CN107230784A - A kind of spherical graphite alkene/mangano-manganic oxide composite and preparation method and application - Google Patents
A kind of spherical graphite alkene/mangano-manganic oxide composite and preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of spherical graphite alkene/mangano-manganic oxide composite and preparation method and application, the microstructure of the composite is：Using spherical graphite alkene as matrix, trimanganese tetroxide nano piece is dispersed in spherical graphite alkene matrix surface, forms the complex microsphere of generally chondritic.Preparation method comprises the following steps：(1) spherical graphite alkene and deionized water are mixed, it is ultrasonically treated, obtain spherical graphite alkene dispersion liquid；Then liquor potassic permanganate, then ultrasonic disperse are added, spherical graphite alkene/potassium permanganate dispersion liquid is obtained；(2) by spherical graphite alkene/potassium permanganate dispersion liquid hydro-thermal reaction, reacted sediment is centrifugally separating to obtain after the completion of reaction, washing precipitate is produced.Above-mentioned spherical graphite alkene/application of the mangano-manganic oxide composite as electrode material in ultracapacitor.Spherical graphite alkene/mangano-manganic oxide composite of the present invention is fabricated to ultracapacitor, and specific capacitance is up to 316.65F/g.
Description
Technical field
The invention belongs to graphene nanocomposite material preparation field, and in particular to a kind of spherical graphite alkene/tetra- aoxidize three
Manganese composite and preparation method thereof and the application in terms of super capacitor electrode.
Background technology
In recent years, with the rapid development of society, the problems such as fossil energy is short, environmental pollution is serious increasingly dashes forward
Go out, force various countries to strive to find the new energy and advanced energy storage technology of sustainable development.As a kind of new type of energy storage device,
Ultracapacitor because with energy density is high, specific capacity is big, have extended cycle life, fast charging and discharging and advantages of environment protection, quilt
Various fields are widely applied to, such as：Aero-Space, military equipment, electrical equipment, communications and transportation and electronic information etc..Super capacitor
The chemical property of device is determined by electrode material, therefore development has high-specific surface area, high conductivity and structural stability
Electrode material be crucial.
Current electrode material is broadly divided into three kinds：Carbon-based material, metal oxide and conducting polymer.Conducting polymer bag
Polyaniline, polypyrrole, polythiophene etc. are included, it has higher electrical conductivity, but in charge and discharge process, its structure disperses is big,
Stability is poor so that such electrode material capacity density is decayed comparatively fast during charge and discharge cycles, therefore improves the material
Chemical stability is technological difficulties.Carbon-based material includes activated carbon, CNT, carbon aerogels, carbon black, carbon fiber, graphene
Deng it has high conductivity and chemical stability.Ultracapacitor carbon material successful commercialization, but its specific capacity and energy
Density needs further raising.Metal oxide includes RuO2, MnO2, Mn3O4, NiO, Co3O4Deng RuO2Chemical property is excellent
It is good, but price is high, MnO2, Mn3O4, NiO, Co3O4Etc. cheap, but electric conductivity is poor.Therefore answering for electrode material is realized
Close, be expected to evade respective shortcoming, play good cooperative effect.
In carbon material, graphene specific surface area is big, electrical conductivity is high, chemical stability is superior, is expected to improve carbon material conduct
The specific capacity of electrode material for super capacitor, but graphene easily stacks in electrode production process, causes specific surface area
Reduction, specific capacity reduction, and the jolt ramming of graphene and compacted density are all very low, therefore, how to avoid graphene in electrode
The graphene for stacking, preparing high-tap density occurs in preparation process, electrode material for super capacitor is used as graphene
It is crucial.In metal oxide, the most electric conductivity of metal oxide of high-energy-density is poor, therefore by realizing graphene and gold
Belonging to the compound composite to develop high-energy-density and high conductivity of oxide turns into the research side of super capacitor material
To.
