CN104064755B - Cobaltosic oxide-graphene-carbon nano tube composite material and its preparation method and application - Google Patents

Cobaltosic oxide-graphene-carbon nano tube composite material and its preparation method and application Download PDF

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CN104064755B
CN104064755B CN201310086366.0A CN201310086366A CN104064755B CN 104064755 B CN104064755 B CN 104064755B CN 201310086366 A CN201310086366 A CN 201310086366A CN 104064755 B CN104064755 B CN 104064755B
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graphene
carbon nano
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composite material
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CN104064755A (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 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
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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
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    • Y02E60/10—Energy storage using batteries
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Abstract

The present invention relates to a kind of preparation method of cobaltosic oxide-graphene-carbon nano tube composite material.This preparation method is low for equipment requirements, technique simply, easily realizes large-scale production.By by graphite oxide and cobalt hydroxide and carbon nano-tube is ultrasonic is mixed to get suspension, when 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, effectively can overcome the problem of cycle performance and high rate performance difference when simple cobaltosic oxide makes electrode material, and the energy storage current potential of cobaltosic oxide is higher, not easily Li dendrite is generated as during electrode material, make lithium ion battery cycle performance and stablize.

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 primarily of the most of composition of positive pole, negative pole, barrier film and electrolyte four.The two large topmost problems that conventional lithium ion battery faces are that stored energy capacitance is low and fail safe is not high, wherein fail safe is not high mainly because lithium ion easily forms Li dendrite on negative material surface, barrier film can be pierced through when Li dendrite produces a certain amount of, both positive and negative polarity is short-circuited, produce a large amount of heats, thus make whole battery spontaneous combustion or blast.Form in negative terminal surface that Li dendrite mainly causes because the charging potential of negative material is lower, when current potential is close to 0VvsLi/Li +time, due to the existence of overpotential, be easy to cause lithium ion to be completely reduced, form Li dendrite.The negative material that conventional lithium ion battery uses is generally graphite.The theoretical capacity of graphite can reach 372mAh/g, but the energy storage potential plateau of graphite is lower, at 0 ~ 0.25VvsLi/Li +between, thus 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 cobaltosic oxide-graphene-carbon nano tube composite material that can effectively prevent Li dendrite from producing when applying as lithium ion battery electrode material and preparation method thereof.
A preparation method for cobaltosic oxide-graphene-carbon nano tube composite material, comprises the steps:
Graphite oxide is added to the water, the suspension of obtained graphite oxide after ultrasonic disperse;
Cobalt hydroxide is added in the suspension of described graphite oxide, ultrasonicly mix and make graphite oxide peel off into graphene oxide, add carbon nano-tube again, ultrasonicly to mix, cobalt hydroxide-graphene oxide-the carbon nano tube suspension obtained, wherein, the mass ratio of graphite oxide, cobalt hydroxide and carbon nano-tube is 10:4 ~ 20:1 ~ 10;
Filtration treatment is carried out to described cobalt hydroxide-graphene oxide-carbon nano tube suspension, after drying, obtains cobalt hydroxide-graphene oxide-carbon nano tube compound material;
Described cobalt hydroxide-graphene oxide-carbon nano tube compound material is placed in protective gas atmosphere; with heating rate to 500 ~ 700 DEG C of 15 ~ 25 DEG C/min; and keep 0.5 ~ 2 hour at the final temperature; make graphene oxide thermal reduction be Graphene and make cobalt hydroxide be decomposed into cobaltosic oxide, obtaining described cobaltosic oxide-graphene-carbon nano tube composite material.
Wherein in an embodiment, described graphite oxide prepares as follows:
Graphite purity being not less than 99.5% is added in the mixed solution of the concentrated sulfuric acid and red fuming nitric acid (RFNA), be uniformly mixed at 0 DEG C, potassium permanganate is added again in mixed solution, stirring reaction makes graphite preliminary oxidation, reaction system is heated to 85 DEG C again and makes graphite complete oxidation, add hydrogenperoxide steam generator in the most backward reaction system and remove excessive potassium permanganate, suction filtration, with watery hydrochloric acid and deionized water, the solids obtained is washed successively, after drying, obtain described graphite oxide.
Wherein 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.
Wherein in an embodiment, in the suspension of described graphite oxide, the concentration of graphite oxide is 0.5 ~ 1mg/mL.
Wherein in an embodiment, the ultrasonic power in the ultrasonic mixed process of two steps is 500 ~ 800W, and ultrasonic time is 1 ~ 3 hour.
