CN107887580A - 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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- CN107887580A CN107887580A CN201711017317.6A CN201711017317A CN107887580A CN 107887580 A CN107887580 A CN 107887580A CN 201711017317 A CN201711017317 A CN 201711017317A CN 107887580 A CN107887580 A CN 107887580A
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
The invention discloses a kind of flower-shaped cobalt oxide/graphene hollow microsphere lithium ion battery negative material and preparation method thereof, the negative material is made up of micron dimension hollow microsphere, the wall of hollow microsphere is generally radially arranged by two-dimensional nano piece to be surrounded, a diameter of 25 nanometers of hole is distributed with two-dimensional nano piece, the material of main part of two-dimensional nano piece is cobaltosic oxide, and its surface attachment has graphene sheet layer.The electrode material has preparation technology 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 problems, such as that nanostructured is easily reunited 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 technology
Now, power lithium-ion battery turns into 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 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 automobile
Development and demand Deng field, therefore, 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 material.In numerous transition metal oxides
In material, cobaltosic oxide has 890mAh/g specific capacities, is 2.5 times of graphite cathode specific capacity, volume and capacity ratio is graphite
7.5 times.However, cobaltosic oxide Volume Changes violent in charge and discharge process cause poor circulation；And four aoxidize
Three cobalt negative materials have relatively low electronic conductivity and show poor high rate performance.These defects seriously hinder four oxygen
Change application of three cobalts as negative material in lithium ion battery.
Current study show that by cobaltosic oxide nano, coated with conductive carbon material, be to improve cobaltosic oxide
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 as lithium ion battery negative material,
Under 100mA/g current densities, 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 of multi-walled carbon nanotube cladding
Cobalt multiaspect composite material, chemical property be improved significantly, under 100mA/g current densities, circulation 100 circle after, specific capacity
Reach 813mAh/g；1000mA/g current densities, specific capacity remain to be maintained at 514mAh/g.Although relevant 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 on four oxygen
Change the modified technique of three cobalt electrode materials and preparation method is carried out by cobaltosic oxide nano or on the basis of nanosizing
Carbon material coats, and technique is more complicated, and cost is higher.
The content of the invention
In order to solve technical problem present in 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, the electrode material has preparation technology simplicity, pattern unique, is prepared into
Although the hollow complex microsphere of the cobalt oxide/graphene arrived is micron dimension, still show preferable cycle performance and times
Rate performance.And the microballoon of micron dimension can solve the problems, such as that nanostructured is easily reunited in charge and discharge process.
Second object of the present invention is to provide above-mentioned flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material
Preparation method.Using dual hydro-thermal method, the cobalt oxide/graphene lithium-ion electric with high-performance special construction is prepared
Pond negative material, preparation technology are easy.
Third object of the present invention is to provide above-mentioned flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material
Application in lithium ion battery negative material is prepared.
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 scheme is that：
A kind of flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material, is made up of micron dimension hollow microsphere,
The wall of hollow microsphere is generally radially arranged by two-dimensional nano piece to be surrounded, and a diameter of 2-5 nanometers are distributed with two-dimensional nano piece
Hole, the material of main part of two-dimensional nano piece is cobaltosic oxide, and its surface attachment has graphene sheet layer.
Preferably, the average grain diameter of the hollow microsphere is 1.6 μm.
It is further preferred that a diameter of 0.7-1.2 μm of the hollow cavity of the hollow microsphere.
Preferably, the specific surface area of the nano-pore in the two-dimensional nano piece is 150-176m2/g。
Preferably, the height of the two-dimensional nano lamella is 150-220nm, thickness 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, comprises the following steps：
1) soluble cobalt is dissolved in organic solvent, hydro-thermal reaction is carried out under design 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) obtained cobalt hydroxide/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), magnetic agitation is carried out in hydrothermal reaction process, the speed of magnetic agitation turns for 100-500/
Minute.
Preferably, in step 1), in addition to the cobalt salt microballoon presoma being prepared is centrifuged, cleans, do
Dry step.