Chinese patent document CN101811696A (application numbers：201010158087.7) disclose one kind graphene-supported four
Co 3 O nano composite material and preparation method thereof, is made up of, cobaltosic oxide is supported on stone graphene and cobaltosic oxide
In black alkene nanometer sheet, the mass fraction of graphene nanometer sheet is 2%-95%wt, and the thickness of graphene nanometer sheet is received for 0.3~50
Rice, the particle diameter of cobaltosic oxide is 1~200 nanometer, and cobaltosic oxide is spherical or sheet.Preparation method is：Take graphite oxide
Alkene solution and divalent cobalt, high molecular surfactant mixing.Then with add oxidant aqueous slkali mixing after stirring or
Ultrasound 0.2~5 hour, is transferred in pyroreaction kettle, and being annealed at 100~250 DEG C obtains product for 3~30 hours, scrubbed,
Dry, produce graphene-supported cobaltosic oxide nano composite material.Also, Chinese patent document CN 103693639A (applications
Number：201310703074.7) a kind of preparation method of iron/Mn oxide doped graphene composite is disclosed, is passed through first
The magnetic graphene composite and Manganese Ferrite of solvent structure difference size Fe3O4 nanoparticles modification are grapheme modified multiple
Condensation material, then using magnetic graphene composite as substrate, manganese sulfate is reducing agent, and potassium permanganate is oxidant, passes through oxygen
Change reduction reaction, the grapheme modified composite of synthesis manganese dioxide/ferroso-ferric oxide.
Although above-mentioned composite can be used in electrode material, and specific capacitance is also higher, and preparation process is complicated, required
Chemical reagent is more, introduces more accessory substances, it is crucial that these composites are all using the sheet stone for being easy to stack
Black alkene is used as carrier, it is impossible to play the advantage of graphene high-specific surface area, limits its practical application.
The content of the invention
In view of the shortcomings of the prior art, specific surface area is low, electric conductivity is poor, utilize stone in especially existing electrode material
Black alkene is prepared in electrode material and easily stacked and the low problem of electrode material volume and capacity ratio, and the present invention provides a kind of spherical graphite
Alkene/mangano-manganic oxide composite and preparation method and application.
Technical scheme is as follows：
A kind of spherical graphite alkene/mangano-manganic oxide composite, the microstructure of the composite is：With spherical graphite alkene
For matrix, trimanganese tetroxide nano piece is dispersed in spherical graphite alkene matrix surface, forms the compound of generally chondritic
Microballoon.
, according to the invention it is preferred to, the mass ratio of mangano-manganic oxide and spherical graphite alkene is in described composite
(0.1:1)~(1.2:1).
, according to the invention it is preferred to, the particle size of described composite is 500nm~4 μm.
, according to the invention it is preferred to, the tap density of described composite is 0.3g/cm3~0.8g/cm3, compare surface
Product is 150~300m2/g。
, according to the invention it is preferred to, the radius of described spherical graphite alkene is at 100nm-5 μm, further preferred 100nm-3
μm, more preferably 300nm-2 μm；
It is preferred that, the tap density of spherical graphite alkene is 0.05g/cm3-0.7g/cm3, further preferred 0.1~0.5g/
cm3, more preferably 0.2~0.5g/cm3；
It is preferred that, the specific surface area of spherical graphite alkene microballoon is 300~3000m2/ g, more preferably 800~
3000m2/ g, more preferably 1200~3000m2/g。
, according to the invention it is preferred to, described spherical graphite alkene is prepared as follows obtaining：
By graphene oxide and/or graphene dispersion into water or other solvents, aoxidized after adding into globule, mixing
The graphene oxide and/or graphene dispersing solution, are then spray-dried, carry it by graphene and/or graphene dispersing solution
It is smelt powdered, after cyclonic separation and high-temperature process, obtains spherical graphite alkene.The spherical graphite alkene is the ball of height rule
Shape.