A kind of cobaltosic oxide-graphene-carbon nano tube composite material adopting 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 carbon nano-tube is ultrasonic is mixed to get suspension, when 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, effectively can overcome the problem of cycle performance and high rate performance difference when simple cobaltosic oxide makes electrode material, and the energy storage current potential of cobaltosic oxide is higher, not easily Li dendrite is generated as during electrode material, make lithium ion battery cycle performance and stablize.
In addition, there is a need to provide a kind of Li dendrite that can effectively prevent to produce and lithium ion battery of stable performance and preparation method thereof.
A kind of lithium ion battery, be included in the positive plate, barrier film and the negative plate that arrange in housing and the electrolyte be filled 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 of mixing, conductive agent and above-mentioned cobaltosic oxide-graphene-carbon nano tube composite material.
Wherein in an embodiment, 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 electrolyte, electrolytical concentration is 1mol/L.
Wherein in an embodiment, 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.
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, obtains electrode slurry;
By described electrode slurry coating on a current collector, after dry, section obtains negative plate;
Negative plate, barrier film and positive plate lamination are arranged and be assembled into battery core, described barrier film between two described electrode slices, then uses 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, not easily Li dendrite is generated as during electrode material, make lithium ion battery cycle performance and stablize, and Graphene and carbon nano-tube have higher conductivity, carbon nano-tube major diameter is longer, effectively can also overcome the problem of cycle performance and high rate performance difference when simple cobaltosic oxide makes electrode material, thus the stable performance of lithium ion battery really.
Accompanying drawing explanation
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, the suspension of obtained graphite oxide after ultrasonic disperse.
Graphite oxide used in present embodiment prepares as follows:
Graphite purity being not less than 99.5% is added in the mixed solution of the concentrated sulfuric acid and red fuming nitric acid (RFNA), be uniformly mixed at 0 DEG C, potassium permanganate is added again in mixed solution, stirring reaction makes graphite preliminary oxidation, reaction system is heated to 85 DEG C again and makes graphite complete oxidation, add hydrogenperoxide steam generator in the most backward reaction system and remove excessive potassium permanganate, suction filtration, with watery hydrochloric acid and deionized water, the solids obtained is washed successively, after drying, 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 peel off into graphene oxide, add carbon nano-tube again, ultrasonicly to mix, cobalt hydroxide-graphene oxide-the carbon nano tube suspension obtained, 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: carry out filtration treatment to cobalt hydroxide-graphene oxide-carbon nano tube suspension, obtains cobalt hydroxide-graphene oxide-carbon nano tube compound material after drying.
Step S140: cobalt hydroxide-graphene oxide-carbon nano tube compound material is placed in protective gas atmosphere; with heating rate to 500 ~ 700 DEG C of 15 ~ 25 DEG C/min; and keep 0.5 ~ 2 hour at the final temperature; make graphene oxide thermal reduction be Graphene and make cobalt hydroxide be decomposed into cobaltosic oxide, obtaining 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 carbon nano-tube is ultrasonic is mixed to get suspension, when 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, effectively can overcome the problem of cycle performance and high rate performance difference when simple cobaltosic oxide makes electrode material, and the energy storage current potential of cobaltosic oxide is higher, not easily Li dendrite is generated as during electrode material, make lithium ion battery cycle performance and stablize.
In addition, present embodiment additionally provide a kind of can effectively prevent Li dendrite produce and lithium ion battery of stable performance and preparation method thereof.
The lithium ion battery of one execution mode, be included in the positive plate, barrier film and the negative plate that arrange in housing and the electrolyte be filled in housing, barrier film is between positive plate and negative plate, negative plate comprises collector and coating electrode slurry on a current collector, and electrode slurry comprises the binding agent of mixing, conductive agent and above-mentioned cobaltosic oxide-graphene-carbon nano tube composite material.
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: prepare cobaltosic oxide-graphene-carbon nano tube composite material according to the preparation method of above-mentioned 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, obtains electrode slurry.
Step S230: by electrode slurry coating on a current collector, after dry, section obtains negative plate.
