CN104064755A - Cobaltosic oxide-graphene-carbon nanotube composite material and preparation method and application thereof - Google Patents

Cobaltosic oxide-graphene-carbon nanotube composite material and preparation method and application thereof Download PDF

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CN104064755A
CN104064755A CN201310086366.0A CN201310086366A CN104064755A CN 104064755 A CN104064755 A CN 104064755A CN 201310086366 A CN201310086366 A CN 201310086366A CN 104064755 A CN104064755 A CN 104064755A
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graphene
oxide
carbon nano
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nano tube
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CN104064755B (en
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周明杰
钟辉
王要兵
刘大喜
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Shenzhen Oceans King Lighting Engineering Co Ltd
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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
    • 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
    • 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
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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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • 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
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    • H01M4/625—Carbon or graphite
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    • 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
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Abstract

The invention relates to a preparation method of a cobaltosic oxide-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 graphite oxide, cobalt hydroxide and carbon nanotubes; graphene oxide is reduced to graphene under a slow heating condition; cobalt hydroxide is pyrolyzed into cobaltosic oxide to obtain the cobaltosic oxide-graphene-carbon nanotube composite material. The cobaltosic oxide 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 cobaltosic oxide used as an electrode material are overcome effectively; meanwhile, cobaltosic oxide 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

Cobaltosic oxide-graphene-carbon nano tube composite material and its preparation method and application
Technical field
The present invention relates to electrode material field, especially relate to a kind of cobaltosic oxide-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 cobaltosic oxide-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 cobaltosic oxide-graphene-carbon nano tube composite material, comprises the steps:
Graphite oxide is added to the water, after ultrasonic dispersion, makes the suspension of graphite oxide;
In the suspension of described graphite oxide, add cobalt hydroxide, ultrasonicly mix and make graphite oxide to peel off into graphene oxide, add again carbon nano-tube, ultrasonic mixing, cobalt hydroxide-graphene oxide-the carbon nano tube suspension obtaining, wherein, the mass ratio of graphite oxide, cobalt hydroxide and carbon nano-tube is 10:4～20:1～10;
Described cobalt hydroxide-graphene oxide-carbon nano tube suspension is carried out to filtration treatment, after being dried, obtain cobalt hydroxide-graphene oxide-carbon nano tube compound material;
Described cobalt hydroxide-graphene oxide-carbon nano tube compound material is placed in to protective gas atmosphere; be heated to 500～700 DEG C with the rate of heat addition of 15～25 DEG C/min; and under final temperature, keep 0.5～2 hour; to make graphene oxide thermal reduction be Graphene and make cobalt hydroxide be decomposed into cobaltosic oxide, obtains described cobaltosic oxide-graphene-carbon nano tube composite material.
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 the suspension of described graphite oxide, the concentration of graphite oxide is 0.5～1mg/mL therein.
In an embodiment, the ultrasonic power in the ultrasonic mixed process of two steps is 500～800W therein, and ultrasonic time is 1～3 hour.
A kind of cobaltosic oxide-graphene-carbon nano tube composite material that adopts the preparation method of above-mentioned cobaltosic oxide-graphene-carbon nano tube composite material to prepare.
The preparation method of above-mentioned cobaltosic oxide-graphene-carbon nano tube composite material is low for equipment requirements, technique simply, easily realizes large-scale production.By by graphite oxide and cobalt hydroxide and the ultrasonic suspension that is mixed to get of carbon nano-tube, in the situation that slowly heating, graphene oxide is reduced to Graphene again, cobalt hydroxide pyrolysis is cobaltosic oxide, obtain cobaltosic oxide-graphene-carbon nano tube composite material, cobaltosic oxide nano 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 cobaltosic oxide and make electrode material time, and the energy storage current potential of cobaltosic oxide 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 cobaltosic oxide-graphene-carbon nano tube composite material that mix.
In an embodiment, the electrolyte in described electrolyte is LiPF therein 6, LiBF 4, LiTFSI or LiFSI, solvent adopts at least one in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate and acetonitrile, and in electrolyte, electrolytical concentration is 1mol/L.
In an embodiment, described positive plate is lithium sheet therein; Described collector is Copper Foil, aluminium foil or nickel foil; Described binding agent is the mixture of butadiene-styrene rubber and sodium carboxymethylcellulose; Described conductive agent is acetylene black, active carbon or carbon black; The mass ratio of described cobaltosic oxide-graphene-carbon nano tube composite material, described binding agent and described conductive agent is 85:5:10.
