CN107887580B - A kind of flower-shaped cobalt oxide/graphene hollow microsphere lithium ion battery negative material and preparation method thereof - Google Patents
A kind of flower-shaped cobalt oxide/graphene hollow microsphere lithium ion battery negative material and preparation method thereof Download PDFInfo
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- CN107887580B CN107887580B CN201711017317.6A CN201711017317A CN107887580B CN 107887580 B CN107887580 B CN 107887580B CN 201711017317 A CN201711017317 A CN 201711017317A CN 107887580 B CN107887580 B CN 107887580B
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Abstract
The invention discloses a kind of flower-shaped cobalt oxide/graphene hollow microsphere lithium ion battery negative materials and preparation method thereof, the negative electrode material is made of micron dimension hollow microsphere, the wall of hollow microsphere is generally radially arranged by two-dimensional nano piece and is surrounded, the hole that diameter is 2-5 nanometers is distributed in two-dimensional nano on piece, the material of main part of two-dimensional nano piece is cobaltosic oxide, and surface is attached with graphene sheet layer.The electrode material has preparation process simplicity, pattern unique, although the hollow complex microsphere of the cobalt oxide/graphene being prepared is micron dimension, still shows preferable cycle performance and high rate performance.And the microballoon of micron dimension can solve the problem of nanostructure is easy to happen reunion in charge and discharge process.
Description
Technical field
The invention belongs to electrochemistry and new energy field, and in particular to a kind of flower-shaped cobalt oxide/graphene of high-performance
Hollow microsphere lithium ion battery negative material and preparation method thereof.
Background technique
Now, power lithium-ion battery becomes the critical bottleneck for restricting new-energy automobile development, researches and develops high-power, high-energy
The new type lithium ion battery that density, energy-efficient, good cycling stability, application life are long, environmental suitability is strong is very urgent.
However, the current negative electrode material such as graphite that commercial Li-ion battery uses both at home and abroad, specific capacity is only 372mAh/g, and is not easy
Fast charging and discharging, super-charge super-discharge electricity all cause irreversible lesion to battery material, have been difficult to meet lithium ion battery electric car
The development and demand in equal fields, for this purpose, it is extremely urgent to research and develop a kind of novel cathode material for lithium ion battery.
Due to its high theoretical specific capacity, transition metal oxide such as cobalt oxide, iron oxide, ferroso-ferric oxide, titanium dioxide
Tin, nickel oxide, mangano-manganic oxide and molybdenum dioxide etc. have been widely used as negative electrode material.In numerous transition metal oxides
In material, it is 2.5 times of graphite cathode specific capacity, volume and capacity ratio is graphite that cobaltosic oxide, which has 890mAh/g specific capacity,
7.5 times.However, cobaltosic oxide volume change violent in charge and discharge process leads to poor circulation；And four aoxidize
Three cobalt negative electrode materials have lower electronic conductivity and show poor high rate performance.These defects seriously hinder four oxygen
Change application of three cobalts as negative electrode material in lithium ion battery.
It is to improve cobaltosic oxide current study show that cobaltosic oxide nano is coated with conductive carbon material
Effective means as lithium ion battery negative material cycle performance and high rate performance.Zhu such as University Of Tianjin et al. (Zhu S,
Li J J,Deng X Y,et al.Ultrathin-Nanosheet-Induced Synthesis of 3D Transition
Metal Oxides Networks for Lithium Ion Battery Anodes[J].Advanced Functional
Materials, 2017,27 (9) .1605017) prepare three-dimensional Co3O4Contiguous network is as lithium ion battery negative material, In
Under 100mA/g current density, specific capacity reaches 1033mAh/g；Changchun Applied Chemistry Research Inst., Chinese Academy of Sciences Huang et al. (Huang
G,Zhang F,Du X,et al.Metal organic frameworks route to in situ insertion of
multiwalled carbon nanotubes in Co3O4polyhedra as anode materials for lithium-
Ion batteries [J] .ACS nano, 2015,9 (2): 1592-1599.) prepare four oxidations three that multi-walled carbon nanotube coats
Cobalt multi-panel composite material, chemical property be improved significantly, under 100mA/g current density, circulation 100 circle after, specific capacity
Reach 813mAh/g；1000mA/g current density, specific capacity remain to be maintained at 514mAh/g.Although related cobaltosic oxide at present
The modification of electrode material has obtained certain progress, but at present most of document including above-mentioned document and patent about four oxygen
The modified technique and preparation method for changing three cobalt electrode materials are carried out by cobaltosic oxide nano or on the basis of nanosizing
Carbon material cladding, technique is more complex, higher cost.