Step S240: negative plate, barrier film and positive plate lamination are arranged and be assembled into battery core, barrier film between two electrode slices, then uses 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, not easily Li dendrite is generated as during electrode material, make lithium ion battery cycle performance and stablize, and Graphene and carbon nano-tube have higher conductivity, carbon nano-tube major diameter is longer, effectively can also overcome the problem of cycle performance and high rate performance difference when simple cobaltosic oxide makes electrode material, thus 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 be 99.5% graphite 1g add by 90mL mass fraction be 98% the concentrated sulfuric acid and 25mL mass fraction be in the mixed solution that forms of red fuming nitric acid (RFNA) of 65%, stirring is carried out 20 minutes under mixed liquor being placed in frozen water mixing bath environment, 6g potassium permanganate is added at leisure again in mixed liquor, stir 1 hour, then mixed liquor be heated to 85 ° of C and keep 30 minutes, add 92mL deionized water afterwards to continue to keep 30 minutes under 85 ° of C, finally add the hydrogenperoxide steam generator that 10mL mass fraction is 30%, stir 10 minutes to remove unreacted potassium permanganate, afterwards suction filtration is carried out to the mixture obtained, with 100mL watery hydrochloric acid and 150mL deionized water, solids is washed respectively successively again, wash three times altogether, last solid matter is dry in 60 ° of C vacuum drying ovens obtains graphite oxide in 12 hours.
(3) cobalt hydroxide-graphene oxide-carbon nano tube compound material: the graphite oxide obtained in (2) is dispersed in water, preparation concentration is the graphite oxide suspension of 0.5mg/mL, cobalt hydroxide is added again in graphite oxide suspension, the final concentration of cobalt hydroxide in mixed liquor is 0.2mg/mL, with the ultrasonic power of 800W ultrasonic 2 hours, graphite oxide is made to occur to peel off generation graphene oxide, and make cobalt hydroxide be dispersed in graphene oxide, adding the final concentration that a certain amount of carbon nano-tube makes carbon nano-tube in mixed liquor is again 0.5mg/mL, continuation ultrasonic 2 hours with the ultrasonic power of 800W, filter, solid product is placed in 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: the cobalt hydroxide-graphene oxide-carbon nano tube compound material of preparation in (3) being placed in flow velocity is under the argon atmosphere of 300mL/ minute, with 20 ° of heating rates of C/ minute, the ambient temperature of mixture is risen to 600 ° of C, keep within 1 hour, making oxygen-containing functional group generation pyrolysis reduction in graphene oxide be Graphene and making cobalt hydroxide pyrolysis be cobaltosic oxide, then the argon atmosphere being 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 be 99.5% graphite 1g add by 95mL mass fraction be 98% the concentrated sulfuric acid and 24mL mass fraction be in the mixed solution that forms of red fuming nitric acid (RFNA) of 65%, stirring is carried out 20 minutes under mixed liquor being placed in frozen water mixing bath environment, 4g potassium permanganate is added at leisure again in mixed liquor, stir 1 hour, then mixed liquor be heated to 85 ° of C and keep 30 minutes, add 92mL deionized water afterwards to continue to keep 30 minutes under 85 ° of C, finally add the hydrogenperoxide steam generator that 6mL mass fraction is 30%, stir 10 minutes to remove unreacted potassium permanganate, afterwards suction filtration is carried out to the mixture obtained, with 100mL watery hydrochloric acid and 150mL deionized water, solids is washed respectively successively again, wash three times altogether, last solid matter is dry in 60 ° of C vacuum drying ovens obtains graphite oxide in 12 hours.
(3) cobalt hydroxide-graphene oxide-carbon nano tube compound material: the graphite oxide obtained in (2) is dispersed in water, preparation concentration is the graphite oxide suspension of 1mg/mL, cobalt hydroxide is added again in graphite oxide suspension, the final concentration of cobalt hydroxide in mixed liquor is 0.5mg/mL, with the ultrasonic power of 500W ultrasonic 3 hours, graphite oxide is made to occur to peel off generation graphene oxide, and make cobalt hydroxide be dispersed in graphene oxide, adding the final concentration that a certain amount of carbon nano-tube makes carbon nano-tube in mixed liquor is again 0.5mg/mL, continuation ultrasonic 3 hours with the ultrasonic power of 500W, filter, solid product is placed in 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: the cobalt hydroxide-graphene oxide-carbon nano tube compound material of preparation in (3) being placed in flow velocity is under the argon atmosphere of 200mL/ minute, with 15 ° of heating rates of C/ minute, the ambient temperature of mixture is risen to 500 ° of C, keep within 2 hours, making oxygen-containing functional group generation pyrolysis reduction in graphene oxide be Graphene and making cobalt hydroxide pyrolysis be cobaltosic oxide, then the argon atmosphere being 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 be 99.5% graphite 1g add by 85mL mass fraction be 98% the concentrated sulfuric acid and 24mL mass fraction be in the mixed solution that forms of red fuming nitric acid (RFNA) of 65%, stirring is carried out 20 minutes under mixed liquor being placed in frozen water mixing bath environment, 4g potassium permanganate is added at leisure again in mixed liquor, stir 1 hour, then mixed liquor be heated to 85 ° of C and keep 30 minutes, add 92mL deionized water afterwards to continue to keep 30 minutes under 85 ° of C, finally add the hydrogenperoxide steam generator that 8mL mass fraction is 30%, stir 10 minutes to remove unreacted potassium permanganate, afterwards suction filtration is carried out to the mixture obtained, with 100mL watery hydrochloric acid and 150mL deionized water, solids is washed respectively successively again, wash three times altogether, last solid matter is dry in 60 ° of C vacuum drying ovens obtains graphite oxide in 12 hours.
