CN105938761B - Magnesium cobalt/cobalt oxide/graphene composite material as electrode material for super capacitor and preparation method thereof - Google Patents
Magnesium cobalt/cobalt oxide/graphene composite material as electrode material for super capacitor and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of magnesium cobalt/cobalt oxide/graphene composite materials as super capacitor material and preparation method thereof.The composite material is made of nanoscale magnesium cobalt/cobalt oxide and graphene, and nanoscale magnesium cobalt/cobalt oxide is petal-shaped cluster structure, and graphene is sheet, is covered on magnesium cobalt/cobalt oxide.The composite material preparation includes 1）The synthesis of modified graphene oxide；2）Magnesium cobalt salt is added in modified graphene oxide solution and alkali source, hydrothermal reduction method prepare magnesium cobalt hydroxide/graphene composite material；3）By obtained magnesium cobalt hydroxide/graphene composite material high-temperature calcination, MgCo is made2O4/ graphene composite material.Compared with existing graphene combination electrode material, the obtained MgCo of the present invention2O4/ graphene composite material provides more preferably design feature, the specific surface area of bigger, smaller resistance to mass tranfer and longer cycle life, has a good application prospect in energy reserves field.
Description
Technical field
The invention belongs to electrochemical energy source domain, more particularly to a kind of magnesium cobalt/cobalt oxide/graphene hybrid supercapacitor
Electrode material and preparation method thereof.
Background technology
Ultracapacitor is divided into double as a kind of emerging energy capture and the device of storage according to its energy storage mechnism difference
Electric layer capacitor and Faraday pseudo-capacitance device, the former is the electric double layer based on electrode and electrolyte surface come storage energy, at present
Common electrode material is mostly carbon-based material, such as activated carbon, carbon black, carbon nanotubes, graphene, carbon fiber；The latter is by electricity
Active material on extremely occurs redox reaction or metal ion and carrys out storage energy in electrode surface generation underpotential deposition,
Currently used material is metal oxide（Such as RuO2, MnO2, Fe3O4, Co3O4）And conducting polymer（Such as polyaniline gathers
Pyrroles and polythiophene）.Electric double layer capacitance electrode material has comparatively ideal specific surface area, electric conductivity, structural stability, multiplying power
Property, power density and cycle life etc., but capacitance is limited by its theoretical value.Faraday pseudo-capacitance electrode material and double electricity
Layer capacitance electrode, which is compared, has higher specific capacitance value, but metal conductive oxide is poor, conducting polymer structures stability
The inferior positions such as difference limit its cyclical stability and forthright again, so as to be unfavorable for its application in practice.
In electric double layer capacitance electrode material, graphene with respect to other materials, have higher electrical conductivity, specific surface area and
Excellent mechanical performance, therefore be widely studied, it is preferable electrode material in ultracapacitor.However, in practical applications,
There are strong model ylid bloom action power between graphene sheet layer, serious stacking phenomenon can occur in preparation process, so as to lose
Substantial amounts of effectively specific surface simultaneously increases the resistance of electrolyte ion transmission, constrains application of the graphene in ultracapacitor.Cause
This how by the fake capacitance material load with high capacity on graphene, both make to generate synergistic effect, improve device
Integral capacitor performance is the hot issue that current researchers explore.
The content of the invention
It is existing to solve the purpose of the present invention is compound by the way that graphene and a kind of metal oxide magnesium cobalt/cobalt oxide are carried out
There are in technology not high electric double layer capacitance electrode material capacitance, wild goose capacitance cyclical stability and technical problems such as forthright difference again, carry
For a kind of while there is high capacity, good times of forthright and cyclical stability magnesium cobalt/cobalt oxide/graphene composite material.
The present invention adopts the following technical scheme that.
A kind of magnesium cobalt/cobalt oxide/graphene composite material as electrode material for super capacitor is provided, utilizes graphene
There is high conductivity, the characteristic of high-specific surface area as electrode material for super capacitor, by electric with the wild goose with high capacity
Capacity materials magnesium cobalt/cobalt oxide is compound, with the defects of both overcoming, by the synergistic effect of composite material, improves the whole electricity of device
Capacitive energy.