It is further preferred that the rotating speed centrifuged 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, the step of hollow cobalt hydroxide/graphene microballoon centrifuges by made from is also included in step 2), from
The rotating 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 is 1-5 DEG C/min, preferably 2-4 DEG C/min；
Holding temperature is 100~600 DEG C, preferably 300-500 DEG C, more 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 densities, and after the circle of circulation 30, actual specific capacity reaches
1545mAh/g, coulombic efficiency are maintained at more than 97%；The discharge and recharge under 1000mA/g high current densities, it is real after circulation 700 is enclosed
Border specific capacity is up to 1172mAh/g, and coulombic efficiency is maintained at more than 99%.
Beneficial effects of the present invention are：
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 prepare electrode material granules particle diameter for 1.6 microns, it is homogeneous it is flower-shaped in
Empty micro-sphere structure.Special construction outermost layer, interted by two-dimensional nano piece and form petal-like structures, two-dimensional nano piece diameter is about
200 nanometers, thickness is about 5 nanometers, while substantial amounts of 2~5 nanometers of hole is distributed with two-dimensional nano 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 ratio surface, while improves electrical conductivity, shorten lithium from
The transmission path of son, improve the high rate performance of material；Hollow structure inside, the nanometer in surface two-dimensional nano piece and nanometer sheet
Hole, Volume Changes caused by embedding lithium takes off lithium can be alleviated in multiple charge and discharge process, improve 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 has 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 nanostructured
Raw agglomeration.
3) the flower-shaped cobalt oxide/graphene hollow microsphere electrode material prepared using this method is because of two wieners on surface
Rice piece, microballoon inner hollow, nano-pore in two-dimensional nano piece and there is very big ratio surface, up to 176m2/g。
Electrode material pattern prepared by the inventive method has good repeatability, and stable circulation with chemical property
Excellent performance.
Brief description of the drawings
The Figure of description for forming the part of the application is used for providing further understanding of the present application, and the application's shows
Meaning property embodiment and its illustrate be used for explain the application, do not form the improper restriction to the application.
The flower-shaped cobalt oxide/graphene hollow microsphere SEM figures that it is the inventive method synthesis that Fig. 1, which is,；
Fig. 2 is SEM figures inside the flower-shaped cobalt oxide/graphene hollow microsphere of the inventive method synthesis；
Fig. 3 is the XRD test results of the flower-shaped cobalt oxide/graphene hollow microsphere of the inventive method synthesis；
Fig. 4,5 are schemed for low current density and the high current density circulation of electrode material of the present invention.
Embodiment
It is noted that described further below is all exemplary, it is intended to provides further instruction to the application.It is unless another
Indicate, all technologies used herein and scientific terminology are with 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 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 singulative
It is also intended to include plural form, additionally, it should be understood that, when in this manual using term "comprising" and/or " bag
Include " when, it indicates existing characteristics, step, operation, device, component and/or combinations thereof.
Embodiment 1
Flower-shaped cobalt oxide/graphene hollow microsphere, is made by the steps：
(1) by 0.5mmol cabaltous nitrate hexahydrates, 4ml glycerine is added to, stirring is completely molten to solid in 15ml glycerine
Solve, 150 DEG C are reacted 10 hours in addition reactor, are cooled to room temperature, are rinsed repeatedly with water with alcohol after liquid is centrifuged, and are collected
Powder obtains cobalt salt microballoon presoma.
(2) by the cobalt salt microballoon presoma powder 0.05g collected in step (1) and 0.001g graphene dispersions to 15ml water
In, 120 DEG C are reacted 4 hours in addition reactor, are cooled to room temperature, are rinsed repeatedly with water with alcohol after liquid is centrifuged, and are collected
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 programming rate, 4 hours are incubated at 200 DEG C, treats that tube furnace is cooled to room temperature, i.e. flower-shaped four oxidation three of obtained black sample
Cobalt/graphene hollow microsphere powder.
