CN106449173A - Cobalt oxide quantum dot-bionic graphene high-energy-storage electrode material and preparation method thereof - Google Patents
Cobalt oxide quantum dot-bionic graphene high-energy-storage electrode material and preparation method thereof Download PDFInfo
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
The invention provides a cobalt oxide quantum dot-bionic graphene high-energy-storage electrode material and a preparation method thereof. The preparation method comprises the following steps: adding cleaned plant stems into ethanol-containing acid mixed liquid for soaking; then, dipping the plant stems into a glucose solution, placing the plant stems into a water solution containing ceric salt and cobalt salt, carrying out magnetic stirring and carrying out cleaning and drying; carrying out high-temperature heat treatment on the plant stems under the protection of nitrogen; carrying out furnace cooling; and transferring the obtained product to a reaction kettle for hydrothermal reaction, and carrying out cleaning and drying to obtain the cobalt oxide quantum dot-bionic graphene high-energy-storage electrode material. The method prepares the high-energy-density electrode material by combining a cobalt oxide quantum dot material having a high specific surface area and graphene in a hierarchical porous structure and having high conductivity, and with cerium oxide nanometer quantum dots being as a stabilizing agent. The required chemical raw materials are small in type and have no toxicity; and the method is simple in process, does not need complex devices for reaction, is low in cost, causes no pollution to environment, is good in experiment repeatability, and has a large industrial popularization value.
Description
Technical field
The invention belongs to technical field of electrochemistry, it is related to a kind of high energy storage electrode material of cobalt oxide quantum dot-bionical Graphene
Material and preparation method thereof and in particular to by plant haulm synthesizing bionic cobalt oxide quantum dot-Graphene high energy storage electrode material and
Its preparation method, is more particularly to be modified with cobalt oxide quantum dot-bionical stone with different types of plant stem for templated synthesis
High energy storage electrode material of black alkene and preparation method thereof.
Background technology
With the rapid growth of mancarried electronic aid and renewable new energy exploitation, the design standard of current battery is no
Method meets actual demand.In the secondary cells such as the ni-mh of commercialization, lithium ion, the charge efficiency existing is low, cycle-index is few,
The defect such as High-current output ability is weak has seriously hindered the development of related industries.Only development has high-energy-density and big work(concurrently
The novel energy-storing equipment of rate density, could meet the routine use demand of people, and reach the purpose of efficient utilization new forms of energy.And
Ultracapacitor between ordinary capacitor and rechargeable battery, as a kind of novel energy-storing element, has higher energy and deposits
The advantages of storage density, the service life cycle surpassing ten thousand times and quick charging and discharging capabilities, just becoming the star of hope of novel battery.
The factor of impact ultracapacitor energy storage ability mainly includes electrode material, the electric conductivity of electrolyte and ionic mobility etc..And
Excellent electrode material is the key point giving full play to electrolyte potentiality.
At present, carbon-based material is the core electrode material of ultracapacitor, because of the electrode specific surface area of its super large and ultrashort
Electrode distance, the energy storage capacity of ultracapacitor can be made to be greatly improved.In addition, it can be as skeleton, by high capacitances such as cobalt, manganese
Metal-oxide or conducting polymer are combined together, and are played a role by two kinds of energy storage mechanisms simultaneously, make ultracapacitor
Energy density surmounts the level of chemical cell.Graphene therein is even more the outstanding person in carbon-based material, and it is with sp2 hydridization even
The preferable two dimensional crystal nano material that the monoatomic layer connecing is constituted, the π key in Graphene crystal plane direction makes it have
Excellent electric conductivity, the high-efficiency heat conduction performance that Graphene originally has in addition, both can improve the heat dispersion of electrode, can effectively drop again
The internal resistance of low capacitor.However, the Graphene yield of traditional solid phase mechanical stripping method preparation is relatively low.Liquid phase rule can cause
Serious acid solution pollution, danger is higher, and final product still comprises substantial amounts of C-O key.And the most accurate vapor phase method, such as high
Warm epitaxial growth method and chemical vapour deposition technique (CVD) are although more complete single-layer graphene film can be produced, but need loaded down with trivial details
Step and complicated technology controlling and process, and rely on high-quality substrate, lead to high cost, and follow-up adhesion between graphene sheet layer
Stablize cobalt, manganese oxide nanoparticles are still in blank with the production technology of additional pseudo potential electric capacity.