Magnesium cobalt/cobalt oxide/graphene composite material provided by the invention as electrode material for super capacitor is by nanoscale
Magnesium cobalt/cobalt oxide and flake graphite alkene composition, wherein nanoscale magnesium cobalt/cobalt oxide are the quality percentage of MgCo2O4, wherein graphene
Content is 1%~20%, further preferably 5%~15%.
Wherein, it is nanoscale magnesium cobalt oxide that the present invention, which controls the magnesium cobalt/cobalt oxide in magnesium cobalt/cobalt oxide/graphene composite material,
Compound, the particle diameter of the nanoscale magnesium cobalt/cobalt oxide is 10nm~20nm.The particle diameter of magnesium cobalt/cobalt oxide is smaller, easier
It is combined with graphene sheet layer, electric conductivity, electrochemical stability and the cycle performance of the composite material formed are better；It is but too small
Particle diameter easily form reunion, be unfavorable for forming electron propagation ducts instead.Therefore the control rational grain of magnesium cobalt/cobalt oxide
Footpath can promote the combination of magnesium cobalt/cobalt oxide and graphene sheet layer, enhance the electric conductivity of composite material, electrochemical stability and follow
Ring performance.
Magnesium cobalt/cobalt oxide/graphene composite material provided by the invention as electrode material for super capacitor, pattern
For：Nanoscale magnesium cobalt/cobalt oxide is petal-shaped cluster structure, emulsion sheet lamellar graphite alkene on flower-shaped nanoscale magnesium cobalt/cobalt oxide；
Sheet graphene is transparent yarn shape, is wrapped in the magnesium cobalt/cobalt oxide surface for the interface that magnesium cobalt/cobalt oxide and graphene are formed.
The appearance structure of the composite material, magnesium cobalt/cobalt oxide are petal-like structures, have comparatively ideal specific surface area to be conducive to electrochemistry survey
Examination intermediate ion transport and the timely progress of redox reaction；And it is compound with Sheet Graphite alkene piece, constitute magnesium cobalt oxidation
The effect of the barrier material as graphene film of object, prevents the aggregation of graphene sheet layer, makes graphene effective ratio area
Increase, enhance the penetration of electrolyte, improve the electric double layer capacitance of graphene；Magnesium cobalt/cobalt oxide can contribute certain puppet simultaneously
Capacitance, and then improve the total capacitance of composite material.
Magnesium cobalt/cobalt oxide/graphene composite material, wherein stone provided by the invention as electrode material for super capacitor
Black alkene is reduced by hydro-thermal reaction for graphene oxide and is made, wherein the graphene oxide have passed through changing for bivalent cation
Property, wherein bivalent cation is Ni2+、Co2+、Cu2+、Mn2+Any one of.Using cation-modified graphene oxide, wherein one
Be using between the negatively charged oxygen functional group on cationic positive charge and graphene oxide by electrostatic interaction the former
Intercalation increases interlamellar spacing between the latter's lamella, reduces and reunites；Second is that magnesium cobalt/cobalt oxide is promoted to be dispersed in graphene oxide
On lamella, good interfacial contact is formed simultaneously.The introducing of bivalent cation, without negative interaction, may additionally facilitate two to electrochemical properties
Each constituent element collaboration contribution, effectively promotes chemical property in first composite material.
The present invention also provides the preparations of magnesium cobalt/cobalt oxide/graphene composite material as electrode material for super capacitor
Method, specific steps include：
Specifically include following steps：
1）It prepares graphene oxide suspension and is pre-processed with cation：Using graphite powder as raw material, pass through Hume's method
Prepare graphene oxide, graphene oxide washed, alcohol washes, dry after, it is levigate it is scattered in aqueous solution, add in cationic forerunner
Body after being stirred, obtains cation-modified graphene oxide after centrifuging, precipitate, wash, dry, the cation is changed
Property graphene oxide it is levigate after it is scattered in aqueous solution, form modified graphene oxide solution.Wherein described cationic presoma
To be any in Nickel Chloride, dichloride copper, cobaltous dichloride and manganous chloride, wherein the cationic presoma added in and oxidation stone
The mass ratio of black alkene is 1%~2%.