(3) cobalt hydroxide-graphene oxide-carbon nano tube compound material: the graphite oxide obtained in (2) is dispersed in water, preparation concentration is the graphite oxide suspension of 0.5mg/mL, cobalt hydroxide is added again in graphite oxide suspension, the final concentration of cobalt hydroxide in mixed liquor is 0.5mg/mL, with the ultrasonic power of 500W ultrasonic 3 hours, graphite oxide is made to occur to peel off generation graphene oxide, and make cobalt hydroxide be dispersed in graphene oxide, adding the final concentration that a certain amount of carbon nano-tube makes carbon nano-tube in mixed liquor is again 0.1mg/mL, continuation ultrasonic 3 hours with the ultrasonic power of 500W, filter, solid product is placed in 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: the cobalt hydroxide-graphene oxide-carbon nano tube compound material of preparation in (3) being placed in flow velocity is under the argon atmosphere of 300mL/ minute, with 25 ° of heating rates of C/ minute, the ambient temperature of mixture is risen to 700 ° of C, keep within 0.5 hour, making oxygen-containing functional group generation pyrolysis reduction in graphene oxide be Graphene and making cobalt hydroxide pyrolysis be cobaltosic oxide, then the argon atmosphere being 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 be 99.5% graphite 1g add by 90mL mass fraction be 98% the concentrated sulfuric acid and 25mL mass fraction be in the mixed solution that forms of red fuming nitric acid (RFNA) of 65%, stirring is carried out 20 minutes under mixed liquor being placed in frozen water mixing bath environment, 4g potassium permanganate is added at leisure again in mixed liquor, stir 1 hour, then mixed liquor be heated to 85 ° of C and keep 30 minutes, add 92mL deionized water afterwards to continue to keep 30 minutes under 85 ° of C, finally add the hydrogenperoxide steam generator that 9mL mass fraction is 30%, stir 10 minutes to remove unreacted potassium permanganate, afterwards suction filtration is carried out to the mixture obtained, with 100mL watery hydrochloric acid and 150mL deionized water, solids is washed respectively successively again, wash three times altogether, last solid matter is dry in 60 ° of C vacuum drying ovens obtains graphite oxide in 12 hours.
(3) cobalt hydroxide-graphene oxide-carbon nano tube compound material: the graphite oxide obtained in (2) is dispersed in water, preparation concentration is the graphite oxide suspension of 0.5mg/mL, cobalt hydroxide is added again in graphite oxide suspension, the final concentration of cobalt hydroxide in mixed liquor is 1mg/mL, with the ultrasonic power of 800W ultrasonic 1 hour, graphite oxide is made to occur to peel off generation graphene oxide, and make cobalt hydroxide be dispersed in graphene oxide, adding the final concentration that a certain amount of carbon nano-tube makes carbon nano-tube in mixed liquor is again 0.05mg/mL, continuation ultrasonic 1 hour with the ultrasonic power of 800W, filter, solid product is placed in 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: the cobalt hydroxide-graphene oxide-carbon nano tube compound material of preparation in (3) being placed in flow velocity is under the argon atmosphere of 300mL/ minute, with 20 ° of heating rates of C/ minute, the ambient temperature of mixture is risen to 500 ° of C, keep within 1 hour, making oxygen-containing functional group generation pyrolysis reduction in graphene oxide be Graphene and making cobalt hydroxide pyrolysis be cobaltosic oxide, then the argon atmosphere being 300mL/ minute at flow velocity drops to room temperature, obtains cobaltosic oxide-graphene-carbon nano tube composite material.
Embodiment 5
(1) be the ratio of 85:5:10 according to mass ratio, hybrid adhesive and the conductive agent acetylene black of cobaltosic oxide-graphene-carbon nano tube composite material, butadiene-styrene rubber and the sodium carboxymethylcellulose embodiment 1 prepared mix, and obtain slurry;
(2) slurry is coated on Copper Foil, makes slicing treatment after drying, the negative plate of obtained lithium ion battery.