Summary of the invention
In order to solve the technical problems existing in the prior art, it is an object of the present invention to provide a kind of flower-shaped four oxygen
Change three cobalts/graphene hollow microsphere combination electrode material, which has preparation process simplicity, pattern unique, be prepared into
Although the hollow complex microsphere of the cobalt oxide/graphene arrived be micron dimension, still show preferable cycle performance and times
Rate performance.And the microballoon of micron dimension can solve the problem of nanostructure is easy to happen reunion in charge and discharge process.
A second object of the present invention is to provide above-mentioned flower-shaped cobalt oxide/graphene hollow microsphere combination electrode materials
Preparation method.Using dual hydro-thermal method, the cobalt oxide/graphene lithium-ion electric with high-performance special construction is prepared
Pond negative electrode material, preparation process are easy.
Third object of the present invention is to provide above-mentioned flower-shaped cobalt oxide/graphene hollow microsphere combination electrode materials
Preparing the application in lithium ion battery negative material.
Fourth object of the present invention is to provide a kind of negative electrode of lithium ion battery, by above-mentioned flower-shaped cobaltosic oxide/graphite
Alkene hollow microsphere combination electrode material is prepared.
In order to solve the above technical problems, the technical solution of the present invention is as follows:
A kind of flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material, is made of micron dimension hollow microsphere,
The wall of hollow microsphere is generally radially arranged by two-dimensional nano piece and is surrounded, and it is 2-5 nanometers that diameter, which is distributed with, in two-dimensional nano on piece
The material of main part in hole, two-dimensional nano piece is cobaltosic oxide, and surface is attached with graphene sheet layer.
Preferably, the average grain diameter of the hollow microsphere is 1.6 μm.
It is further preferred that the diameter of the hollow cavity of the hollow microsphere is 0.7-1.2 μm.
Preferably, the specific surface area of the nano-pore of the two-dimensional nano on piece is 150-176m2/g。
Preferably, the height of the two-dimensional nano lamella is 150-220nm, with a thickness of 3-5nm.
Preferably, the carbon content in the flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material is 4-
5%.
The preparation method of above-mentioned flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material, includes the following steps:
1) soluble cobalt is dissolved in organic solvent, hydro-thermal reaction is carried out under set temperature, react setting time, be made
Cobalt salt microballoon presoma；
2) graphene is added into cobalt salt microballoon presoma, and mixture is dispersed in water, at a set temperature hydro-thermal
Setting time is reacted, hollow cobalt hydroxide/graphene microballoon is made；
3) cobalt hydroxide obtained/graphene microballoon is heat-treated under a shielding gas, flower-shaped cobaltosic oxide/stone is made
Black alkene hollow microsphere.
Preferably, in step 1), the organic solvent is glycerine or isopropanol.
Preferably, in step 1), the soluble cobalt is cobalt nitrate.
Cobalt nitrate can be cabaltous nitrate hexahydrate or anhydrous nitric acid cobalt.
Preferably, in step 1), the temperature of hydro-thermal reaction is 120-200 DEG C, and the time of hydro-thermal reaction is 2-16 hours.
Preferably, in step 1), carry out magnetic agitation in hydrothermal reaction process, the rate of magnetic agitation be 100-500 turn/
Minute.
It preferably, further include that the cobalt salt microballoon presoma that will be prepared is centrifuged, cleans, does in step 1)
Dry step.
It is further preferred that the revolving speed of centrifuge separation is 3000-8000 revs/min, cleaned repeatedly using alcohol and water.