2）Prepare the mixing precursor liquid of magnesium cobalt salt and graphene oxide：According to molar ratio it is 2 by cobalt acetate and magnesium acetate:1
It is dissolved in nitric acid, obtains cobalt nitrate and magnesium nitrate mixed solution, total concentration is the mol/L of 0.015 mol/L~0.15；It is mixed at this
It closes addition alkaline conditioner in solution and pH is adjusted to 6.5~7.0, add in step 1）In modified graphene oxide solution obtained,
The modified graphene oxide addition is magnesium cobalt/cobalt oxide MgCo2O4The 5%~15% of quality, is thoroughly mixed.Wherein institute
The alkaline conditioner stated is mainly used to adjust pH to 6.5~7, and for additive amount depending on required pH, effect is to promote metal ion
Hydrolysis and oxide formation, ammonium hydroxide or aqueous ethanolamine can be selected.
3）Prepare magnesium cobalt hydroxide/graphene composite material：By step 2）Last mixed liquor sealing obtained is warming up to
170 DEG C~180 DEG C, reaction 8 it is small when~24 it is small when postcooling, collect solid product, through deionized water and absolute ethyl alcohol alternating it is anti-
After backwashing is washed, dry, obtains magnesium cobalt hydroxide/graphene composite material.In the step, control suitable reaction temperature and when
Between, it is formed beneficial to magnesium cobalt/cobalt oxide and graphene oxide is reduced into graphene, while control of nanoscale magnesium cobalt/cobalt oxide
Particle size.Reducing agent need not be used in this method, graphene oxide is reduced into graphite by hydro-thermal reaction under the high temperature conditions
Alkene.
4）Prepare magnesium cobalt/cobalt oxide/graphene composite material：By step 3）Magnesium cobalt hydroxide/graphene obtained is compound
Material in 350 DEG C~750 DEG C under air atmosphere calcining 3 it is small when, it is multiple that cooled to room temperature obtains magnesium cobalt/cobalt oxide/graphene
Condensation material.
Magnesium cobalt/cobalt oxide/graphene composite material prepared by the present invention, during as electrode material for super capacitor, than electricity
Capacitance is under the constant current discharge of 1 A/g up to 1625 F/g；And when increasing current strength to 10 A/g, specific capacitance value retains
More than 80%, it is forthright excellent again；After 10000 constant current cycle charge-discharges are undergone, specific capacitance value can retain more than 93%, Xun Huan
Stability is good.
And the present invention prepares magnesium cobalt/cobalt oxide/graphene composite material, technique using hydro-thermal reaction method and calcination processing
Simply, it is at low cost, the cycle is short, low energy consumption, be suitble to industrialized production.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of magnesium cobalt/cobalt oxide/graphene composite material made from embodiment 1.
Fig. 2 is magnesium cobalt/cobalt oxide/graphene composite material made from embodiment 1 in magnesium cobalt/cobalt oxide and graphene interface
Transmission electron microscope picture.
Fig. 3 is the charging and discharging curve under 1 A/g constant currents of magnesium cobalt/cobalt oxide/graphene composite material made from embodiment 1
Figure.
Fig. 4 is magnesium cobalt/cobalt oxide made from embodiment 1/specific capacitance of the graphene composite material under different current strength
Value.
Fig. 5 is the charge and discharge cycles under 20 A/g constant currents of magnesium cobalt/cobalt oxide/graphene composite material made from embodiment 1
The attenuation of 10000 specific capacitances.
Fig. 6 is magnesium cobalt/cobalt oxide made from embodiment 1/cyclic voltammetry curve of the graphene composite material under 10 mV/s
Figure.
Specific embodiment
Here is part specific embodiment, and based on the embodiments of the present invention, those skilled in the art are not making
The every other embodiment obtained under the premise of creative work, belongs to the scope of protection of the invention.
