasonic processing 4 hours before adding,
Step S130: add reducing agent in lithium titanate-graphene oxide-carbon nano tube suspension, and be heated to 90～130 DEG C, stirring reaction makes graphene oxide be reduced to Graphene, filters and wash the solid product obtaining, and obtains lithium titanate-graphene-carbon nano tube composite material after oven dry.
In the present embodiment, reducing agent is sodium borohydride or hydrazine hydrate.The mass ratio of reducing agent and graphene oxide is 9～48:15～120, and further, the mass ratio of graphene oxide, lithium titanate, carbon nano-tube and reducing agent is 15～120:120:5～60:9～48.
In stirring reaction process, stir speed (S.S.) is 200～300 revs/min, and the stirring reaction time is 2 hours.
The preparation method of above-mentioned lithium titanate-graphene-carbon nano tube composite material is low for equipment requirements, technique simply, easily realizes large-scale production.By by graphene oxide and lithium titanate nano particle and the ultrasonic suspension that is mixed to get of carbon nano-tube, again under the effect of reducing agent, graphene oxide is reduced to Graphene, obtain lithium titanate-graphene-carbon nano tube composite material, lithium titanate nano particle and even carbon nanotube are dispersed in the lamellar structure of Graphene, because Graphene and carbon nano-tube have higher conductivity, and carbon nano-tube major diameter is longer, cycle performance and the poor problem of high rate performance can effectively overcome simple lithium titanate nano particle and make electrode material time, and the energy storage current potential of lithium titanate is higher, during as electrode material, be difficult for generating Li dendrite, make lithium ion battery cycle performance and stablize.
In addition, present embodiment also provides a kind of lithium ion battery that can effectively prevent Li dendrite generation and stable performance and preparation method thereof.
The lithium ion battery of one execution mode, be included in positive plate, barrier film and the negative plate arranging in housing and be filled in the electrolyte in housing, barrier film is between positive plate and negative plate, negative plate comprises collector and is coated in the electrode slurry on collector, and electrode slurry comprises the binding agent, conductive agent and the above-mentioned lithium titanate-graphene-carbon nano tube composite material that mix.
In the present embodiment, positive plate is lithium sheet.Electrolyte in electrolyte is LiPF
6, LiBF
4, LiTFSI (LiN (SO
2cF
3)
2) or LiFSI (LiN (SO
2f)
2), solvent adopts at least one in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate and acetonitrile, as LiPF
6/ dimethyl carbonate electrolyte, LiBF
4/ diethyl carbonate electrolyte, LiTFSI/ propene carbonate electrolyte or LiFSI/ ethylene carbonate/second cyanogen electrolyte etc.In electrolyte, electrolytical concentration is 1mol/L.Collector is Copper Foil, aluminium foil or nickel foil etc.Binding agent is the mixture of butadiene-styrene rubber and sodium carboxymethylcellulose.Conductive agent is acetylene black, active carbon or carbon black etc.The mass ratio of lithium titanate-graphene-carbon nano tube composite material, binding agent and conductive agent is 85:5:10.
As shown in Figure 2, the preparation method of above-mentioned lithium ion battery, comprises the steps:
Step S210: the preparation method according to above-mentioned lithium titanate-graphene-carbon nano tube composite material prepares lithium titanate-graphene-carbon nano tube composite material.
Step S220: lithium titanate-graphene-carbon nano tube composite material, binding agent are mixed with conductive agent, obtain electrode slurry.
Step S230: electrode slurry is coated on collector, and dry rear section obtains negative plate.
Step S240: negative plate, barrier film and the setting of positive plate lamination are assembled into battery core, and barrier film, between two electrode slices, then is used packaging shell battery core, injects electrolyte, obtains lithium ion battery.