Biological template method based on the self assembly of biomolecule, the special construction of available biological tissue is constructed to be had
Specific physics, the new material of chemical property, the method operation is simple, and easily extension produces, and has become as current material technology
The focus of development.Through development for many years, multiple Research Teams by the use of natural plant material as template, output several
High performance carbon material.Professor Huang Jianguo as department of chemistry of Zhejiang University organizes by the use of paper fiber as template, synthesizing porous carbon nanometer
Fiber pipe is simultaneously used for light degradation organic dyestuff coated with the titanium oxide of the anatase titanium dioxide of 12 nm.And Electroanalytical Chemistry country of Chinese Academy of Sciences weight
Dong Shaojun of point laboratory etc., then with bean milk as template, has synthesized the fluorescence nano point of doping nitrogen, this new material is in hydrogen reduction
Good electrocatalysis characteristic has been embodied in reaction.
The stalk of plant has a preferable mechanical strength, the biomolecule such as cellulose of composition stalk be rich in carboxyl and
Hydroxyl etc. can produce, with metal ion, the functional group linking, and be both suitable as preparing the template of carbons material, be also easy in carbon materials
Nano-particle is introduced in material.Currently, with respect to plant stem synthesize electrode material for super capacitor Patents there is not been reported.
Content of the invention
The technical problem solving：In view of the shortcomings of the prior art, the invention provides cobalt oxide quantum dot-bionical stone
High energy storage electrode material of black alkene and preparation method thereof.Preparation method provided by the present invention is with low cost, process is simple, it is to avoid
The in the past various chemistry higher to equipment requirements and physics prepare tedious steps, the higher one-tenth that graphene composite material method is brought
Basis and complicated technology, and stablize cobalt oxide quantum dot, thus significantly carrying by mixing the oxide nano particles of rare-earth element cerium
The electric property of high electrode material.
Technical scheme：The preparation method of the high energy storage electrode material of cobalt oxide quantum dot-bionical Graphene that the present invention provides,
Comprise the following steps：
The first step：The pre-treatment of plant stem
By containing porous and the higher plant haulm raw material of water content is cleaned, standby；Ethanol and ultra-pure water are made into mixed liquor, and adjust
Section pH of mixed is 1 ~ 4, standby；The plant haulm cleaned is completely soaked and carries out activation processing in described mixed liquor；
Second step：The post processing of plant stem
Plant stem after soaking is taken out, then impregnated in glucose solution and carry out net mending process, take out and clean, it
It is placed in afterwards in salt containing cerium and the aqueous solution of cobalt salt, and magnetic agitation, take out and clean and be dried；
3rd step：Heat treatment
Under nitrogen protection, the plant stem being dried is carried out calcining heat treatment, its calcining heat treatment condition is：It is to slowly warm up to
700～900 DEG C, it is incubated 2 h ~ 4 h；
4th step：Cooling
After calcining terminates, cool to room temperature with the furnace；
5th step：The growth in situ of oxide
Product after cooling is added in the ultra-pure water containing ammonia, is transferred to after stirring in reactor, is placed in baking oven
Carry out hydro-thermal reaction, after completion of the reaction, wash and be dried, obtain final product the high energy storage electrode material of cobalt oxide quantum dot-bionical Graphene.
Wherein, in the 5th step, hydrothermal reaction condition is：120 DEG C, 6 h；The filling rate of described reactor be 45% ~
60%；The addition of described ammonia is the volume of the described ultra-pure water of 1/10 ~ 1/15 volume.
Wherein, in second step, the mass fraction of the middle glucose of described glucose solution is 5 % ~ 10 %.
Wherein, in second step, in second step, the amount of the material of described cerium salt and cobalt salt is than for 1:4.
Wherein, described plant haulm is containing porous and the higher plant haulm of water content；Preferably, described plant haulm is
One of rape flower cane, corn stem, Canna generalis Bailey cane, hyacinth cane, Epipremnum aureum (Linde et Andre) (Bunting.) cane, red palm cane.