Embodiment 1
The first step：1）Using graphite as raw material, graphene oxide is prepared by Hume's method, it will be through overpickling, after alcohol washes, dries
Graphene oxide it is levigate, by its ultrasonic disperse in deionized water, obtain 2 mg/mL graphene oxide aqueous dispersions of concentration；
2) 190 mg are weighed（0.80 mmol）NiCl2·6H2O is scattered in 20 mL 1) in obtained graphene oxide aqueous dispersions,
80 mL are diluted with water to, stirring evenly makes it fully dissolve；3）Successively through centrifuging, precipitate, deionization washing, it is dry after obtain
Nickel ion modified graphene oxide, its is scattered in after levigate obtained in deionized water 2 mg/mL modified graphene oxide it is molten
Liquid.
Second step：It is 2 by molar ratio:1 Co (CH3COO)2·4H2O and Mg (CH3COO)2·4H2O is dissolved in dust technology,
It is configured to the Co of 80 mL2+And Mg2+Total concentration is the solution of 0.015 mol/L, and the ammonium hydroxide for adding in 25 wt% is adjusted as alkalescence
PH is adjusted in the range of 6.5~7 by agent, add the 20 mL first steps made from modified graphene oxide solution, mixed through ultrasonic disperse
It closes and uniformly, is placed in the autoclave that capacity is 100 mL, reaction kettle sealing, when reaction 12 is small at 170 DEG C, natural cooling
To room temperature；Solid reaction product is collected, product is washed through deionized water and absolute ethyl alcohol alternate repetition, it is dry, obtain gel
Magnesium cobalt hydroxide/graphene composite material of shape.Grinding, gelatinous magnesium cobalt hydroxide/graphene after grinding is compound
Material in air atmosphere at 350 DEG C calcining 3 it is small when, you can obtain magnesium cobalt/cobalt oxide/graphene composite material, after tested, stone
Mass percentage of the black alkene in magnesium cobalt/cobalt oxide/graphene composite material is 5%.
Embodiment 2
The first step：1）Using graphite as raw material, graphene oxide is prepared by Hume's method, it will be through overpickling, after alcohol washes, dries
Graphene oxide it is levigate, by its ultrasonic disperse in deionized water, obtain 2 mg/mL graphene oxide aqueous dispersions of concentration；
2) 136 mg are weighed（0.80 mmol）CuCl2·2H2O is scattered in 20 mL 1) in obtained graphene oxide aqueous dispersions,
80 mL are diluted with water to, stirring evenly makes it fully dissolve；3）Successively through centrifuging, precipitate, deionization washing, it is dry after obtain
Copper ion modified graphene oxide, its is scattered in after levigate obtained in deionized water 2 mg/mL modified graphene oxide it is molten
Liquid.
Second step：It is 2 by molar ratio:1 Co (CH3COO)2·4H2O and Mg (CH3COO)2·4H2O is dissolved in dust technology,
It is configured to the Co of 80 mL2+And Mg2+Total concentration is the solution of 0.05 mol/L, will as alkaline conditioner by the use of 25 wt% ammonium hydroxide
PH is adjusted in the range of 6.5~7, adds modified graphene oxide solution made from the 20 mL first steps, is mixed through ultrasonic disperse equal
It is even, it is placed in the autoclave that capacity is 100 mL, reaction kettle sealing when reaction 10 is small at 172 DEG C, naturally cools to room
Temperature；Solid reaction product is collected, product is washed through deionized water and absolute ethyl alcohol alternate repetition, it is dry, it obtains gelatinous
Magnesium cobalt hydroxide/graphene composite material.Grinding, by gelatinous magnesium cobalt hydroxide/graphene composite material after grinding
When calcining 3 is small at 450 DEG C in air atmosphere, you can obtain magnesium cobalt/cobalt oxide/graphene composite material, after tested, graphene
Mass percentage in magnesium cobalt/cobalt oxide/graphene composite material is 8%.
Embodiment 3
The first step：1）Using graphite as raw material, graphene oxide is prepared by Hume's method, it will be through overpickling, after alcohol washes, dries
Graphene oxide it is levigate, by its ultrasonic disperse in deionized water, obtain 2 mg/mL graphene oxide aqueous dispersions of concentration；
2) 190 mg are weighed（0.80 mmol）CoCl2·6H2O is scattered in 20 mL 1) in obtained graphene oxide aqueous dispersions,
80 mL are diluted with water to, stirring evenly makes it fully dissolve；3）Successively through centrifuging, precipitate, deionization washing, it is dry after obtain
Cobalt ions modified graphene oxide, by it from being scattered in modified graphene oxide that 2 mg/mL are obtained in deionized water after levigate
Solution.