Above-mentioned lithium ion battery is by using the lithium titanate-graphene-carbon nano tube composite material of multiplying power property and good cycle as electrode material, because the energy storage current potential of lithium titanate is higher, during as electrode material, be difficult for generating Li dendrite, make lithium ion battery cycle performance and stablize, and Graphene and carbon nano-tube have higher conductivity, carbon nano-tube major diameter is longer, cycle performance and the poor problem of high rate performance can also effectively overcome simple lithium titanate nano particle and make electrode material time, thereby the stable performance of lithium ion battery really.
Be below specific embodiment part:
Embodiment 1
The technological process of Graphene-hard carbon composite material prepared by the present embodiment is as follows: graphite → graphite oxide → lithium titanate-graphene-carbon nano tube composite material, and concrete preparation process is as follows:
(1) graphite: purity 99.5%.
(2) graphite oxide: take above-mentioned purity and be in the mixed solution that red fuming nitric acid (RFNA) that 99.5% the graphite 1g concentrated sulfuric acid that to add by 90mL mass fraction be 98% and 25mL mass fraction are 65% forms, mixed liquor is placed under frozen water mixing bath environment and is stirred 20 minutes, in mixed liquor, add 6g potassium permanganate at leisure again, stir 1 hour, then mixed liquor is heated to 85 ° of C and keeps 30 minutes, add afterwards 92mL deionized water to continue to keep 30 minutes under 85 ° of C, finally adding 10mL mass fraction is 30% hydrogenperoxide steam generator, stir 10 minutes to remove unreacted potassium permanganate, afterwards the mixture obtaining 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 for 12 hours in 60 ° of C vacuum drying ovens.
(3) graphene-carbon nano tube composite material: the graphite oxide of preparation in (2) is joined in the mixed solvent that volume ratio is 1:1 deionized water and ethanol, the concentration of graphite oxide in mixed solvent is 1mg/mL, the suspension of graphite oxide is carried out to ultrasonic processing, ultrasonic power is 500W, after 1 hour, stop ultrasonic, obtain the suspension of graphene oxide, be the lithium titanate particle of 20nm to adding particle diameter in suspension, lithium titanate nano particle 5mg/mL in mixed solvent, continue ultrasonic 1 hour, adding volume is the carbon nano tube suspension that the concentration of ultrasonic 4 hours of 10mL is 0.02mg/mL again, the mass ratio of graphene oxide and carbon nano-tube is 2:1, in mixed solution, add hydrazine hydrate again, the concentration of hydrazine hydrate is 0.5mg/mL, mixed solution is heated to 100 ° of C, stir 2 hours, stir speed (S.S.) is 200 revs/min, then filter, solid matter is placed on by deionized water washes clean in the vacuum drying oven of 60 ° of C and dries 12 hours, obtain lithium titanate-graphene-carbon nano tube composite material.
Embodiment 2
The technological process of Graphene-hard carbon composite material prepared by the present embodiment is as follows: graphite → graphite oxide → lithium titanate-graphene-carbon nano tube composite material, and concrete preparation process is as follows:
(1) graphite: purity 99.5%.
(2) graphite oxide: take above-mentioned purity and be in the mixed solution that red fuming nitric acid (RFNA) that 99.5% the graphite 1g concentrated sulfuric acid that to add by 95mL mass fraction be 98% and 24mL mass fraction are 65% forms, mixed liquor is placed under frozen water mixing bath environment and is stirred 20 minutes, in mixed liquor, add 4g potassium permanganate at leisure again, stir 1 hour, then mixed liquor is heated to 85 ° of C and keeps 30 minutes, add afterwards 92mL deionized water to continue to keep 30 minutes under 85 ° of C, finally adding 6mL mass fraction is 30% hydrogenperoxide steam generator, stir 10 minutes to remove unreacted potassium permanganate, afterwards the mixture obtaining 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 for 12 hours in 60 ° of C vacuum drying ovens.