Wherein, in second step, in described aqueous solution, the concentration of cobalt salt is 5 ~ 15 g/L, described plant stem and cobalt salt
Mass ratio is 5 ~ 20:1.
Wherein, in second step, described dip time is 12 ~ 24 h；The volume of described glucose solution is not less than 10
ML/g plant stem.
Wherein, in the third step, described heating rate is 2 DEG C/min.
Wherein, in the first step, in described mixed liquor, the volume ratio of ethanol and ultra-pure water is 1:3；Described soak time is
36 h~72 h.
Wherein, in second step, described magnetic stirring speed is 500 ~ 1500 r/min, and mixing time is 8 ~ 24 h；?
In second step, described baking temperature is 40 DEG C, and drying time is 6-12 h；In the 5th step, described drying condition is：50
DEG C, 12 h.
Wherein, in the first step, the consumption of described mixed liquor is at least can be completely soaked plant stem to be advisable, real one
Apply in example, the consumption of described mixed liquor is 10mL/g plant haulm, but its concrete consumption not limited to this.In second step, described
Glucose solution consumption is at least can be completely soaked plant stem to be advisable, in one embodiment, the use of described glucose solution
Measure as 10mL/g plant haulm, but its concrete consumption not limited to this.
Wherein, described cobalt salt is one of inorganic cobalt salts such as nitrate, sulfate, chlorate and the carbonate of cobalt.Make
For preferred, described cobalt salt is cobalt nitrate.Described cerium salt cobalt is the Inorganic Ceriums such as nitrate, sulfate, chlorate and the carbonate of cerium
One of salt.Preferably, described cerium salt is cerous nitrate.
The high energy storage electrode material of cobalt oxide quantum dot-bionical Graphene that the present invention provides, described electrode material has above-mentioned
Described preparation method is prepared from.
The nano structure electrode material that design and exploitation have high specific capacitance is to improve the having of ultracapacitor energy storage density
Efficacious prescriptions method, but at present, industrial difficult point is always with the nanometer electroactive material that low cost produces high-quality.
Beneficial effects of the present invention：
（1）The present invention passes through with the porous stalk of variety classes plant as biological template, and introduces metal ion entrance plant mould
The loose structure of plate, then removed the impurity in template by the lower high-temperature calcination of nitrogen protection, pass through afterwards to control the hydro-thermal reaction time and
Temperature adjusting nanocrystal size, thus obtaining high-quality electrode material.The present invention passes through synthesis and has high-specific surface area
The Graphene of cobalt oxide quanta point material and the graded porous structure with high conductivity combines, on the one hand with nano-oxide
Quantum dot provides enough electroactive units for faraday's reaction, and the Graphene of another aspect graded porous structure can guarantee that foot
Enough electrolyte ions and atom participate in faraday's reaction with two-forty, thus the energy of electrode material is greatly improved simultaneously
Metric density.
（2）The present invention by carrying out pre-treatment to plant haulm, can activate the biomolecule such as cellulose in plant haulm,
It is made to produce the functional group that can link carboxyl and hydroxyl etc. with metal ion.Using appropriate concentration in the preparation method of the present invention
The dipping of glucose solution, so can carry out net mending to the plant membrane after processing, so that the generation of follow-up sheet Graphene.
（3）The present invention passes through to mix rare-earth element cerium, using cerium oxide nano quantum dot as stabilizer, can be effectively steady
Determine cobalt oxide quantum dot, it is to avoid large-scale crystal formed by cobalt oxide, it so can be greatly improved as the electrochemistry of electrode material
Can, there is larger commercial introduction and be worth.
（4）Preparation method provided by the present invention is with low cost, process is simple, it is to avoid conventional various to equipment requirements relatively
High chemistry and physics prepare tedious steps, higher cost and the complicated technology that graphene composite material method is brought.The present invention
The preparation method being provided has filled up the blank of the cobalt oxide quantum dot-bionical Graphene preparation aspect of high energy storage.