Second step：It is 2 by molar ratio:1 Co (CH3COO)2·4H2O and Mg (CH3COO)2·4H2O is dissolved in dust technology,
It is configured to 80 mL Co2+And Mg2+Total concentration is the solution of 0.10 mol/L, by the use of 25 wt% ammonium hydroxide as alkaline conditioner by pH
It is adjusted in the range of 6.5~7, the modified graphene oxide solution added in the 20 mL first steps is uniformly mixed through ultrasonic disperse, is put
In the autoclave for being 100 mL in capacity, reaction kettle sealing, when reaction 9 is small at 176 DEG C, cooled to room temperature；It receives
Collect solid reaction product, product is washed through deionized water and absolute ethyl alcohol alternate repetition, it is dry, obtain gelatinous magnesium cobalt hydrogen
Oxide/graphene composite material.By gelatinous magnesium cobalt hydroxide/graphene composite material after grinding in air atmosphere
At 550 DEG C calcining 3 it is small when, you can obtain magnesium cobalt/cobalt oxide/graphene composite material, after tested, graphene magnesium cobalt/cobalt oxide/
Mass percentage in graphene composite material is 12%.
Embodiment 4
The first step：1）Using graphite as raw material, graphene oxide is prepared by Hume's method, it will be through overpickling, after alcohol washes, dries
Graphene oxide it is levigate, by its ultrasonic disperse in deionized water, obtain 2 mg/mL graphene oxide aqueous dispersions of concentration；
2) 158 mg are weighed（0.80 mmol）MnCl2·4H2O is scattered in 20 mL 1) in obtained graphene oxide aqueous dispersions,
80 mL are diluted with water to, stirring evenly makes it fully dissolve；3）Successively through centrifuging, precipitate, deionization washing, it is dry after obtain
Manganese ion modified graphene oxide, its is scattered in after levigate obtained in deionized water 2 mg/mL modified graphene oxide it is molten
Liquid.
Second step：It is 2 by molar ratio:1 Co (CH3COO)2·4H2O and Mg (CH3COO)2·4H2O is dissolved in dust technology,
It is configured to 80 mL Co2+And Mg2+Total concentration is the solution of 0.15 mol/L, by the use of 25 wt% ammonium hydroxide as alkaline conditioner by pH
It is adjusted in the range of 6.5~7, the modified graphene oxide solution added in the 20 mL first steps is uniformly mixed through ultrasonic disperse, is put
In the autoclave for being 100 mL in capacity, reaction kettle sealing, when reaction 8 is small at 180 DEG C, cooled to room temperature；It receives
Collect solid reaction product, product is washed through deionized water and absolute ethyl alcohol alternate repetition, it is dry, obtain gelatinous magnesium cobalt hydrogen
Oxide/graphene composite material.By gelatinous magnesium cobalt hydroxide/graphene composite material after grinding in air atmosphere
At 750 DEG C calcining 3 it is small when, you can obtain magnesium cobalt/cobalt oxide/graphene composite material, after tested, graphene magnesium cobalt/cobalt oxide/
Mass percentage in graphene composite material is 15%.
Magnesium cobalt/cobalt oxide/graphene composite material made from each embodiment is tested for the property.
1）Scanning electron microscope is carried out（SEM）And transmission electron microscope（TEM）Test.Such as the magnesium cobalt oxide made from embodiment 1 of attached drawing 1
The sem test figure of compound/graphene composite material, by can see on figure：Flower-shaped nanoscale magnesium cobalt/cobalt oxide overlying
Cover plate shape graphene, the particle diameter of nanoscale magnesium cobalt/cobalt oxide is 10 nanometers ~ 20 nanometers, is petal-shaped cluster structure.Attached drawing 2
It, can on figure for transmission electron microscope picture of the magnesium cobalt/cobalt oxide/graphene composite material in magnesium cobalt/cobalt oxide and graphene interface on chip
See, graphene sheet layer is transparent yarn shape, is wrapped in the magnesium cobalt/cobalt oxide surface of interface.