Preferably, in step 2), the graphene is single-layer graphene, bilayer graphene or multi-layer graphene.
Preferably, in step 2), the temperature of hydro-thermal reaction is 120-180 DEG C, and the time of hydro-thermal reaction is 1-12 hours.
Preferably, further include the steps that for hollow cobalt hydroxide obtained/graphene microballoon being centrifugated in step 2), from
The revolving speed of the heart is 4000-6000 revs/min.
Preferably, in step 3), the protective gas is inert gas or reducibility gas, and inert gas is argon gas, nitrogen
Gas or helium, reducibility gas are hydrogen, alkenes gas or acetylenic gas.
Preferably, in step 3), in heat treatment process, heating rate be 1-5 DEG C/min, preferably 2-4 DEG C/min；
Holding temperature is 100~600 DEG C, preferably 300-500 DEG C, further preferably 350-450 DEG C.
Soaking time is 1-4 hours, preferably 2-3 hours.
Above-mentioned flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material is preparing lithium ion battery negative material
In application.
A kind of negative electrode of lithium ion battery, by above-mentioned flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material system
It is standby to form.
The negative electrode of lithium ion battery of preparation is under 50mA/g current density, and after 30 circle of circulation, actual specific capacity reaches
1545mAh/g, coulombic efficiency are maintained at 97% or more；The charge and discharge under 1000mA/g high current density, it is real after circulation 700 is enclosed
Border specific capacity is up to 1172mAh/g, and coulombic efficiency is maintained at 99% or more.
The invention has the benefit that
The present invention uses dual hydro-thermal method, prepares with high-performance special construction cobalt oxide/graphene lithium ion
Cell negative electrode material.The special construction be primarily referred to as preparation electrode material granules partial size be 1.6 microns, it is uniform it is flower-shaped in
Empty micro-sphere structure.Special construction outermost layer, is interted by two-dimensional nano piece and constitutes petal-like structures, and two-dimensional nano piece diameter is about
200 nanometers, thickness is about 5 nanometers, while a large amount of 2~5 nanometers of hole is distributed in two-dimensional nano on piece；In the inside configuration
Sky, directly about 1.0 microns.A certain amount of graphene is added in the structure simultaneously, graphene sheet layer is attached to flower-shaped four oxidation three
In cobalt/graphene hollow microsphere laminated structure.The structure has very big specific surface, while improving conductivity, shorten lithium from
The transmission path of son, improves the high rate performance of material；Hollow structure inside, the nanometer in surface two-dimensional nano piece and nanometer sheet
Hole can be relieved embedding lithium in multiple charge and discharge process and take off volume change caused by lithium, improves the cyclical stability of material.The synthesis side
The flower-shaped cobalt oxide/graphene hollow microsphere electrode material of method synthesis has good pattern, while also having excellent
Electrochemical properties.
The advantage of the flower-shaped cobalt oxide/graphene hollow microsphere electrode material prepared with this method is:
1) the flower-shaped cobalt oxide/graphene hollow microsphere of special appearance is prepared, uniform particle sizes are unified, trace graphite alkene
Addition greatly improve the high rate performance of electrode material.
2) particle prepared is micron order, 1.6 microns of average grain diameter, is not easy to send out in charge and discharge process compared to nanostructure
Raw agglomeration.
3) using the flower-shaped cobalt oxide/graphene hollow microsphere electrode material of this method preparation because of two wieners on surface
Rice piece, microballoon inner hollow, the nano-pore of two-dimensional nano on piece and have very big specific surface, up to 176m2/g。
The electrode material pattern and chemical property of inventive method preparation have good repeatability, and stable circulation
It has excellent performance.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.