（5）Chemical raw material species needed for the present invention is less and avirulence, the equipment that reaction need not be complicated, and cost is relatively low, right
Environmental nonpollution, assay reproducibility is good, has larger commercial introduction to be worth.
Brief description
Fig. 1 is the scanning electron microscope (SEM) photograph of the electrode material of embodiment 1 gained in the present invention；
Fig. 2 is the high-resolution-ration transmission electric-lens figure of the electrode material of embodiment 1 gained in the present invention；
Fig. 3 is the Raman spectrogram of the electrode material of embodiment 1 gained in the present invention；
Fig. 4 is the ratio capacity measurement figure of the electrode material of embodiment 1 gained in the present invention.
Specific embodiment
For a further understanding of the present invention, with reference to embodiment, the preferred embodiment of the invention is described, but
It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention
Limit.
Embodiment 1
The first step：10 g rape flower canes are washed away floating dust with 100 mL distilled water immersion 10 min, ethanol and ultra-pure water are pressed
Volume ratio 1:3 are made into mixed liquor, and the use of salt acid for adjusting pH are 4, soak rape flower cane 60 using this mixed liquor 100 mL
h；
Second step：Rape flower cane after soaking is taken out, is then put in the glucose solution that 100 mL contain 8 %, dipping
24 h, are repeatedly washed with ultra-pure water afterwards.By 0.25 g Ce (NO3)3•6H2O and 1 g Co (NO3)2•6H2O puts into 100
Configure cerium cobalt liquor in mL distilled water solution, stalk is transferred in cerium cobalt liquor, after magnetic agitation 8 h under 600 r/min
Repeatedly wash, be laid in culture dish, in 40 DEG C of baking oven, 6 hs are dried；
3rd step：Dried plant stem is put into corundum porcelain boat, is placed in tube furnace, pass to nitrogen protection, by 2 DEG C/
Min ramp to 800 DEG C, isothermal reaction 3 h；
4th step：After calcining terminates, cool to room temperature with the furnace；
5th step：The ultra-pure water containing ammonia will be added through bionical Graphene（50mL ultra-pure water+5mL ammonia）In, stirring
It is transferred in reactor after uniformly, reactor is placed in 120 DEG C of baking oven and reacts 6 h.After hydro-thermal reaction terminates, by it
Take out sucking filtration, 50 DEG C of drying 12 h, you can obtain the high energy storage electrode material of cobalt oxide quantum dot-bionical Graphene.
Using scanning electron microscope and transmission electron microscope, sample structure is observed, by the prepared stone obtaining of Raman spectrum test
Black alkene fault of construction, and material is bonded to formation electrode in foam nickel sheet, it is characterized by electrochemical workstation and compares capacitance size.
The scanning of the high energy storage electrode material of cobalt oxide quantum dot-bionical Graphene being obtained by the technological parameter of embodiment 1
Electron microscope picture, as shown in figure 1, material integrally assumes the biomimetic porous multiple structure with stalk loose structure.Sample
Transmission electron microscope figure, as shown in Figure 2 it can be seen that be distributed with the preferable cobalt oxide-oxidation of dispersibility on graphene sheet layer
Cerium nano-quantum point, wherein illustration are the high-resolution transmission image of oxide particle, further demonstrate that its particle diameter in 5-8 nm
Between, it is high-quality quantum dot.The Raman collection of illustrative plates of material is as shown in figure 3, D, G and 2D peak therein belongs to the knot of Graphene
Structure, the Raman peaks corresponding to oxide structure are also high-visible.The high energy storage electrode material of cobalt oxide quantum dot-bionical Graphene
Ratio capacity measurement figure, as shown in figure 4, unipolar reached 221F g than electric capacity-1, far super typical electrode materials.