According to the preparation method of spherical graphite alkene of the present invention, it is preferred that described graphene oxide or the particle diameter of graphene
In 300nm~300 μm；The graphene oxide and/or graphene are (50 with the mass ratio into globule:1)~(1:5) one, is entered
Step is preferably (50:1)~(1:2) (25, are more preferably:1)~(1:1) it is most preferably, (10:1)~(5:1).
According to the preparation method of spherical graphite alkene of the present invention, it is preferred that the temperature of spray drying is 100 DEG C~400 DEG C, is entered
One step is preferably 100 DEG C~300 DEG C, more preferably 150 DEG C~250 DEG C；Adding into the condition mixed after globule is：15 DEG C~
100 DEG C of stirrings 30s~24h, more preferably preferably 1min~12h, 5min~12h.
According to the preparation method of spherical graphite alkene of the present invention, it is preferred that the condition of high-temperature process is：100 DEG C~1200
1~48h is heated at DEG C；
More preferably：After 100 DEG C~300 DEG C 1~12h of processing, then after 300 DEG C~450 DEG C handle 1~12h,
450 DEG C~600 DEG C 1~12h of processing, then handle 1~12h at 600 DEG C~900 DEG C；
More preferably：2~48h is handled in 300 DEG C~600 DEG C, inert atmosphere, 600 DEG C~1200 DEG C are then heated to,
5~48h is handled in the inert atmosphere containing vapor or carbon dioxide or nitrogen or argon gas.
According to the preparation method of spherical graphite alkene of the present invention, it is preferred that other described solvents are polar solvent or non-pole
Property solvent.
According to the preparation method of spherical graphite alkene of the present invention, it is preferred that it is described be at least into globule in following material one
Kind, including organic molecule, organic nano material, inorganic nonmetallic nanometer material, metal oxide nano-material it is independent into
Globule, or graphene are individually combined into globule with foregoing into what globule was composited；
It is preferred that, organic nano material includes high molecule nano material, conducting polymer nano material, molecule tree nanometer material
Material；The macromolecule for forming high molecule nano material includes but is not limited to polyethylene, polypropylene, polyvinyl chloride, polyelectrolyte；Formed
The macromolecule of conducting polymer nano material includes but is not limited to polyacetylene, polypyrrole, polyaniline, polythiophene, poly- enedioxy
Thiophene phenol；Molecule tree nano-material surface has positive charge group, negative electrical charge group or neutral group, with 1-6 for chondritic,
Particle diameter 1-10nm；
It is preferred that, inorganic nonmetallic nanometer material include carbon nanomaterial, carbon nanomaterial include but is not limited to nano-sized carbon,
Single armed CNT, multi-walled carbon nanotube, acetylene black, graphene, graphene quantum dot, graphene oxide；Metal nano material
Including but not limited to gold, silver, copper, iron, cobalt, nickel, ruthenium, platinum, palladium；Forming the metal of metal oxide nano-material includes but does not limit
In gold, silver, copper, iron, cobalt, nickel, ruthenium, platinum, palladium；Non-metal simple-substance nano material includes but is not limited to：Sulphur, carbon, silicon, phosphorus.
According to the present invention, the preparation method of above-mentioned spherical graphite alkene/mangano-manganic oxide composite comprises the following steps：
(1) by spherical graphite alkene and deionized water according to mass ratio (1:300)~(1:700) at ratio mixing, ultrasound
10-20min is managed, spherical graphite alkene dispersion liquid is obtained；Then liquor potassic permanganate, then ultrasonic disperse 5-10min are added, is mixed
Close uniform spherical graphite alkene/potassium permanganate dispersion liquid；
(2) by spherical graphite alkene/potassium permanganate dispersion liquid at 100-300 DEG C hydro-thermal reaction 8-15h, after the completion of reaction from
The isolated reacted sediment of the heart, washing precipitate produces spherical graphite alkene/mangano-manganic oxide composite.
According to the preparation method of composite of the present invention, it is preferred that by spherical graphite alkene and potassium permanganate in step (1)
Mass ratio is 1：(2~4) liquor potassic permanganate is added；
It is preferred that, the molar concentration of liquor potassic permanganate is 0.05~0.15mol/L.