A preparation method for lithium ion battery, comprises the steps:
Above-mentioned cobaltosic oxide-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
Above-mentioned lithium ion battery is by using the cobaltosic oxide-graphene-carbon nano tube composite material of multiplying power property and good cycle as electrode material, because the energy storage current potential of cobaltosic oxide 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 cobaltosic oxide 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 cobaltosic oxide-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 cobaltosic oxide-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 cobaltosic oxide-graphene-carbon nano tube composite material of an execution mode, comprises the steps:
Step S110: graphite oxide is added to the water, makes the suspension of graphite oxide 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 the suspension of graphite oxide, the concentration of graphite oxide is 0.5～1mg/mL.
Step S120: add cobalt hydroxide in the suspension of graphite oxide, ultrasonicly mix and make graphite oxide to peel off into graphene oxide, add again carbon nano-tube, ultrasonic mixing, cobalt hydroxide-graphene oxide-the carbon nano tube suspension obtaining, wherein, the mass ratio of graphite oxide, cobalt hydroxide and carbon nano-tube is 10:4～20:1～10.
Ultrasonic power in the ultrasonic mixed process of two steps is 500～800W, and ultrasonic time is 1～3 hour.
Step S130: cobalt hydroxide-graphene oxide-carbon nano tube suspension is carried out to filtration treatment, obtain cobalt hydroxide-graphene oxide-carbon nano tube compound material after being dried.
Step S140: cobalt hydroxide-graphene oxide-carbon nano tube compound material is placed in to protective gas atmosphere; be heated to 500～700 DEG C with the rate of heat addition of 15～25 DEG C/min; and under final temperature, keep 0.5～2 hour; to make graphene oxide thermal reduction be Graphene and make cobalt hydroxide be decomposed into cobaltosic oxide, obtains cobaltosic oxide-graphene-carbon nano tube composite material.
The preparation method of above-mentioned cobaltosic oxide-graphene-carbon nano tube composite material is low for equipment requirements, technique simply, easily realizes large-scale production.By by graphite oxide and cobalt hydroxide and the ultrasonic suspension that is mixed to get of carbon nano-tube, in the situation that slowly heating, graphene oxide is reduced to Graphene again, cobalt hydroxide pyrolysis is cobaltosic oxide, obtain cobaltosic oxide-graphene-carbon nano tube composite material, cobaltosic oxide nano 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 cobaltosic oxide and make electrode material time, and the energy storage current potential of cobaltosic oxide 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 cobaltosic oxide-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.Binding agent is the mixture of butadiene-styrene rubber and sodium carboxymethylcellulose.Conductive agent is acetylene black, active carbon or carbon black.The mass ratio of cobaltosic oxide-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 cobaltosic oxide-graphene-carbon nano tube composite material prepares cobaltosic oxide-graphene-carbon nano tube composite material.
Step S220: cobaltosic oxide-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 cobaltosic oxide-graphene-carbon nano tube composite material of multiplying power property and good cycle as electrode material, because the energy storage current potential of cobaltosic oxide 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 cobaltosic oxide 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 → cobalt hydroxide-graphene oxide-carbon nano tube compound material → cobaltosic oxide-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) cobalt hydroxide-graphene oxide-carbon nano tube compound material: the graphite oxide obtaining in (2) is dispersed in water, the graphite oxide suspension that preparation concentration is 0.5mg/mL, in graphite oxide suspension, add cobalt hydroxide again, the final concentration of cobalt hydroxide in mixed liquor is 0.2mg/mL, with the ultrasonic power of 800W ultrasonic 2 hours, make graphite oxide peel off generation graphene oxide, and cobalt hydroxide is dispersed in graphene oxide, adding a certain amount of carbon nano-tube to make the final concentration of carbon nano-tube in mixed liquor is 0.5mg/mL again, continuation ultrasonic 2 hours with the ultrasonic power of 800W, filter, solid product is placed in to dry 12 hours of the vacuum drying oven that temperature is 60 ° of C, obtain cobalt hydroxide-graphene oxide-carbon nano tube compound material,