Embodiment 2
The first step：10 g corn stems are washed away floating dust with 100 mL distilled water immersion 10 min, ethanol and ultra-pure water are pressed body
Amass and compare 1:3 are made into mixed liquor, and the use of salt acid for adjusting pH are 3, using this mixed liquor 100 mL soaking corn cane 48 h；
Second step：Corn stem after soaking is taken out, is then put in the glucose solution that 150 mL contain 6 %, impregnates 24
H, is repeatedly washed with ultra-pure water afterwards.By 0.125 g Ce (NO3)3•6H2O and 0.5 g Co (NO3)2•6H2O puts into 100
Configure cerium cobalt liquor in mL distilled water solution, stalk is transferred in cerium cobalt liquor, after magnetic agitation 24 h under 500 r/min
Repeatedly wash, be laid in culture dish, in 40 DEG C of baking oven, 12 hs are dried；
3rd step：Dried plant stem is put into corundum porcelain boat, is placed in tube furnace, pass to nitrogen protection, by 2 DEG C/
Min ramp to 800 DEG C, isothermal reaction 3 h；
4th step：After calcining terminates, cool to room temperature with the furnace；
5th step：The ultra-pure water containing ammonia will be added through bionical Graphene（45mL ultra-pure water+3mL ammonia）In, stir
After be transferred in reactor, reactor is placed in 120 DEG C of baking oven and reacts 6 h.After hydro-thermal reaction terminates, it is drawn off
Sucking filtration, 50 DEG C of drying 12 h, you can obtain the high energy storage electrode material of cobalt oxide quantum dot-bionical Graphene.
Embodiment 3
The first step：10 g Canna generalis Bailey canes are washed away floating dust with 100 mL distilled water immersion 10 min, ethanol and ultra-pure water are pressed
Volume ratio 1:3 are made into mixed liquor, and the use of salt acid for adjusting pH are 2, soak Canna generalis Bailey cane 72 using this mixed liquor 100 mL
h；
Second step：Canna generalis Bailey cane after soaking is taken out, is then put in the glucose solution that 100 mL contain 5 %, dipping
18 h, are repeatedly washed with ultra-pure water afterwards.By 0.375 g Ce (NO3)3•6H2O and 1.5 g Co (NO3)2•6H2O puts into
Configure cerium cobalt liquor in 100 mL distilled water solutions, stalk is transferred in cerium cobalt liquor, magnetic agitation 8 under 1500 r/min
Repeatedly wash after h, be laid in culture dish, in 40 DEG C of baking oven, 6 hs are dried；
3rd step：Dried plant stem is put into corundum porcelain boat, is placed in tube furnace, pass to nitrogen protection, by 2 DEG C/
Min ramp to 900 DEG C, isothermal reaction 4 h；
4th step：After calcining terminates, cool to room temperature with the furnace；
5th step：The ultra-pure water containing ammonia will be added through bionical Graphene（60mL ultra-pure water+6mL ammonia）In, stir
After be transferred in reactor, reactor is placed in 120 DEG C of baking oven and reacts 6 h.After hydro-thermal reaction terminates, it is drawn off
Sucking filtration, 50 DEG C of drying 12 h, you can obtain the high energy storage electrode material of cobalt oxide quantum dot-bionical Graphene.
Embodiment 4
The first step：10 g hyacinth canes are washed away floating dust with 100 mL distilled water immersion 10 min, ethanol and ultra-pure water are pressed
Volume ratio 1:3 are made into mixed liquor, and the use of salt acid for adjusting pH are 4, soak hyacinth cane 36 using this mixed liquor 150 mL
h；
Second step：Hyacinth cane after soaking is taken out, is then put in the glucose solution that 100 mL contain 10 %, dipping
24 h, are repeatedly washed with ultra-pure water afterwards.By 0.2 g Ce (NO3)3•6H2O and 0.8 g Co (NO3)2•6H2O puts into 100
Configure cerium cobalt liquor in mL distilled water solution, stalk is transferred in cerium cobalt liquor, after magnetic agitation 8 h under 1000 r/min
Repeatedly wash, be laid in culture dish, in 40 DEG C of baking oven, 10 hs are dried；
3rd step：Dried plant stem is put into corundum porcelain boat, is placed in tube furnace, pass to nitrogen protection, by 2 DEG C/
Min ramp to 700 DEG C, isothermal reaction 2 h；
4th step：After calcining terminates, cool to room temperature with the furnace；
5th step：The ultra-pure water containing ammonia will be added through bionical Graphene（50mL ultra-pure water+5mL ammonia）In, stir
After be transferred in reactor, reactor is placed in 120 DEG C of baking oven and reacts 6 h.After hydro-thermal reaction terminates, it is drawn off
Sucking filtration, dries 12 h for 50 DEG C and can get the high energy storage electrode material of cobalt oxide quantum dot-bionical Graphene.