According to the preparation method of composite of the present invention, it is preferred that the hydro-thermal reaction described in step (2) is with poly- four
Carried out in the stainless steel cauldron of PVF liner, the volume compactedness of spherical graphite alkene/potassium permanganate dispersion liquid is 60-
80%；
It is preferred that, the rotating speed of centrifugation is 10000rpm, and centrifugation time is 5-40min；
It is preferred that, the mode of washing precipitate is：It is washed with deionized three times, ethanol washed once.
According to the present invention, above-mentioned spherical graphite alkene/mangano-manganic oxide composite is as electrode material in ultracapacitor
In application.
Graphene and the Mn of high-energy-density of the invention by high-tap density3O4It is compound to obtain electrode for super capacitor
The preferable composite of material.The spherical graphite alkene of the present invention has superhigh specific surface area and higher tap density, keeps it
While high specific surface area, it is to avoid common graphite alkene easily occurs to stack phenomenon in electrode production process, with high-energy
Composite after the mangano-manganic oxide of density is combined can make full use of the advantage of the two, not only solve graphene agglomeration traits,
And improve the conductance of mangano-manganic oxide.The spherical composite of the present invention is effectively improved compared with sheet layer material
Volume and capacity ratio, electric conductivity and the stability of electrode material.
Beneficial effects of the present invention are as follows：
1st, spherical graphite alkene/mangano-manganic oxide composite of the invention has fully gathered graphene and mangano-manganic oxide two
The advantage of material is planted, spherical graphite alkene tool has superhigh specific surface area and higher tap density, four compared with common graphite alkene
Mn 3 O nanometer sheet is scattered in the specific surface area that spherical graphite alkene surface adds composite, significantly reduces composite
Internal resistance, be conducive to the transfer of electric charge, thus add the chemical property of composite so that it is in fields such as energy storages
Have broad application prospects.
2nd, the radius for the spherical graphite alkene that the present invention is used is 300nm-20 μm, and tap density is 0.2~0.5g/cm3,
Specific surface area is 1200~3000m2/g.Its high-specific surface area and high-tap density, it is to avoid common graphite alkene is prepared in electrode
During the problem of stack, and ensure that high-specific surface area and high-volume and capacity ratio.
3rd, spherical graphite alkene/mangano-manganic oxide composite material and preparation method thereof of the invention is simple to operation, directly using stone
Black alkene is not required to add extra go back original reagent, reduces cost, reduce follow-up operating process as the source of reducing agent carbon,
And it is environment-friendly pollution-free, it is adapted to large-scale production.
4th, ultracapacitor is fabricated to using spherical graphite alkene/mangano-manganic oxide composite of the present invention, specific capacitance is high
Up to 316.65F/g.
Brief description of the drawings
Fig. 1 is the X ray diffracting spectrum of the gained spherical graphite alkene of embodiment 1/mangano-manganic oxide composite；
Fig. 2 is the Raman collection of illustrative plates of the gained spherical graphite alkene of embodiment 1/mangano-manganic oxide composite；
Fig. 3 is the scanning electron microscope (SEM) photograph of spherical graphene used in embodiment 1；
Fig. 4 is the scanning electron microscope (SEM) photograph of the gained spherical graphite alkene of embodiment 1/mangano-manganic oxide composite；
Fig. 5-6 is the chemical property curve of the gained spherical graphite alkene of embodiment 1/mangano-manganic oxide composite, wherein：
Fig. 5 is the different cyclic voltammetry curves swept under speed, and Fig. 6 is the charging and discharging curve under different current densities.
Embodiment
For a better understanding of the present invention, further illustrated below by specific embodiment, but be not used in limitation originally
Invention.