Fig. 1, Fig. 2 are the SEM pictures of flower-shaped cobalt oxide/graphene hollow microsphere sample, it is found that the inventive method is closed
Into particle be microspheroidal, microsphere particle particle diameter 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, contrasted with standard card, products therefrom is cobaltosic oxide, and graphene is non-due to addition
It is often small, fail to show diffraction maximum, and there is no other impurities.
Electrode is made as follows with the flower-shaped cobalt oxide/graphene hollow microsphere composite of the gained of embodiment 1：
With 7:2:1 mass ratio weighs flower-shaped cobalt oxide/graphene hollow microsphere composite material, carbon black respectively
And tetrafluoroethene, after grinding, the 1-METHYLPYRROLIDONE of certain volume is added, continues grinding 2~3 hours, is coated uniformly on copper
Electrode is made on paper tinsel, uses metal lithium sheet as positive pole, electrolyte is 1mol/L LiPF6/ EC-DEC, barrier film are micro- from polypropylene
Hole barrier film, it is assembled into 2032 half-cells.Fig. 4, Fig. 5 are the cycle performance under 50mA/g, 1000mA/g current densities respectively.This
Invention electrode material is under 50mA/g current densities, and after the circle of circulation 50, actual specific capacity reaches 1545mAh/g, and coulombic efficiency is protected
Hold more than 97%；Electrode material of the present invention discharge and recharge under 1000mA/g high current densities, after circulation 700 is enclosed, actual specific volume
Amount reaches 1172mAh/g, and coulombic efficiency is maintained at more than 99%.
Embodiment 2
Flower-shaped cobalt oxide/graphene hollow microsphere, is made by the steps：
(1) by 0.75mmol cabaltous nitrate hexahydrates, 6ml glycerine is added to, stirring is complete to solid in 23ml glycerine
Dissolve, 150 DEG C are reacted 10 hours in addition reactor, are cooled to room temperature, are rinsed repeatedly with water with alcohol after liquid is centrifuged, and are received
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 dispersions to 15ml water
In, 120 DEG C are reacted 4 hours in addition reactor, are cooled to room temperature, are rinsed repeatedly with water with alcohol after liquid is centrifuged, and are collected
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 programming rate, 4 hours are incubated at 200 DEG C, treats that tube furnace is cooled to room temperature, 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 hexahydrates, 8ml glycerine is added to, stirring is completely molten to solid in 30ml glycerine
Solve, 150 DEG C are reacted 10 hours in addition reactor, are cooled to room temperature, are rinsed repeatedly with water with alcohol after liquid is centrifuged, and are collected
Powder obtains cobalt salt microballoon presoma.
(2) by the cobalt salt microballoon presoma powder 0.05g collected in step (1) and 0.001g graphene dispersions to 15ml water
In, 120 DEG C are reacted 4 hours in addition reactor, are cooled to room temperature, are rinsed repeatedly with water with alcohol after liquid is centrifuged, and are collected
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 programming rate, 4 hours are incubated at 200 DEG C, treats that tube furnace is cooled to room temperature, 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 hexahydrates, 8ml glycerine is added to, stirring is completely molten to solid in 30ml glycerine
Solve, 150 DEG C are reacted 10 hours in addition reactor, are cooled to room temperature, are rinsed repeatedly with water with alcohol after liquid is centrifuged, and are collected
Powder obtains cobalt salt microballoon presoma.
(2) by the cobalt salt microballoon presoma powder 0.05g collected in step (1) and 0.001g graphene dispersions to 15ml water
In, 140 DEG C are reacted 4 hours in addition reactor, are cooled to room temperature, are rinsed repeatedly with water with alcohol after liquid is centrifuged, and are collected
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 programming rate, 4 hours are incubated at 200 DEG C, treats that tube furnace is cooled to room temperature, 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 hexahydrates, 8ml glycerine is added to, stirring is completely molten to solid in 30ml glycerine
Solve, 150 DEG C are reacted 10 hours in addition reactor, are cooled to room temperature, are rinsed repeatedly with water with alcohol after liquid is centrifuged, and are collected
Powder obtains cobalt salt microballoon presoma.