(3) graphene-carbon nano tube composite material: the graphite oxide of preparation in (2) is joined in the mixed solvent that volume ratio is 2:1 deionized water and ethanol, the concentration of graphite oxide in mixed solvent is 0.5mg/mL, the suspension of graphite oxide is carried out to ultrasonic processing, ultrasonic power is 800W, after 1 hour, stop ultrasonic, obtain the suspension of graphene oxide, be the lithium titanate particle of 50nm to adding particle diameter in suspension, lithium titanate nano particle 4mg/mL in mixed solvent, continue ultrasonic 1 hour, adding volume is the carbon nano tube suspension that the concentration of ultrasonic 4 hours of 20mL is 0.1mg/mL again, the mass ratio of graphene oxide and carbon nano-tube is 3:1, in mixed solution, add hydrazine hydrate again, the concentration of hydrazine hydrate is 0.3mg/mL, mixed solution is heated to 120 ° of C, stir 2 hours, stir speed (S.S.) is 300 revs/min, then filter, solid matter is placed on by deionized water washes clean in the vacuum drying oven of 60 ° of C and dries 12 hours, obtain lithium titanate-graphene-carbon nano tube composite material.
Embodiment 3
The technological process of Graphene-hard carbon composite material prepared by the present embodiment is as follows: graphite → graphite oxide → lithium titanate-graphene-carbon nano tube composite material, and concrete preparation process is as follows:
(1) graphite: purity 99.5%.
(2) graphite oxide: take above-mentioned purity and be in the mixed solution that red fuming nitric acid (RFNA) that 99.5% the graphite 1g concentrated sulfuric acid that to add by 85mL mass fraction be 98% and 24mL mass fraction are 65% forms, mixed liquor is placed under frozen water mixing bath environment and is stirred 20 minutes, in mixed liquor, add 4g potassium permanganate at leisure again, stir 1 hour, then mixed liquor is heated to 85 ° of C and keeps 30 minutes, add afterwards 92mL deionized water to continue to keep 30 minutes under 85 ° of C, finally adding 8mL mass fraction is 30% hydrogenperoxide steam generator, stir 10 minutes to remove unreacted potassium permanganate, afterwards the mixture obtaining 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 for 12 hours in 60 ° of C vacuum drying ovens.
(3) graphene-carbon nano tube composite material: the graphite oxide of preparation in (2) is joined in the mixed solvent that volume ratio is 1:1 deionized water and ethanol, the concentration of graphite oxide in mixed solvent is 0.5mg/mL, the suspension of graphite oxide is carried out to ultrasonic processing, ultrasonic power is 1000W, after 1 hour, stop ultrasonic, obtain the suspension of graphene oxide, be the lithium titanate particle of 30nm to adding particle diameter in suspension, lithium titanate nano particle 1mg/mL in mixed solvent, continue ultrasonic 1 hour, adding volume is the carbon nano tube suspension that the concentration of ultrasonic 4 hours of 5mL is 2.4mg/mL again, the mass ratio of graphene oxide and carbon nano-tube is 3:1, in mixed solution, add hydrazine hydrate again, the concentration of hydrazine hydrate is 0.4mg/mL, mixed solution is heated to 90 ° of C, stir 2 hours, stir speed (S.S.) is 200 revs/min, then filter, solid matter is placed on by deionized water washes clean in the vacuum drying oven of 60 ° of C and dries 12 hours, obtain lithium titanate-graphene-carbon nano tube composite material.
Embodiment 4
The technological process of Graphene-hard carbon composite material prepared by the present embodiment is as follows: graphite → graphite oxide → lithium titanate-graphene-carbon nano tube composite material, and concrete preparation process is as follows:
(1) graphite: purity 99.5%.
(2) graphite oxide: take above-mentioned purity and be in the mixed solution that red fuming nitric acid (RFNA) that 99.5% the graphite 1g concentrated sulfuric acid that to add by 90mL mass fraction be 98% and 25mL mass fraction are 65% forms, mixed liquor is placed under frozen water mixing bath environment and is stirred 20 minutes, in mixed liquor, add 4g potassium permanganate at leisure again, stir 1 hour, then mixed liquor is heated to 85 ° of C and keeps 30 minutes, add afterwards 92mL deionized water to continue to keep 30 minutes under 85 ° of C, finally adding 9mL mass fraction is 30% hydrogenperoxide steam generator, stir 10 minutes to remove unreacted potassium permanganate, afterwards the mixture obtaining 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 for 12 hours in 60 ° of C vacuum drying ovens.