Spherical graphite alkene used is prepared as follows obtaining in embodiment：
By 0.1g graphene dispersions into water, 0.05-0.1g is added as into globule, graphene dispersion is obtained after mixing
Graphene dispersing solution, is then spray-dried by liquid, is refined into it powdered, after cyclonic separation and high-temperature process, obtains
Spherical graphite alkene.The spherical graphite alkene is spherical for height rule.
The temperature of spray drying is 150 DEG C~250 DEG C, and adding into the condition mixed after globule is：Stirred at 15 DEG C~100 DEG C
Mix 2h.
The condition of high-temperature process is：2~48h is handled in 300 DEG C~600 DEG C, inert atmosphere, 600 DEG C are then heated to
~1200 DEG C, 5~48h is handled in the inert atmosphere containing vapor or carbon dioxide or nitrogen or argon gas.
The scanning electron microscope (SEM) photograph of gained spherical graphite alkene as shown in figure 3, the radius of gained spherical graphite alkene is at 300nm-20 μm,
The tap density of spherical graphite alkene is 0.2~0.5g/cm3, the specific surface area of spherical graphite alkene microballoon is 1200~3000m2/g。
Embodiment 1
First 50mg spherical graphite alkene is dispersed in 30mL deionized waters, ultrasonically treated 20min；Add 10mL
0.1mol/L liquor potassic permanganate, ultrasonic disperse 10min；Then well mixed graphene/potassium permanganate dispersion liquid is turned
In the reactor for moving to 50mL, at this moment the volume compactedness of reactor reaches 80% or so, and reactor then is placed on into high temperature furnace
In react 10h at 200 DEG C；Reacted sediment is centrifuged out under 10000rpm rotating speed, and 3 are washed with deionized respectively
Secondary, ethanol is washed 1 time, in the air dry oven for being finally placed on 60 DEG C, is dried 12h, is produced spherical graphite alkene/mangano-manganic oxide
Composite.The mass ratio of mangano-manganic oxide and spherical graphite alkene is 1 in composite obtained by the present embodiment：3.
X ray diffracting spectrum such as Fig. 1 institutes of the composite for spherical graphite alkene/mangano-manganic oxide that the present embodiment is obtained
Show, as shown in Figure 1, the diffraction maximum of XRD diffraction maximums and graphene in composite and the PDF cards basic one of mangano-manganic oxide
Cause.
The Raman collection of illustrative plates of the composite for spherical graphite alkene/mangano-manganic oxide that the present embodiment is obtained as shown in Fig. 2 by
Fig. 2 is understood, obvious D peaks and G peaks is shown in Raman spectrum, the activation more larger than confirming composite of its larger peak intensity
Degree.
The scanning electron microscope (SEM) photograph of the composite for spherical graphite alkene/mangano-manganic oxide that the present embodiment is obtained as shown in figure 4, by
Fig. 4 understands that the microstructure of the composite is：Using spherical graphite alkene as matrix, trimanganese tetroxide nano piece is dispersed in
Spherical graphite alkene matrix surface, forms the complex microsphere of generally chondritic, and the particle size of composite is the μ of 700nm~3
m。
The composite of spherical graphite alkene/mangano-manganic oxide made from the present embodiment is made into working electrode, according to as follows
It is prepared by method：Composite, acetylene black and ptfe emulsion (concentration ratio) are uniformly mixed by 80: 15: 5 mass ratio
Close, obtained slurry is coated uniformly on area for 1x1cm by addition ethanol in proper amount stirring2Nickel foam on.By the bubble after coating
Foam nickel is dried in vacuo after 10h at 100 DEG C, and electrode slice is pressed into 7MPa pressure.
The chemical property of test compound material：With the supercapacitive of three-electrode system test compound material at room temperature
Matter, wherein reference electrode are saturated calomel electrode, are platinum electrode to electrode.Electrolyte is 1mol/L metabisulfite solutions.Circulation volt
Peace and constant current charge-discharge test are carried out on CHI660E type electrochemical workstations.Cyclic voltammetric and constant current charge-discharge test voltage
Scope is 0-1.0V.