Fig. 1 is the flower-shaped cobalt oxide/graphene hollow microsphere SEM figure for being the method for the present invention synthesis；
Fig. 2 is SEM figure inside the flower-shaped cobalt oxide/graphene hollow microsphere of the method for the present invention synthesis；
Fig. 3 is the XRD test result of the flower-shaped cobalt oxide/graphene hollow microsphere of the method for the present invention synthesis；
Fig. 4,5 are schemed for low current density and the high current density circulation of electrode material of the present invention.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
Embodiment 1
Flower-shaped cobalt oxide/graphene hollow microsphere, is made by the steps:
(1) by 0.5mmol cabaltous nitrate hexahydrate, it is added to 4ml glycerine, stirring is completely molten to solid in 15ml glycerine
Solution is added in reaction kettle and reacts 10 hours for 150 DEG C, is cooled to room temperature, and with alcohol and water repeated flushing after liquid is centrifuged, collects
Powder obtains cobalt salt microballoon presoma.
(2) by the cobalt salt microballoon presoma powder 0.05g collected in step (1) and 0.001g graphene dispersion to 15ml water
In, it is added in reaction kettle and reacts 4 hours for 120 DEG C, be cooled to room temperature, with alcohol and water repeated flushing after liquid is centrifuged, collect
Powder obtains hollow cobalt hydroxide/graphene microballoon.
(3) by the hollow cobalt hydroxide/graphene microballoon collected in step (2) in nitrogen atmosphere tube furnace, with 1 DEG C/
Minute heating rate keeps the temperature 4 hours at 200 DEG C, is cooled to room temperature to tube furnace, i.e. flower-shaped four oxidation three of obtained black sample
Cobalt/graphene hollow microsphere powder.
Fig. 1, Fig. 2 are the SEM picture of flower-shaped cobalt oxide/graphene hollow microsphere sample, it is found that the inventive method is closed
At particle be microspheroidal, microsphere particle partial size is in 1.6 microns；Microballoon outermost layer, which is that two-dimensional nano piece is interspersed, to be formed, and is received
Rice piece diameter is about 200 nanometers, and thickness is about 5 nanometers；It is hollow structure inside microballoon.Fig. 3 is flower-shaped cobaltosic oxide/graphite
Alkene hollow microsphere sample XRD spectra is compared with standard card, and products therefrom is cobaltosic oxide, and graphene is non-due to additive amount
It is often small, fail to show diffraction maximum, and there is no other impurities.
Electrode is made as follows with the 1 flower-shaped cobalt oxide/graphene hollow microsphere composite material of gained of embodiment:
Flower-shaped cobalt oxide/graphene hollow microsphere composite material material, carbon black are weighed respectively with the mass ratio of 7:2:1
And tetrafluoroethene, after grinding, the N-Methyl pyrrolidone of certain volume is added, continues grinding 2~3 hours, is coated uniformly on copper
Electrode is made on foil, uses metal lithium sheet for anode, electrolyte is the LiPF of 1mol/L6/ EC-DEC, diaphragm select polypropylene micro-
Hole diaphragm is assembled into 2032 half-cells.Fig. 4, Fig. 5 are the cycle performance at 50mA/g, 1000mA/g current density respectively.This
Invention electrode material is under 50mA/g current density, and after 50 circle of circulation, actual specific capacity reaches 1545mAh/g, and coulombic efficiency is protected
It holds 97% or more；Electrode material of the present invention charge and discharge under 1000mA/g high current density, after circulation 700 is enclosed, practical specific volume
Amount reaches 1172mAh/g, and coulombic efficiency is maintained at 99% or more.
Embodiment 2
Flower-shaped cobalt oxide/graphene hollow microsphere, is made by the steps:
(1) by 0.75mmol cabaltous nitrate hexahydrate, it is added to 6ml glycerine, stirring is complete to solid in 23ml glycerine
Dissolution is added in reaction kettle and reacts 10 hours for 150 DEG C, is cooled to room temperature, and with alcohol and water repeated flushing after liquid is centrifuged, receives
Collection powder obtains cobalt salt microballoon presoma.
(2) by the cobalt salt microballoon presoma powder 0.05g collected in step (1) and 0.001g graphene dispersion to 15ml water
In, it is added in reaction kettle and reacts 4 hours for 120 DEG C, be cooled to room temperature, with alcohol and water repeated flushing after liquid is centrifuged, collect
Powder obtains hollow cobalt hydroxide/graphene microballoon.