Embodiment 5
The first step：12 g Epipremnum aureum (Linde et Andre) (Bunting.) canes are washed away floating dust with 100 mL distilled water immersion 10 min, ethanol and ultra-pure water are pressed body
Amass and compare 1:3 are made into mixed liquor, and the use of salt acid for adjusting pH are 4, soak Epipremnum aureum (Linde et Andre) (Bunting.) cane 36 h using this mixed liquor 120 mL；
Second step：Epipremnum aureum (Linde et Andre) (Bunting.) cane after soaking is taken out, is then put in the glucose solution that 120 mL contain 5 %, impregnates 24
H, is repeatedly washed with ultra-pure water afterwards.By 0.25 g Ce (NO3)3•6H2O and 1 g Co (NO3)2•6H2O puts into 100 mL
Configure cerium cobalt liquor in distilled water solution, stalk is transferred in cerium cobalt liquor, many after magnetic agitation 8 h under 600 r/min
Secondary washing, is laid in culture dish, in 40 DEG C of baking oven, 6 hs is dried；
3rd step：Dried plant stem is put into corundum porcelain boat, is placed in tube furnace, pass to nitrogen protection, by 2 DEG C/
Min ramp to 800 DEG C, isothermal reaction 2 h；
4th step：After calcining terminates, cool to room temperature with the furnace；
5th step：To add in reactor through bionical Graphene, and add a small amount of ammonia, reactor will be placed in 120 DEG C of baking
6 h are reacted in case.After hydro-thermal reaction terminates, be drawn off sucking filtration, 50 DEG C drying 12 h, you can obtain cobalt oxide quantum dot-
The high energy storage electrode material of bionical Graphene.
Embodiment 6
The first step：Red for 10 g palm cane is washed away floating dust with 100 mL distilled water immersion 10 min, ethanol and ultra-pure water are pressed body
Amass and compare 1:3 are made into mixed liquor, and the use of salt acid for adjusting pH are 3, soak red palm cane 48 h using this mixed liquor 100 mL；
Second step：Red palm cane after soaking is taken out, is then put in the glucose solution that 140 mL contain 10 %, impregnates 12
H, is repeatedly washed with ultra-pure water afterwards.By 0.25 g Ce (NO3)3•6H2O and 1 g Co (NO3)2•6H2O puts into 100 mL
Configure cerium cobalt liquor in distilled water solution, stalk is transferred in cerium cobalt liquor, many after magnetic agitation 8 h under 600 r/min
Secondary washing, is laid in culture dish, in 40 DEG C of baking oven, 6 hs is dried；
3rd step：Dried plant stem is put into corundum porcelain boat, is placed in tube furnace, pass to nitrogen protection, by 2 DEG C/
Min ramp to 800 DEG C, isothermal reaction 2 h；
4th step：After calcining terminates, cool to room temperature with the furnace；
5th step：The ultra-pure water containing ammonia will be added through bionical Graphene（50mL ultra-pure water+5mL ammonia）In, stir
After be transferred in reactor, reactor is placed in 120 DEG C of baking oven and reacts 6 h.After hydro-thermal reaction terminates, it is drawn off
Sucking filtration, 50 DEG C of drying 12 h, you can obtain the high energy storage electrode material of cobalt oxide quantum dot-bionical Graphene.
Described above to the disclosed embodiments, makes professional and technical personnel in the field be capable of or uses the present invention.
Multiple modifications to these embodiments will be apparent from for those skilled in the art, as defined herein
General Principle can be realized without departing from the spirit or scope of the present invention in other embodiments.Therefore, the present invention
It is not intended to be limited to the embodiments shown herein, and be to fit to and principles disclosed herein and features of novelty phase one
The scope the widest causing.