Under 10mV/s sweep speed, the specific capacitance of the spherical graphite alkene/mangano-manganic oxide composite of the present embodiment
Up to 316.65F/g.
Spherical graphite alkene/mangano-manganic oxide composite obtained by the present embodiment in the different cyclic voltammetry curves swept under speed such as
Shown in Fig. 5, as shown in Figure 5, increase with sweep speed, composite remains to keep preferable stable circulation performance；In different electricity
Charging and discharging curve under current density is as shown in fig. 6, it will be appreciated from fig. 6 that under different current densities, charging and discharging curve all remains
Almost symmetrical triangle, illustrates that composite has excellent electric capacity invertibity.
Embodiment 2
First 50mg spherical graphite alkene is dispersed in 30mL deionized waters, ultrasonically treated 20min；Add 10mL
0.1mol/L liquor potassic permanganate, ultrasonic disperse 10min；Then well mixed graphene/potassium permanganate dispersion liquid is turned
In the reactor for moving to 50mL, at this moment the volume compactedness of reactor reaches 80% or so, and reactor then is placed on into high temperature furnace
In react 8h at 200 DEG C；Reacted sediment is centrifuged out under 10000rpm rotating speed, is washed with deionized respectively 3 times,
Ethanol is washed 1 time, in the air dry oven for being finally placed on 60 DEG C, is dried 12h, is produced answering for spherical graphite alkene/mangano-manganic oxide
Condensation material.
Electrochemical Characterization is carried out to spherical graphite alkene/mangano-manganic oxide composite of preparation, as a result shown, in 10mV/s
Sweep speed under, the specific capacitance of spherical graphite alkene/mangano-manganic oxide composite is up to 207.74F/g, significantly larger than simple
The specific capacitance of graphene.
Embodiment 3
First 50mg spherical graphite alkene is dispersed in 30mL deionized waters, ultrasonically treated 20min；Add 10mL
0.1mol/L liquor potassic permanganate, ultrasonic disperse 10min；Then well mixed graphene/potassium permanganate dispersion liquid is turned
In the reactor for moving to 50mL, at this moment the volume compactedness of reactor reaches 80% or so, and reactor then is placed on into high temperature furnace
In react 12h at 200 DEG C；Reacted sediment is centrifuged out under 10000rpm rotating speed, and 3 are washed with deionized respectively
Secondary, ethanol is washed 1 time, in the air dry oven for being finally placed on 60 DEG C, is dried 12h, is produced spherical graphite alkene/mangano-manganic oxide
Composite.
Electrochemical Characterization is carried out to spherical graphite alkene/mangano-manganic oxide composite of preparation, as a result shown, in 10mV/s
Sweep speed under, the specific capacitance of spherical graphite alkene/mangano-manganic oxide composite is up to 239.38F/g.
Embodiment 4
First 50mg spherical graphite alkene is dispersed in 30mL deionized waters, ultrasonically treated 20min；Add 10mL
0.1mol/L liquor potassic permanganate, ultrasonic disperse 10min；Then well mixed graphene/potassium permanganate dispersion liquid is turned
In the reactor for moving to 50mL, at this moment the volume compactedness of reactor reaches 80% or so, and reactor then is placed on into high temperature furnace
In react 15h at 200 DEG C；Reacted sediment is centrifuged out under 10000rpm rotating speed, and 3 are washed with deionized respectively
Secondary, ethanol is washed 1 time, in the air dry oven for being finally placed on 60 DEG C, is dried 12h, is produced spherical graphite alkene/mangano-manganic oxide
Composite.
Electrochemical Characterization is carried out to spherical graphite alkene/mangano-manganic oxide composite of preparation, as a result shown, in 10mV/s
Sweep speed under, the specific capacitance of spherical graphite alkene/mangano-manganic oxide composite is up to 238.84F/g.