2）Specific capacitance is tested：By the various embodiments described above, finally magnesium cobalt/cobalt oxide/graphene composite material obtained is made respectively
Three-electrode system is assembled into electrode slice and carries out constant current charge-discharge test, and current density is to be surveyed under the constant current charge-discharge of 1 A/g
Examination, if the magnesium cobalt/cobalt oxide/graphene hybrid supercapacitor electrode material made from embodiment 1 of attached drawing 3 is in 1 A/g constant currents
Charge and discharge electrograph can be calculated its specific capacitance value up to 1625 F/g according to curve.Magnesium cobalt/cobalt oxide/graphite made from embodiment 2
Alkene composite material under 1 A/g constant current charge-discharges specific capacitance up to 1265 F/g；Magnesium cobalt/cobalt oxide/graphite made from embodiment 3
Specific capacitance is up to 1200 F/g under 1 A/g constant current charge-discharges of alkene composite material；Magnesium cobalt/cobalt oxide/graphene made from embodiment 4
Specific capacitance is up to 1088 F/g under 1 A/g constant current charge-discharges of hybrid supercapacitor material.
Fig. 4 is strong in different electric currents for magnesium cobalt/cobalt oxide/graphene hybrid supercapacitor electrode material made from embodiment 1
The specific capacitance value of lower test is spent, specific capacitance is 1625 F/g under 1 A/g, and increasing under 10 A/g still there are 1300 F/g, is retained
80 % are shown forthright again well.
3）Cycle charge discharge electrical testing：By the various embodiments described above, finally magnesium cobalt/cobalt oxide/graphene composite material obtained divides
Electrode slice is not made and is assembled into three-electrode system progress charge and discharge cycles test.Such as Fig. 5 magnesium cobalt oxidations made from embodiment 1
Object/graphene composite material is 20 A/g constant current charge-discharge cyclic curves in current density, it can be seen that Xun Huan 10000 times
Specific capacitance value can retain more than 93%, show good cyclical stability.
4）Cyclic voltammetry curve is tested：By the last magnesium cobalt/cobalt oxide/graphene composite material obtained of the various embodiments described above
Cyclic voltammetry curve sweep test is carried out, such as the following for magnesium cobalt/cobalt oxide/graphene composite material of the acquisition of embodiment 1 of attached drawing 6
Ring volt-ampere curve figure shown in figure, the cyclic voltammetry curve of material be clearly distinguishable from typical double layer capacitor close to square
There are two peak values in the shape of shape, it was demonstrated that the capacitance of the composite material includes the contribution for the wild goose capacitance for coming from magnesium cobalt/cobalt oxide.
The confirmation of more than performance test data, magnesium cobalt/cobalt oxide/graphene composite material produced by the present invention, electric double layer capacitance
Material graphene and Faraday pseudo-capacitance material magnesium cobalt/cobalt oxide realize compound in the preparation process of the present invention, and reach
With reference to the former high power is forthright, the goal of the invention of the advantage of high circulation stability and the latter's high specific capacitance, the fake capacitance of high capacity
Material magnesium cobalt/cobalt oxide is supported on sheet graphene, and the two generates synergistic effect, improves the integral capacitor performance of device.
Claims (7)
1. magnesium cobalt/cobalt oxide/graphene composite material as electrode material for super capacitor, it is characterised in that：The magnesium cobalt oxide
Compound/graphene composite material is made of nanoscale magnesium cobalt/cobalt oxide and graphene, and the nanoscale magnesium cobalt/cobalt oxide is
MgCo2O4；
The nanoscale magnesium cobalt/cobalt oxide is petal-shaped cluster structure；The graphene is sheet；The nanoscale magnesium
Emulsion sheet lamellar graphite alkene on cobalt/cobalt oxide；The sheet graphene is transparent yarn shape, is wrapped in magnesium cobalt/cobalt oxide and graphite
The magnesium cobalt/cobalt oxide surface for the interface that alkene is formed；
The graphene is reduced by hydro-thermal reaction for graphene oxide and is made, and the graphene oxide have passed through bivalent cation
Modification, the bivalent cation be Ni2+、Co2+、Cu2+、Mn2+Any one of.