(3) using lithium sheet as positive plate, by the negative plate obtained in lithium sheet, barrier film and (2) in order stack of laminations dress up battery core, then use housing seal battery core, toward the liquid injection port be arranged on housing, in housing, implantation concentration is the LiPF of 1mol/mL subsequently 6/ dimethyl carbonate electrolyte, sealing liquid injection port, obtains lithium ion battery.
Embodiment 6 ~ 8
Preparation method is with embodiment 5, and the negative material just on negative plate is respectively cobaltosic oxide-graphene-carbon nano tube composite material prepared by embodiment 2 ~ 4, and electrolyte is the LiBF of 1mol/L respectively 4the LiTFSI/ propene carbonate electrolyte of/diethyl carbonate electrolyte, 1mol/L, the LiFSI/ ethylene carbonate/acetonitrile electrolyte of 1mol/L, the collector adopted is Copper Foil, nickel foil and aluminium foil respectively, and the conductive agent of employing is respectively active carbon, carbon black and acetylene black.
Table 1 encloses for lithium ion battery prepared by embodiment 5 ~ 8 carries out charge-discharge test the 2nd under 0.1C electric current and the 501st encloses the stored energy capacitance obtained, as follows:
Table 1
As can be seen from Table 1, after lithium ion battery circulation 500 circle adopting the cobaltosic oxide-graphene-carbon nano tube composite material of embodiment 1 ~ 4 to prepare, capability retention all more than 85%, is up to 93%, has excellent cycle performance.
The lithium ion battery that table 2 is embodiment 5 ~ 8 preparation 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 adopting the 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 only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but therefore can not 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 (9)

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, the suspension of obtained graphite oxide after ultrasonic disperse;
Cobalt hydroxide is added in the suspension of described graphite oxide, ultrasonicly mix and make graphite oxide peel off into graphene oxide, add carbon nano-tube again, ultrasonicly to mix, cobalt hydroxide-graphene oxide-the carbon nano tube suspension obtained, 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;
Filtration treatment is carried out to described cobalt hydroxide-graphene oxide-carbon nano tube suspension, after drying, obtains cobalt hydroxide-graphene oxide-carbon nano tube compound material;
Described cobalt hydroxide-graphene oxide-carbon nano tube compound material is placed in protective gas atmosphere; with heating rate to 500 ~ 700 DEG C of 15 ~ 25 DEG C/min; and keep 0.5 ~ 2 hour at the final temperature; make graphene oxide thermal reduction be Graphene and make cobalt hydroxide be decomposed into cobaltosic oxide, obtaining 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, it is characterized in that, described graphite oxide prepares as follows:
Graphite purity being not less than 99.5% is added in the mixed solution of the concentrated sulfuric acid and red fuming nitric acid (RFNA), be uniformly mixed at 0 DEG C, potassium permanganate is added again in mixed solution, stirring reaction makes graphite preliminary oxidation, reaction system is heated to 85 DEG C again and makes graphite complete oxidation, add hydrogenperoxide steam generator in the most backward reaction system and remove excessive potassium permanganate, suction filtration, with watery hydrochloric acid and deionized water, the solids obtained is washed successively, after drying, 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, it is characterized in that, in the suspension of described graphite oxide, the concentration of graphite oxide is 0.5 ~ 1mg/mL.
5. cobaltosic oxide-the graphene-carbon nano tube composite material adopting the preparation method of the cobaltosic oxide-graphene-carbon nano tube composite material according to any one of Claims 1 to 4 to prepare.
6. a lithium ion battery, be included in the positive plate, barrier film and the negative plate that arrange in housing and the electrolyte be filled 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 of mixing, conductive agent and cobaltosic oxide-graphene-carbon nano tube composite material as claimed in claim 5.
7. lithium ion battery as claimed in claim 6, it 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.
8. lithium ion battery as claimed in claim 6, it 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.
9. a preparation method for lithium ion battery, is characterized in that, comprises the steps:
Cobaltosic oxide-graphene-carbon nano tube composite material according to claim 5, binding agent are mixed with conductive agent, obtains electrode slurry;
By described electrode slurry coating on a current collector, after dry, section obtains negative plate;
Negative plate, barrier film and positive plate lamination are arranged and be assembled into battery core, barrier film between two electrode slices, then uses battery core described in packaging shell, injects electrolyte, obtains described lithium ion battery.
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