Embodiment 5
First 50mg spherical graphite alkene is dispersed in 25mL deionized waters, ultrasonically treated 20min；Add 5mL
0.1mol/L liquor potassic permanganate, ultrasonic disperse 10min；Then well mixed graphene/potassium permanganate dispersion liquid is turned
In the reactor for moving to 50mL, at this moment the volume compactedness of reactor reaches 60% or so, and reactor then is placed on into high temperature furnace
In react 15h at 100 DEG C；Reacted sediment is centrifuged out under 10000rpm rotating speed, and 3 are washed with deionized respectively
Secondary, ethanol is washed 1 time, in the air dry oven for being finally placed on 60 DEG C, is dried 12h, is produced spherical graphite alkene/mangano-manganic oxide
Composite.
Embodiment 6
First 50mg spherical graphite alkene is dispersed in 25mL deionized waters, ultrasonically treated 20min；Add 15mL
0.1mol/L liquor potassic permanganate, ultrasonic disperse 10min；Then well mixed graphene/potassium permanganate dispersion liquid is turned
In the reactor for moving to 50mL, at this moment the volume compactedness of reactor reaches 80% or so, and reactor then is placed on into high temperature furnace
In react 8h at 300 DEG C；Reacted sediment is centrifuged out under 10000rpm rotating speed, is washed with deionized respectively 3 times,
Ethanol is washed 1 time, in the air dry oven for being finally placed on 60 DEG C, is dried 12h, is produced answering for spherical graphite alkene/mangano-manganic oxide
Condensation material.
Comparative example 1
First 50mg common graphite alkene is dispersed in 30mL deionized waters, ultrasonically treated 20min；Add 10mL
0.1mol/L liquor potassic permanganate, ultrasonic disperse 10min；Then well mixed common graphite alkene/potassium permanganate is disperseed
Liquid is transferred in 50mL reactor, and at this moment the compactedness of reactor reaches 80% or so, and reactor then is placed on into high temperature furnace
In react 10h at 200 DEG C；Reacted sediment is centrifuged out under 10000rpm rotating speed, and 3 are washed with deionized respectively
Secondary, ethanol is washed 1 time, in the air dry oven for being finally placed on 60 DEG C, is dried 12h, is produced common graphite alkene/mangano-manganic oxide
Composite.
Under 10mV/s sweep speed, the specific capacitance of common graphite alkene/mangano-manganic oxide composite reaches 135.62F/
g。
Comparative example 2
Particle diameter is spray-dried for 300nm graphene oxide aqueous dispersions, spray drying temperature is 100 DEG C, whirlwind point
From obtaining irregular microballoon.Muffle kiln roasting is placed on, argon gas protection, temperature programming, heating schedule is 100 DEG C and is warming up to
300 DEG C, 10 DEG C/min, 300 DEG C of 1h, 300 DEG C are warming up to 450 DEG C, 10 DEG C/min, 450 DEG C of 1h, and 450 DEG C are warming up to 600 DEG C, 10
DEG C/min, 600 DEG C of 1h, 600 DEG C are warming up to 900 DEG C, 10 DEG C/min, 900 DEG C of 1h.Obtain irregular graphene microballoon.
The irregular graphene microballoons of 50mg are dispersed in 30mL deionized waters, ultrasonically treated 20min；Add 10mL
0.1mol/L liquor potassic permanganate, ultrasonic disperse 10min；Then by well mixed irregular graphene/potassium permanganate point
Dispersion liquid is transferred in 50mL reactor, and at this moment the compactedness of reactor reaches 80% or so, and reactor then is placed on into high temperature
In stove 10h is reacted at 200 DEG C；Reacted sediment is centrifuged out under 10000rpm rotating speed, and 3 are washed with deionized respectively
Secondary, ethanol is washed 1 time, in the air dry oven for being finally placed on 60 DEG C, is dried 12h, is produced irregular graphene/mangano-manganic oxide
Composite.