2. magnesium cobalt/cobalt oxide/graphene composite material according to claim 1 as electrode material for super capacitor,
It is characterized in that：The mass percentage of graphene is 1%~20% in the magnesium cobalt/cobalt oxide/graphene composite material.
3. magnesium cobalt/cobalt oxide/graphene composite material according to claim 2 as electrode material for super capacitor,
It is characterized in that：The mass percentage of graphene is 5%~15% in the magnesium cobalt/cobalt oxide/graphene composite material.
4. magnesium cobalt/cobalt oxide/graphene composite material according to claim 1 as electrode material for super capacitor,
It is characterized in that：The particle diameter of the nanoscale magnesium cobalt/cobalt oxide is 10 nanometers~20 nanometers.
5. it is multiple to prepare magnesium cobalt/cobalt oxide/graphene of the Claims 1 to 4 any one of them as electrode material for super capacitor
The method of condensation material, comprises the following steps：
1) prepare graphene oxide suspension and pre-processed with cation：Using graphite powder as raw material, prepared by Hume's method
Graphene oxide washes graphene oxide, alcohol washes, dry after, it is levigate it is scattered add in cationic presoma in aqueous solution,
After being stirred, cation-modified graphene oxide is obtained after centrifuging, precipitate, wash, dry, by the cation-modified oxygen
Disperse in aqueous solution, to form modified graphene oxide solution after graphite alkene is levigate；
2) the mixing precursor liquid of magnesium cobalt salt and graphene oxide is prepared：According to molar ratio it is 2 by cobalt acetate and magnesium acetate:1 is dissolved in
In nitric acid, cobalt nitrate and magnesium nitrate mixed solution are obtained, total concentration is 0.015mol/L~0.15mol/L；In the mixed solution
PH is adjusted to 6.5~7.0 by middle addition alkaline conditioner, adds in modified graphene oxide solution made from step 1)；Described changes
Property graphene oxide addition be magnesium cobalt/cobalt oxide MgCo2O4The 5%~15% of quality, is thoroughly mixed；
3) magnesium cobalt hydroxide/graphene composite material is prepared：The last mixed liquor sealing obtained of step 2) is warming up to 170 DEG C
~180 DEG C, reaction 8 it is small when~24 it is small when postcooling, collect solid product, washed through deionized water and absolute ethyl alcohol alternate repetition
It washs, it is dry, obtain magnesium cobalt hydroxide/graphene composite material；
4) magnesium cobalt/cobalt oxide/graphene composite material is prepared：By magnesium cobalt hydroxide/graphene composite material made from step 3)
After being calcined in 350 DEG C~750 DEG C under air atmosphere, it is compound that cooled to room temperature obtains the magnesium cobalt/cobalt oxide/graphene
Material；
Wherein, the cationic presoma is selected from Nickel Chloride, dichloride copper, cobaltous dichloride and manganous chloride.
6. preparation method according to claim 5, which is characterized in that the cationic presoma additive amount is cation
The mass ratio of presoma and graphene oxide is 1%~2%.
7. preparation method according to claim 5, which is characterized in that the alkaline conditioner is selected from ammonium hydroxide and ethanolamine
Aqueous solution.
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| CN101740233B (en) * | 2010-02-09 | 2011-06-29 | 暨南大学 | Vermicular mesoporous carbon/Bi2O3 composite electrode material as well as preparation method and application thereof |
| CN104576075A (en) * | 2014-12-31 | 2015-04-29 | 江苏江大环保科技开发有限公司 | Preparation method of 3D coralline graphene/NiCo2O4 composite material and application of same in super capacitor |
| CN104701035A (en) * | 2015-03-20 | 2015-06-10 | 中国科学院青海盐湖研究所 | Preparation method of metal oxide/graphene or multi-metal oxide/graphene composite electrode material |
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