Claims (10)
1. the preparation method of the high energy storage electrode material of cobalt oxide quantum dot-bionical Graphene is it is characterised in that include following walking
Suddenly：
The first step：The pre-treatment of plant stem
Plant haulm raw material is cleaned, standby；Ethanol and ultra-pure water are made into mixed liquor, and adjust pH of mixed for 1 ~ 4, standby
With；The plant haulm cleaned is completely soaked and carries out activation processing in described mixed liquor；
Second step：The post processing of plant stem
Plant stem after soaking is taken out, then impregnated in glucose solution and carry out net mending process, take out and clean, it
It is placed in afterwards in salt containing cerium and the aqueous solution of cobalt salt, and magnetic agitation, take out and clean and be dried；
3rd step：Heat treatment
Under nitrogen protection, the plant stem being dried is carried out calcining heat treatment, its calcining heat treatment condition is：It is to slowly warm up to
700 ~ 900 DEG C, it is incubated 2 h ~ 4 h；
4th step：Cooling
After calcining terminates, cool to room temperature with the furnace；
5th step：The growth in situ of oxide
Product after cooling is added in the ultra-pure water containing ammonia, is transferred to after stirring in reactor, carries out hydro-thermal anti-
Should, after completion of the reaction, wash and be dried, obtain final product the high energy storage electrode material of cobalt oxide quantum dot-bionical Graphene.
2. the preparation method of the high energy storage electrode material of cobalt oxide quantum dot-bionical Graphene according to claim 1, it is special
Levy and be, in the 5th step, described hydrothermal reaction condition is：120 DEG C, 6 h；The filling rate of described reactor is 45% ~ 60%；
The addition of described ammonia is the volume of the described ultra-pure water of 1/10 ~ 1/15 volume.
3. the preparation method of the high energy storage electrode material of cobalt oxide quantum dot-bionical Graphene according to claim 1, it is special
Levy and be, in second step, the mass fraction of the middle glucose of described glucose solution is 5 % ~ 10 %.
4. the preparation method according to the high energy storage electrode material of claim 1 or cobalt oxide quantum dot described in 2 or 3-bionical Graphene,
It is characterized in that, in second step, the amount of the material of described cerium salt and cobalt salt is than for 1:4.
5. the preparation method according to the high energy storage electrode material of claim 1 or cobalt oxide quantum dot described in 2 or 3-bionical Graphene,
It is characterized in that, described plant haulm be rape flower cane, corn stem, Canna generalis Bailey cane, hyacinth cane, Epipremnum aureum (Linde et Andre) (Bunting.) cane,
One of red palm cane.
6. according to claim 1 or 3 the high energy storage electrode material of cobalt oxide quantum dot-bionical Graphene preparation method, its
It is characterised by, in second step, in described aqueous solution, the concentration of cobalt salt is 5 ~ 15 g/L, the quality of described plant stem and cobalt salt
Than for 5 ~ 20:1；In second step, described dip time is 12 ~ 24 h；The volume of described glucose solution is not less than 10 mL/g
Plant stem.
7. the preparation side according to the high energy storage electrode material of claim 1 or cobalt oxide quantum dot described in 2 or 3-bionical Graphene
It is characterised in that in the third step, described heating rate is 2 DEG C/min to method.
8. the preparation side according to the high energy storage electrode material of claim 1 or cobalt oxide quantum dot described in 2 or 3-bionical Graphene
It is characterised in that in the first step, in described mixed liquor, the volume ratio of ethanol and ultra-pure water is 1 to method:3；Described soak time is
36 h~72 h.
9. the preparation side according to the high energy storage electrode material of claim 1 or cobalt oxide quantum dot described in 2 or 3-bionical Graphene
It is characterised in that in second step, described magnetic stirring speed is 500 ~ 1500 r/min, mixing time is 8 ~ 24 h to method；?
In second step, described baking temperature is 40 DEG C, and drying time is 6-12 h；In the 5th step, described drying condition is：50
DEG C, 12 h.
10. cobalt oxide quantum dot-bionical high energy storage electrode material of Graphene is it is characterised in that described electrode material will by right
The preparation method described in any one of 1-9 is asked to be prepared from.
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