(3) by the hollow cobalt hydroxide/graphene microballoon collected in step (2) in nitrogen atmosphere tube furnace, with 1 DEG C/
Minute heating rate keeps the temperature 4 hours at 200 DEG C, is cooled to room temperature to tube furnace, i.e. flower-shaped four oxidation three of obtained black sample
Cobalt/graphene hollow microsphere powder.
Embodiment 3
Flower-shaped cobalt oxide/graphene hollow microsphere, is made by the steps:
(1) by 1.0mmol cabaltous nitrate hexahydrate, it is added to 8ml glycerine, stirring is completely molten to solid in 30ml glycerine
Solution is added in reaction kettle and reacts 10 hours for 150 DEG C, is cooled to room temperature, and with alcohol and water repeated flushing after liquid is centrifuged, collects
Powder obtains cobalt salt microballoon presoma.
(2) by the cobalt salt microballoon presoma powder 0.05g collected in step (1) and 0.001g graphene dispersion to 15ml water
In, it is added in reaction kettle and reacts 4 hours for 120 DEG C, be cooled to room temperature, with alcohol and water repeated flushing after liquid is centrifuged, collect
Powder obtains hollow cobalt hydroxide/graphene microballoon.
(3) by the hollow cobalt hydroxide/graphene microballoon collected in step (2) in nitrogen atmosphere tube furnace, with 1 DEG C/
Minute heating rate keeps the temperature 4 hours at 200 DEG C, is cooled to room temperature to tube furnace, i.e. flower-shaped four oxidation three of obtained black sample
Cobalt/graphene hollow microsphere powder.
Embodiment 4
Flower-shaped cobalt oxide/graphene hollow microsphere, is made by the steps:
1) by 1.0mmol cabaltous nitrate hexahydrate, it is added to 8ml glycerine, stirring is completely molten to solid in 30ml glycerine
Solution is added in reaction kettle and reacts 10 hours for 150 DEG C, is cooled to room temperature, and with alcohol and water repeated flushing after liquid is centrifuged, collects
Powder obtains cobalt salt microballoon presoma.
(2) by the cobalt salt microballoon presoma powder 0.05g collected in step (1) and 0.001g graphene dispersion to 15ml water
In, it is added in reaction kettle and reacts 4 hours for 140 DEG C, be cooled to room temperature, with alcohol and water repeated flushing after liquid is centrifuged, collect
Powder obtains hollow cobalt hydroxide/graphene microballoon.
(3) by the hollow cobalt hydroxide/graphene microballoon collected in step (2) in nitrogen atmosphere tube furnace, with 1 DEG C/
Minute heating rate keeps the temperature 4 hours at 200 DEG C, is cooled to room temperature to tube furnace, i.e. flower-shaped four oxidation three of obtained black sample
Cobalt/graphene hollow microsphere powder.
Embodiment 5
Flower-shaped cobalt oxide/graphene hollow microsphere, is made by the steps:
1) by 1.0mmol cabaltous nitrate hexahydrate, it is added to 8ml glycerine, stirring is completely molten to solid in 30ml glycerine
Solution is added in reaction kettle and reacts 10 hours for 150 DEG C, is cooled to room temperature, and with alcohol and water repeated flushing after liquid is centrifuged, collects
Powder obtains cobalt salt microballoon presoma.
(2) by the cobalt salt microballoon presoma powder 0.05g collected in step (1) and 0.001g graphene dispersion to 15ml water
In, it is added in reaction kettle and reacts 4 hours for 160 DEG C, be cooled to room temperature, with alcohol and water repeated flushing after liquid is centrifuged, collect
Powder obtains hollow cobalt hydroxide/graphene microballoon.
(3) by the hollow cobalt hydroxide/graphene microballoon collected in step (2) in nitrogen atmosphere tube furnace, with 1 DEG C/
Minute heating rate keeps the temperature 4 hours at 200 DEG C, is cooled to room temperature to tube furnace, i.e. flower-shaped four oxidation three of obtained black sample
Cobalt/graphene hollow microsphere powder.