(2) by the cobalt salt microballoon presoma powder 0.05g collected in step (1) and 0.001g graphene dispersions to 15ml water
In, 160 DEG C are reacted 4 hours in addition reactor, are cooled to room temperature, are rinsed repeatedly with water with alcohol after liquid is centrifuged, and are collected
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 programming rate, 4 hours are incubated at 200 DEG C, treats that tube furnace is cooled to room temperature, 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 hexahydrates, 8ml glycerine is added to, stirring is completely molten to solid in 30ml glycerine
Solve, 150 DEG C are reacted 10 hours in addition reactor, are cooled to room temperature, are rinsed repeatedly with water with alcohol after liquid is centrifuged, and are collected
Powder obtains cobalt salt microballoon presoma.
(2) by the cobalt salt microballoon presoma powder 0.05g collected in step (1) and 0.001g graphene dispersions to 15ml water
In, 120 DEG C are reacted 4 hours in addition reactor, are cooled to room temperature, are rinsed repeatedly with water with alcohol after liquid is centrifuged, and are collected
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 programming rate, 4 hours are incubated at 100 DEG C, treats that tube furnace is cooled to room temperature, 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 hexahydrates, 8ml glycerine is added to, stirring is completely molten to solid in 30ml glycerine
Solve, 150 DEG C are reacted 10 hours in addition reactor, are cooled to room temperature, are rinsed repeatedly with water with alcohol after liquid is centrifuged, and are collected
Powder obtains cobalt salt microballoon presoma.
(2) by the cobalt salt microballoon presoma powder 0.05g collected in step (1) and 0.001g graphene dispersions to 15ml water
In, 120 DEG C are reacted 4 hours in addition reactor, are cooled to room temperature, are rinsed repeatedly with water with alcohol after liquid is centrifuged, and are collected
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 programming rate, 4 hours are incubated at 300 DEG C, treats that tube furnace is cooled to room temperature, 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 hexahydrates, 8ml glycerine is added to, stirring is completely molten to solid in 30ml glycerine
Solve, 150 DEG C are reacted 10 hours in addition reactor, are cooled to room temperature, are rinsed repeatedly with water with alcohol after liquid is centrifuged, and are collected
Powder obtains cobalt salt microballoon presoma.
(2) by the cobalt salt microballoon presoma powder 0.05g collected in step (1) and 0.001g graphene dispersions to 15ml water
In, 120 DEG C are reacted 4 hours in addition reactor, are cooled to room temperature, are rinsed repeatedly with water with alcohol after liquid is centrifuged, and are collected
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 programming rate, 4 hours are incubated at 400 DEG C, treats that tube furnace is cooled to room temperature, 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 hexahydrates, 8ml glycerine is added to, stirring is completely molten to solid in 30ml glycerine
Solve, 170 DEG C are reacted 10 hours in addition reactor, are cooled to room temperature, are rinsed repeatedly with water with alcohol after liquid is centrifuged, and are collected
Powder obtains cobalt salt microballoon presoma.
(2) by the cobalt salt microballoon presoma powder 0.05g collected in step (1) and 0.001g graphene dispersions to 15ml water
In, 120 DEG C are reacted 4 hours in addition reactor, are cooled to room temperature, are rinsed repeatedly with water with alcohol after liquid is centrifuged, and are collected
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 programming rate, 4 hours are incubated at 200 DEG C, treats that tube furnace is cooled to room temperature, 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 hexahydrates, 8ml glycerine is added to, stirring is completely molten to solid in 30ml glycerine
Solve, 190 DEG C are reacted 10 hours in addition reactor, are cooled to room temperature, are rinsed repeatedly with water with alcohol after liquid is centrifuged, and are collected
Powder obtains cobalt salt microballoon presoma.