(4) cobaltosic oxide-graphene-carbon nano tube composite material: it is under the argon atmosphere of 300mL/ minute that the cobalt hydroxide-graphene oxide-carbon nano tube compound material of preparation in (3) is placed in to flow velocity, with 20 ° of heating rates of C/ minute, the ambient temperature of mixture is risen to 600 ° of C, keeping making for 1 hour in graphene oxide oxygen-containing functional group generation pyrolysis to be reduced to Graphene and to make cobalt hydroxide pyrolysis is cobaltosic oxide, then the argon atmosphere that is 300mL/ minute at flow velocity drops to room temperature, obtains cobaltosic oxide-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 → cobalt hydroxide-graphene oxide-carbon nano tube compound material → cobaltosic oxide-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) cobalt hydroxide-graphene oxide-carbon nano tube compound material: the graphite oxide obtaining in (2) is dispersed in water, the graphite oxide suspension that preparation concentration is 1mg/mL, in graphite oxide suspension, add cobalt hydroxide again, the final concentration of cobalt hydroxide in mixed liquor is 0.5mg/mL, with the ultrasonic power of 500W ultrasonic 3 hours, make graphite oxide peel off generation graphene oxide, and cobalt hydroxide is dispersed in graphene oxide, adding a certain amount of carbon nano-tube to make the final concentration of carbon nano-tube in mixed liquor is 0.5mg/mL again, continuation ultrasonic 3 hours with the ultrasonic power of 500W, filter, solid product is placed in to dry 12 hours of the vacuum drying oven that temperature is 60 ° of C, obtain cobalt hydroxide-graphene oxide-carbon nano tube compound material,
(4) cobaltosic oxide-graphene-carbon nano tube composite material: it is under the argon atmosphere of 200mL/ minute that the cobalt hydroxide-graphene oxide-carbon nano tube compound material of preparation in (3) is placed in to flow velocity, with 15 ° of heating rates of C/ minute, the ambient temperature of mixture is risen to 500 ° of C, keeping making for 2 hours in graphene oxide oxygen-containing functional group generation pyrolysis to be reduced to Graphene and to make cobalt hydroxide pyrolysis is cobaltosic oxide, then the argon atmosphere that is 200mL/ minute at flow velocity drops to room temperature, obtains cobaltosic oxide-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 → cobalt hydroxide-graphene oxide-carbon nano tube compound material → cobaltosic oxide-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) cobalt hydroxide-graphene oxide-carbon nano tube compound material: the graphite oxide obtaining in (2) is dispersed in water, the graphite oxide suspension that preparation concentration is 0.5mg/mL, in graphite oxide suspension, add cobalt hydroxide again, the final concentration of cobalt hydroxide in mixed liquor is 0.5mg/mL, with the ultrasonic power of 500W ultrasonic 3 hours, make graphite oxide peel off generation graphene oxide, and cobalt hydroxide is dispersed in graphene oxide, adding a certain amount of carbon nano-tube to make the final concentration of carbon nano-tube in mixed liquor is 0.1mg/mL again, continuation ultrasonic 3 hours with the ultrasonic power of 500W, filter, solid product is placed in to dry 12 hours of the vacuum drying oven that temperature is 60 ° of C, obtain cobalt hydroxide-graphene oxide-carbon nano tube compound material,
(4) cobaltosic oxide-graphene-carbon nano tube composite material: it is under the argon atmosphere of 300mL/ minute that the cobalt hydroxide-graphene oxide-carbon nano tube compound material of preparation in (3) is placed in to flow velocity, with 25 ° of heating rates of C/ minute, the ambient temperature of mixture is risen to 700 ° of C, keeping making for 0.5 hour in graphene oxide oxygen-containing functional group generation pyrolysis to be reduced to Graphene and to make cobalt hydroxide pyrolysis is cobaltosic oxide, then the argon atmosphere that is 300mL/ minute at flow velocity drops to room temperature, obtains cobaltosic oxide-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 → cobalt hydroxide-graphene oxide-carbon nano tube compound material → cobaltosic oxide-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) cobalt hydroxide-graphene oxide-carbon nano tube compound material: the graphite oxide obtaining in (2) is dispersed in water, the graphite oxide suspension that preparation concentration is 0.5mg/mL, in graphite oxide suspension, add cobalt hydroxide again, the final concentration of cobalt hydroxide in mixed liquor is 1mg/mL, with the ultrasonic power of 800W ultrasonic 1 hour, make graphite oxide peel off generation graphene oxide, and cobalt hydroxide is dispersed in graphene oxide, adding a certain amount of carbon nano-tube to make the final concentration of carbon nano-tube in mixed liquor is 0.05mg/mL again, continuation ultrasonic 1 hour with the ultrasonic power of 800W, filter, solid product is placed in to dry 12 hours of the vacuum drying oven that temperature is 60 ° of C, obtain cobalt hydroxide-graphene oxide-carbon nano tube compound material,
(4) cobaltosic oxide-graphene-carbon nano tube composite material: it is under the argon atmosphere of 300mL/ minute that the cobalt hydroxide-graphene oxide-carbon nano tube compound material of preparation in (3) is placed in to flow velocity, with 20 ° of heating rates of C/ minute, the ambient temperature of mixture is risen to 500 ° of C, keeping making for 1 hour in graphene oxide oxygen-containing functional group generation pyrolysis to be reduced to Graphene and to make cobalt hydroxide pyrolysis is cobaltosic oxide, then the argon atmosphere that is 300mL/ minute at flow velocity drops to room temperature, obtains cobaltosic oxide-graphene-carbon nano tube composite material.