(3) graphene-carbon nano tube composite material: the graphite oxide of preparation in (2) is joined in the mixed solvent that volume ratio is 3:1 deionized water and ethanol, the concentration of graphite oxide in mixed solvent is 1mg/mL, the suspension of graphite oxide is carried out to ultrasonic processing, ultrasonic power is 500W, after 1 hour, stop ultrasonic, obtain the suspension of graphene oxide, be the lithium titanate particle of 40nm to adding particle diameter in suspension, lithium titanate nano particle 1mg/mL in mixed solvent, continue ultrasonic 1 hour, adding volume is the carbon nano tube suspension that the concentration of ultrasonic 4 hours of 10mL is 2.4mg/mL again, the mass ratio of graphene oxide and carbon nano-tube is 4:1, in mixed solution, add hydrazine hydrate again, the concentration of hydrazine hydrate is 0.3mg/mL, mixed solution is heated to 130 ° of C, stir 2 hours, stir speed (S.S.) is 200 revs/min, then filter, solid matter is placed on by deionized water washes clean in the vacuum drying oven of 60 ° of C and dries 12 hours, obtain lithium titanate-graphene-carbon nano tube composite material.
Embodiment 5
(1) ratio that is 85:5:10 according to mass ratio, the hybrid adhesive of lithium titanate-graphene-carbon nano tube composite material prepared by embodiment 1, butadiene-styrene rubber and sodium carboxymethylcellulose and conductive agent acetylene black mix, and obtain slurry;
(2) slurry is coated on Copper Foil, makes after drying slicing treatment, make the negative plate of lithium ion battery.
(3) using lithium sheet as positive plate, by the negative plate obtaining in lithium sheet, barrier film and (2) in order stack of laminations dress up battery core, then use housing seal battery core, subsequently toward LiPF that to be arranged on liquid injection port on housing be 1mol/mL toward implantation concentration in housing
6/ dimethyl carbonate electrolyte, sealing liquid injection port, obtains lithium ion battery.
Embodiment 6～8
Preparation method is with embodiment 5, just the negative material on negative plate is respectively the lithium titanate-graphene-carbon nano tube composite material of embodiment 2～4 preparations, electrolyte is respectively the LiBF4/ diethyl carbonate electrolyte of 1mol/L, the LiTFSI/ propene carbonate electrolyte of 1mol/L, LiFSI/ ethylene carbonate/acetonitrile electrolyte of 1mol/L, the collector adopting is respectively Copper Foil, nickel foil and aluminium foil, and the conductive agent of employing is respectively active carbon, carbon black and acetylene black.
Table 1 encloses for the lithium ion battery of embodiment 5～8 preparations carries out charge-discharge test the 2nd circle and the 501st under 0.1C electric current the stored energy capacitance obtaining, as follows:
Table 1
As can be seen from Table 1, after lithium ion battery circulation 500 circles prepared by lithium titanate-graphene-carbon nano tube composite material of employing embodiment 1～4, capability retention, all more than 85%, is up to 91%, has excellent cycle performance.
The lithium ion battery that table 2 is prepared for embodiment 5～8 carries out the stored energy capacitance of charge-discharge test under 0.1C and 2C electric current, as follows:
Table 2
As can be seen from Table 2, when the lithium ion battery that adopts lithium titanate-graphene-carbon nano tube composite material of embodiment 1～4 to prepare rises to 2C from 0.1C, capability retention, all more than 80%, is up to 85%, has excellent high rate performance.