Embodiment 6
Flower-shaped cobalt oxide/graphene hollow microsphere, is made by the steps:
1) by 1.0mmol cabaltous nitrate hexahydrate, it is added to 8ml glycerine, stirring is completely molten to solid in 30ml glycerine
Solution is added in reaction kettle and reacts 10 hours for 150 DEG C, is cooled to room temperature, and with alcohol and water repeated flushing after liquid is centrifuged, collects
Powder obtains cobalt salt microballoon presoma.
(2) by the cobalt salt microballoon presoma powder 0.05g collected in step (1) and 0.001g graphene dispersion to 15ml water
In, it is added in reaction kettle and reacts 4 hours for 120 DEG C, be cooled to room temperature, with alcohol and water repeated flushing after liquid is centrifuged, collect
Powder obtains hollow cobalt hydroxide/graphene microballoon.
(3) by the hollow cobalt hydroxide/graphene microballoon collected in step (2) in nitrogen atmosphere tube furnace, with 1 DEG C/
Minute heating rate keeps the temperature 4 hours at 100 DEG C, is cooled to room temperature to tube furnace, i.e. flower-shaped four oxidation three of obtained black sample
Cobalt/graphene hollow microsphere powder.
Embodiment 7
Flower-shaped cobalt oxide/graphene hollow microsphere, is made by the steps:
1) by 1.0mmol cabaltous nitrate hexahydrate, it is added to 8ml glycerine, stirring is completely molten to solid in 30ml glycerine
Solution is added in reaction kettle and reacts 10 hours for 150 DEG C, is cooled to room temperature, and with alcohol and water repeated flushing after liquid is centrifuged, collects
Powder obtains cobalt salt microballoon presoma.
(2) by the cobalt salt microballoon presoma powder 0.05g collected in step (1) and 0.001g graphene dispersion to 15ml water
In, it is added in reaction kettle and reacts 4 hours for 120 DEG C, be cooled to room temperature, with alcohol and water repeated flushing after liquid is centrifuged, collect
Powder obtains hollow cobalt hydroxide/graphene microballoon.
(3) by the hollow cobalt hydroxide/graphene microballoon collected in step (2) in nitrogen atmosphere tube furnace, with 1 DEG C/
Minute heating rate keeps the temperature 4 hours at 300 DEG C, is cooled to room temperature to tube furnace, i.e. flower-shaped four oxidation three of obtained black sample
Cobalt/graphene hollow microsphere powder.
Embodiment 8
Flower-shaped cobalt oxide/graphene hollow microsphere, is made by the steps:
1) by 1.0mmol cabaltous nitrate hexahydrate, it is added to 8ml glycerine, stirring is completely molten to solid in 30ml glycerine
Solution is added in reaction kettle and reacts 10 hours for 150 DEG C, is cooled to room temperature, and with alcohol and water repeated flushing after liquid is centrifuged, collects
Powder obtains cobalt salt microballoon presoma.
(2) by the cobalt salt microballoon presoma powder 0.05g collected in step (1) and 0.001g graphene dispersion to 15ml water
In, it is added in reaction kettle and reacts 4 hours for 120 DEG C, be cooled to room temperature, with alcohol and water repeated flushing after liquid is centrifuged, collect
Powder obtains hollow cobalt hydroxide/graphene microballoon.
(3) by the hollow cobalt hydroxide/graphene microballoon collected in step (2) in nitrogen atmosphere tube furnace, with 1 DEG C/
Minute heating rate keeps the temperature 4 hours at 400 DEG C, is cooled to room temperature to tube furnace, i.e. flower-shaped four oxidation three of obtained black sample
Cobalt/graphene hollow microsphere powder.
Embodiment 9
Flower-shaped cobalt oxide/graphene hollow microsphere, is made by the steps:
1) by 1.0mmol cabaltous nitrate hexahydrate, it is added to 8ml glycerine, stirring is completely molten to solid in 30ml glycerine
Solution is added in reaction kettle and reacts 10 hours for 170 DEG C, is cooled to room temperature, and with alcohol and water repeated flushing after liquid is centrifuged, collects
Powder obtains cobalt salt microballoon presoma.