(2) by the cobalt salt microballoon presoma powder 0.05g collected in step (1) and 0.001g graphene dispersions to 15ml water
In, 120 DEG C are reacted 4 hours in addition reactor, are cooled to room temperature, are rinsed repeatedly with water with alcohol after liquid is centrifuged, and are collected
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 programming rate, 4 hours are incubated at 200 DEG C, treats that tube furnace is cooled to room temperature, i.e. flower-shaped four oxidation three of obtained black sample
Cobalt/graphene hollow microsphere powder.
The preferred embodiment of the application is the foregoing is only, is not limited to the application, for the skill of this area
For art personnel, the application can have various modifications and variations.It is all within spirit herein and principle, made any repair
Change, equivalent substitution, improvement etc., should be included within the protection domain of the application.
Claims (10)
- A kind of 1. flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material, it is characterised in that：It is hollow by micron dimension Microballoon is formed, and the wall of hollow microsphere is generally radially arranged by two-dimensional nano piece to be surrounded, and is distributed with two-dimensional nano piece a diameter of The hole of 2-5 nanometers, the material of main part of two-dimensional nano piece is cobaltosic oxide, and its surface attachment has graphene sheet layer.
- 2. flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material according to claim 1, its feature exist In：The average grain diameter of the hollow microsphere is 1.6 μm；Preferably, a diameter of 0.7-1.2 μm of the hollow cavity of the hollow microsphere.
- 3. flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material according to claim 1, its feature exist In：The specific surface area of nano-pore in the two-dimensional nano piece is 150-176m2/g；Preferably, the height of the two-dimensional nano lamella is 150-220nm, thickness 3-5nm.
- 4. flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material according to claim 1, its feature exist In：Carbon content in the flower-shaped cobalt oxide/graphene hollow microsphere combination electrode material is 4-5%.
- 5. the preparation method of any flower-shaped cobalt oxide/graphene hollow microsphere combination electrode materials of claim 1-4, It is characterized in that：Comprise the following steps：1) soluble cobalt is dissolved in organic solvent, hydro-thermal reaction is carried out under design 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 Setting time, hollow cobalt hydroxide/graphene microballoon is made；3) obtained cobalt hydroxide/graphene microballoon is heat-treated under a shielding gas, flower-shaped cobalt oxide/graphene is made Hollow microsphere.
- 6. preparation method according to claim 5, it is characterised in that：In step 1), the organic solvent be glycerine or Isopropanol；Preferably, in step 1), the soluble cobalt is cobalt nitrate；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), magnetic agitation is carried out in hydrothermal reaction process, the speed of magnetic agitation is 100-500 revs/min Clock；Preferably, in step 1), in addition to the cobalt salt microballoon presoma being prepared is centrifuged, is cleaned, is dried Step；It is further preferred that the rotating speed centrifuged is 3000-8000 revs/min, cleaned repeatedly using alcohol and water.
- 7. preparation method according to claim 5, it is characterised in that：In step 2), the graphene be 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, the step of hollow cobalt hydroxide/graphene microballoon centrifuges by made from is also included in step 2), centrifugation Rotating speed is 4000-6000 revs/min.
- 8. preparation method according to claim 5, it is characterised in that：In step 3), the protective gas is inert gas Or reducibility gas, inert gas are argon gas, nitrogen or helium, reducibility gas is hydrogen, alkenes gas or acetylenic gas；Preferably, in step 3), in heat treatment process, heating rate is 1-5 DEG C/min, preferably 2-4 DEG C/min；Holding temperature is 100~600 DEG C, preferably 300-500 DEG C, more preferably 350-450 DEG C；Soaking time is 1-4 hours, preferably 2-3 hours.
- 9. any flower-shaped cobalt oxide/graphene hollow microsphere combination electrode materials of claim 1-4 prepare lithium from Application in sub- cell negative electrode material.
- A kind of 10. negative electrode of lithium ion battery, it is characterised in that：By any flower-shaped cobaltosic oxide/graphite of claim 1-4 Alkene hollow microsphere combination electrode material is prepared.
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