Embodiment 5
(1) ratio that is 85:5:10 according to mass ratio, the hybrid adhesive of cobaltosic oxide-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, and just the negative material on negative plate is respectively the cobaltosic oxide-graphene-carbon nano tube composite material of embodiment 2～4 preparations, and electrolyte is respectively the LiBF of 1mol/L 4the LiTFSI/ propene carbonate electrolyte of/diethyl carbonate electrolyte, 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 cobaltosic oxide-graphene-carbon nano tube composite material of employing embodiment 1～4, capability retention, all more than 85%, is up to 93%, 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 cobaltosic oxide-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 90%, 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 cobaltosic oxide-graphene-carbon nano tube composite material, is characterized in that, comprises the steps:
Graphite oxide is added to the water, after ultrasonic dispersion, makes the suspension of graphite oxide;
In the suspension of described graphite oxide, add cobalt hydroxide, ultrasonicly mix and make graphite oxide to peel off into graphene oxide, add again carbon nano-tube, ultrasonic mixing, cobalt hydroxide-graphene oxide-the carbon nano tube suspension obtaining, wherein, the mass ratio of graphite oxide, cobalt hydroxide and carbon nano-tube is 10:4～20:1～10;
Described cobalt hydroxide-graphene oxide-carbon nano tube suspension is carried out to filtration treatment, after being dried, obtain cobalt hydroxide-graphene oxide-carbon nano tube compound material;
Described cobalt hydroxide-graphene oxide-carbon nano tube compound material is placed in to protective gas atmosphere; be heated to 500～700 DEG C with the rate of heat addition of 15～25 DEG C/min; and under final temperature, keep 0.5～2 hour; to make graphene oxide thermal reduction be Graphene and make cobalt hydroxide be decomposed into cobaltosic oxide, obtains described cobaltosic oxide-graphene-carbon nano tube composite material.
2. the preparation method of cobaltosic oxide-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 cobaltosic oxide-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 cobaltosic oxide-graphene-carbon nano tube composite material as claimed in claim 1, is characterized in that, in the suspension of described graphite oxide, the concentration of graphite oxide is 0.5～1mg/mL.
5. the preparation method of cobaltosic oxide-graphene-carbon nano tube composite material as claimed in claim 1, is characterized in that, the ultrasonic power in the ultrasonic mixed process of two steps is 500～800W, and ultrasonic time is 1～3 hour.
6. cobaltosic oxide-graphene-carbon nano tube composite material that the preparation method of the employing cobaltosic oxide-graphene-carbon nano tube composite material as described in any one in claim 1～5 prepares.
7. 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 cobaltosic oxide-graphene-carbon nano tube composite material as claimed in claim 6 that mix.
8. lithium ion battery as claimed in claim 7, is characterized in that, the electrolyte in described electrolyte is LiPF 6, LiBF 4, LiTFSI or LiFSI, solvent adopts at least one in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate and acetonitrile, and in described electrolyte, electrolytical concentration is 1mol/L.
9. lithium ion battery as claimed in claim 7, is characterized in that, described positive plate is lithium sheet; Described collector is Copper Foil, aluminium foil or nickel foil; Described binding agent is the mixture of butadiene-styrene rubber and sodium carboxymethylcellulose; Described conductive agent is acetylene black, active carbon or carbon black; The mass ratio of described cobaltosic oxide-graphene-carbon nano tube composite material, described binding agent and described conductive agent is 85:5:10.
10. a preparation method for lithium ion battery, is characterized in that, comprises the steps:
Cobaltosic oxide-graphene-carbon nano tube composite material claimed in claim 6, 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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