(2) by the cobalt salt microballoon presoma powder 0.05g collected in step (1) and 0.001g graphene dispersion to 15ml water
In, it is added in reaction kettle and reacts 4 hours for 120 DEG C, be cooled to room temperature, with alcohol and water repeated flushing after liquid is centrifuged, collect
Powder obtains hollow cobalt hydroxide/graphene microballoon.
(3) by the hollow cobalt hydroxide/graphene microballoon collected in step (2) in nitrogen atmosphere tube furnace, with 1 DEG C/
Minute heating rate keeps the temperature 4 hours at 200 DEG C, is cooled to room temperature to tube furnace, i.e. flower-shaped four oxidation three of obtained black sample
Cobalt/graphene hollow microsphere powder.
Embodiment 10
Flower-shaped cobalt oxide/graphene hollow microsphere, is made by the steps:
1) by 1.0mmol cabaltous nitrate hexahydrate, it is added to 8ml glycerine, stirring is completely molten to solid in 30ml glycerine
Solution is added in reaction kettle and reacts 10 hours for 190 DEG C, is cooled to room temperature, and with alcohol and water repeated flushing after liquid is centrifuged, collects
Powder obtains cobalt salt microballoon presoma.
(2) by the cobalt salt microballoon presoma powder 0.05g collected in step (1) and 0.001g graphene dispersion to 15ml water
In, it is added in reaction kettle and reacts 4 hours for 120 DEG C, be cooled to room temperature, with alcohol and water repeated flushing after liquid is centrifuged, collect
Powder obtains hollow cobalt hydroxide/graphene microballoon.
(3) by the hollow cobalt hydroxide/graphene microballoon collected in step (2) in nitrogen atmosphere tube furnace, with 1 DEG C/
Minute heating rate keeps the temperature 4 hours at 200 DEG C, is cooled to room temperature to tube furnace, i.e. flower-shaped four oxidation three of obtained black sample
Cobalt/graphene hollow microsphere powder.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for the skill of this field
For art personnel, various changes and changes are possible in this application.Within the spirit and principles of this application, made any to repair
Change, equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (23)
1. a kind of flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material, it is characterised in that: hollow by micron dimension
Microballoon composition, the wall of hollow microsphere is generally radially arranged by two-dimensional nano piece to be surrounded, and two-dimensional nano on piece is distributed with diameter and is
The material of main part in 2-5 nanometers of hole, two-dimensional nano piece is cobaltosic oxide, and surface is attached with graphene sheet layer；
Preparation method includes the following steps:
1) soluble cobalt is dissolved in organic solvent, hydro-thermal reaction is carried out under set temperature, react setting time, cobalt salt is made
Microballoon presoma；
2) graphene is added into cobalt salt microballoon presoma, and mixture is dispersed in water, at a set temperature hydro-thermal reaction
Hollow cobalt hydroxide/graphene microballoon is made in setting time；
3) cobalt hydroxide obtained/graphene microballoon is heat-treated under a shielding gas, flower-shaped cobalt oxide/graphene is made
Hollow microsphere.
2. flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material according to claim 1, feature exist
In: the average grain diameter of the hollow microsphere is 1.6 μm.
3. flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material according to claim 1, feature exist
In: the diameter of the hollow cavity of the hollow microsphere is 0.7-1.2 μm.
4. flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material according to claim 1, feature exist
In: the specific surface area of the nano-pore of the two-dimensional nano on piece is 150-176m2/g。
5. flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material according to claim 1, feature exist
In: the height of the two-dimensional nano piece is 150-220nm, with a thickness of 3-5nm.
6. flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material according to claim 1, feature exist
In: the carbon content in the flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material is 4-5%.
7. flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material according to claim 1, feature exist
In: in step 1), the organic solvent is glycerine or isopropanol.
8. flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material according to claim 1, feature exist
In: in step 1), the soluble cobalt is cobalt nitrate.
9. flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material according to claim 1, feature exist
In: in step 1), the temperature of hydro-thermal reaction is 120-200 DEG C, and the time of hydro-thermal reaction is 2-16 hours.
10. flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material according to claim 1, feature exist
In: in step 1), magnetic agitation is carried out in hydrothermal reaction process, the rate of magnetic agitation is 100-500 revs/min.
11. flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material according to claim 1, feature exist
In: in step 1), include the steps that the cobalt salt microballoon presoma that will be prepared is centrifuged, cleans, dries.
12. flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material according to claim 11, feature exist
In: the revolving speed of centrifuge separation is 3000-8000 revs/min, is cleaned repeatedly using alcohol and water.
13. flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material according to claim 1, feature exist
In: in step 2), the graphene is single-layer graphene or multi-layer graphene.
14. flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material according to claim 1, feature exist
In: in step 2), the temperature of hydro-thermal reaction is 120-180 DEG C, and the time of hydro-thermal reaction is 1-12 hours.
15. flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material according to claim 1, feature exist
In: further include the steps that, by hollow cobalt hydroxide obtained/graphene microballoon centrifuge separation, the revolving speed of centrifugation is in step 2)
4000-6000 revs/min.
16. flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material according to claim 1, feature exist
In: in step 3), the protective gas is inert gas or reducibility gas, and inert gas is argon gas, nitrogen or helium, reduction
Property gas be hydrogen, alkenes gas or acetylenic gas.
17. flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material according to claim 1, feature exist
In: in step 3), in heat treatment process, heating rate is 1-5 DEG C/min.
18. flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material according to claim 1, feature exist
In: in step 3), in heat treatment process, heating rate is 2-4 DEG C/min.
19. flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material according to claim 1, feature exist
In: heat treatment holding temperature is 100~600 DEG C in step 3).
20. flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material according to claim 1, feature exist
In: heat treatment holding temperature is 300-500 DEG C in step 3).
21. flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material according to claim 1, feature exist
In: heat treatment holding temperature is 350-450 DEG C in step 3).
22. flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material according to claim 1, feature exist
In: heat treatment soaking time is 1-4 hours in step 3).
23. flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material according to claim 1, feature exist
In: heat treatment soaking time is 2-3 hours in step 3).
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863518A (en) * | 2010-07-01 | 2010-10-20 | 上海应用技术学院 | Co3O4 nano hollow sphere material and preparation method and application thereof |
| CN102842710A (en) * | 2012-07-18 | 2012-12-26 | 上海大学 | Preparation method of Co3O4/graphene nanocomposite material |
| CN103086369A (en) * | 2013-01-18 | 2013-05-08 | 湖南元素密码石墨烯研究院（有限合伙） | Preparation method of graphene/nano cobaltosic oxide composite material |
| CN103490044A (en) * | 2012-06-11 | 2014-01-01 | 海洋王照明科技股份有限公司 | Preparation method of cobalt oxide (II,III)-graphene composite material |
| CN103633318A (en) * | 2012-08-24 | 2014-03-12 | 海洋王照明科技股份有限公司 | Preparation method for cobaltosic oxide-graphene composite material and preparation method for lithium ion battery |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863518A (en) * | 2010-07-01 | 2010-10-20 | 上海应用技术学院 | Co3O4 nano hollow sphere material and preparation method and application thereof |
| CN103490044A (en) * | 2012-06-11 | 2014-01-01 | 海洋王照明科技股份有限公司 | Preparation method of cobalt oxide (II,III)-graphene composite material |
| CN102842710A (en) * | 2012-07-18 | 2012-12-26 | 上海大学 | Preparation method of Co3O4/graphene nanocomposite material |
| CN103633318A (en) * | 2012-08-24 | 2014-03-12 | 海洋王照明科技股份有限公司 | Preparation method for cobaltosic oxide-graphene composite material and preparation method for lithium ion battery |
| CN103086369A (en) * | 2013-01-18 | 2013-05-08 | 湖南元素密码石墨烯研究院（有限合伙） | Preparation method of graphene/nano cobaltosic oxide composite material |
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