Under 10mV/s sweep speed, the specific capacitance of irregular graphene/mangano-manganic oxide composite reaches
172.37F/g
Embodiment 1 is compared with comparative example 1 and the index of comparative example 2 and performance, and comparing result is as shown in table 1.Spherical stone
The specific capacitance of black alkene/mangano-manganic oxide composite is carried respectively compared with the specific capacitance of common graphite alkene/mangano-manganic oxide composite
Rise 133.5% and 83.2%.
Table 1
| Index numbering | Embodiment 1 | Comparative example 1 | Comparative example 2 |
| Composite shapes | Regular spherical | Flakey | It is irregular spherical |
| Tap density (g/cm3) | 0.23-0.52 | 0.01-0.07 | 0.02-0.13 |
| Specific surface area (m2/g) | 1200-3000 | 300-800 | 400-1000 |
| Specific capacitance (F/g) | 316.65 | 135.62 | 172.37 |
Claims (10)
1. a kind of spherical graphite alkene/mangano-manganic oxide composite, it is characterised in that the microstructure of the composite is：With
Spherical graphite alkene is matrix, and trimanganese tetroxide nano piece is dispersed in spherical graphite alkene matrix surface, is formed generally spherical
The complex microsphere of structure.
2. spherical graphite alkene/mangano-manganic oxide composite according to claim 1, it is characterised in that described is compound
The mass ratio of mangano-manganic oxide and spherical graphite alkene is (0.1 in material:1)~(1.2:1).
3. spherical graphite alkene/mangano-manganic oxide composite according to claim 1, it is characterised in that described is compound
The particle size of material is 500nm~4 μm.
4. spherical graphite alkene/mangano-manganic oxide composite according to claim 1, it is characterised in that described is compound
The tap density of material is 0.3g/cm3~0.8g/cm3, specific surface area is 150~300m2/g。
5. spherical graphite alkene/mangano-manganic oxide composite according to claim 1, it is characterised in that described is spherical
The radius of graphene is at 100nm-5 μm, and the tap density of spherical graphite alkene is 0.05g/cm3-0.7g/cm3, spherical graphite alkene is micro-
The specific surface area of ball is 300~3000m2/g。
6. spherical graphite alkene/mangano-manganic oxide composite according to claim 1, it is characterised in that described is spherical
Graphene is prepared as follows obtaining：
By graphene oxide and/or graphene dispersion into water or other solvents, graphite oxide is obtained after adding into globule, mixing
The graphene oxide and/or graphene dispersing solution, are then spray-dried, are refined into it by alkene and/or graphene dispersing solution
It is powdered, after cyclonic separation and high-temperature process, obtain spherical graphite alkene.
7. the preparation method of spherical graphite alkene/mangano-manganic oxide composite described in claim any one of 1-6, including it is as follows
Step：
(1) by spherical graphite alkene and deionized water according to mass ratio (1:300)~(1:700) ratio mixing, ultrasonically treated 10-
20min, obtains spherical graphite alkene dispersion liquid；Then liquor potassic permanganate, then ultrasonic disperse 5-10min are added, mixing is obtained equal
Even spherical graphite alkene/potassium permanganate dispersion liquid；
(2) by spherical graphite alkene/potassium permanganate dispersion liquid at 100-300 DEG C hydro-thermal reaction 8-15h, after the completion of reaction centrifugation point
From reacted sediment is obtained, washing precipitate produces spherical graphite alkene/mangano-manganic oxide composite.
8. preparation method according to claim 7, it is characterised in that spherical graphite alkene and potassium permanganate are pressed in step (1)
Mass ratio be 1：(2~4) liquor potassic permanganate is added；
It is preferred that, the molar concentration of liquor potassic permanganate is 0.05~0.15mol/L.
9. preparation method according to claim 7, it is characterised in that the hydro-thermal reaction described in step (2) is with poly-
Carried out in the stainless steel cauldron of tetrafluoroethene liner, the volume compactedness of spherical graphite alkene/potassium permanganate dispersion liquid is 60-
80%.
10. spherical graphite alkene/mangano-manganic oxide composite described in claim any one of 1-6 is as electrode material super
Application in capacitor.
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