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. a preparation method for lithium titanate-graphene-carbon nano tube composite material, is characterized in that, comprises the steps:
Graphite oxide is added in the mixed solvent of water and ethanol, after ultrasonic dispersion, make graphene oxide suspension;
In described graphene oxide suspension, add lithium titanate nano particle, after ultrasonic mixing, add again the carbon nano tube suspension of ultrasonic processing, obtain lithium titanate-graphene oxide-carbon nano tube suspension, wherein, the mass ratio of graphene oxide, lithium titanate and carbon nano-tube is 15～120:120:5～60;
In described lithium titanate-graphene oxide-carbon nano tube suspension, add reducing agent, and be heated to 90～130 DEG C, stirring reaction makes graphene oxide be reduced to Graphene, filters and wash the solid product obtaining, and obtains described lithium titanate-graphene-carbon nano tube composite material after oven dry.
2. the preparation method of lithium titanate-graphene-carbon nano tube composite material as claimed in claim 1, is characterized in that, described graphite oxide prepares as follows:
Purity being not less than to 99.5% graphite is added in the mixed solution of the concentrated sulfuric acid and red fuming nitric acid (RFNA), at 0 DEG C, be uniformly mixed, in mixed solution, add potassium permanganate again, stirring reaction is tentatively oxidized graphite, reaction system is heated to 85 DEG C again and makes graphite complete oxidation, in the most backward reaction system, add hydrogenperoxide steam generator to remove excessive potassium permanganate, suction filtration, with watery hydrochloric acid and deionized water, the solids obtaining is washed successively, after being dried, obtain described graphite oxide.
3. the preparation method of lithium titanate-graphene-carbon nano tube composite material as claimed in claim 2, it is characterized in that, the mass concentration of the described concentrated sulfuric acid is 98%, the mass concentration of described red fuming nitric acid (RFNA) is 65%, the mass fraction of described hydrogenperoxide steam generator is 30%, every gram of described graphite correspondence 85～95mL concentrated sulfuric acid, 24～25mL red fuming nitric acid (RFNA), 4～6g potassium permanganate and 6～10mL hydrogen peroxide.
4. the preparation method of lithium titanate-graphene-carbon nano tube composite material as claimed in claim 1, it is characterized in that, in described mixed solvent, the volume ratio of water and ethanol is 1～3:1, and in described graphene oxide suspension, the concentration of graphene oxide is 0.5～1mg/mL.
5. the preparation method of lithium titanate-graphene-carbon nano tube composite material as claimed in claim 1, it is characterized in that, the carbon nano tube suspension of described ultrasonic processing is the ultrasonic 4 hours concentration after treatment suspension of carbon nano-tube in water that is 1～20mg/mL.
6. the preparation method of lithium titanate-graphene-carbon nano tube composite material as claimed in claim 1, is characterized in that, described reducing agent is sodium borohydride or hydrazine hydrate, and the mass ratio of described reducing agent and described graphene oxide is 9～48:15～120.
7. the preparation method of lithium titanate-graphene-carbon nano tube composite material as claimed in claim 1, it is characterized in that, it is 200～300 revs/min that described stirring reaction makes graphene oxide be reduced to stir speed (S.S.) in the process of Graphene, and the stirring reaction time is 2 hours.
8. lithium titanate-graphene-carbon nano tube composite material that the preparation method of the lithium titanate-graphene-carbon nano tube composite material as described in any one in claim 1～7 prepares.
9. a lithium ion battery, be included in positive plate, barrier film and the negative plate arranging in housing and be filled in the electrolyte in described housing, described barrier film is between described positive plate and described negative plate, described negative plate comprises collector and is coated in the electrode slurry on described collector, it is characterized in that, described electrode slurry comprises the binding agent, conductive agent and the lithium titanate-graphene-carbon nano tube composite material as claimed in claim 8 that mix.
10. a preparation method for lithium ion battery, is characterized in that, comprises the steps:
Lithium titanate-graphene-carbon nano tube composite material claimed in claim 8, binding agent are mixed with conductive agent, obtain electrode slurry;
Described electrode slurry is coated on collector, and dry rear section obtains negative plate;
Negative plate, barrier film and the setting of positive plate lamination are assembled into battery core, and described barrier film, between two described electrode slices, then is used battery core described in packaging shell, injects electrolyte, obtains described lithium ion battery.
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