CN107170589B - A kind of MnO2It is the preparation method of tri compound electrode material for super capacitor - Google Patents
A kind of MnO2It is the preparation method of tri compound electrode material for super capacitor Download PDFInfo
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- CN107170589B CN107170589B CN201710244672.0A CN201710244672A CN107170589B CN 107170589 B CN107170589 B CN 107170589B CN 201710244672 A CN201710244672 A CN 201710244672A CN 107170589 B CN107170589 B CN 107170589B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention belongs to electrode material for super capacitor preparation fields, and in particular to a kind of design preparation method of the ternary nano composite material with core nucleocapsid heterojunction structure.The cobaltosic oxide prepared using hydro-thermal method is kernel, the polyaniline of constant potential electrodeposition process electrochemical polymerization is outer core, manganese dioxide prepared by hydro-thermal method is shell, a kind of electrode material for super capacitor with good chemical property is made, the process is simple, of low cost, easily controllable, it is environmentally safe, there is good application value.
Description
Technical field
The present invention relates to a kind of preparation methods of ternary nano composite material, refer in particular to cobaltosic oxide (Co3O4) it is interior
Core, polyaniline (PANI) are outer core, manganese dioxide (MnO2) prepared for the ternary nano composite material of core-nucleocapsid structure of shell.
Background technology
As environmentally protective energy stores/conversion equipment, ultracapacitor is widely used in each side of human lives
Face also causes the research interest of numerous scholars.Determine that the key factor of performance of the supercapacitor is exactly the quality of electrode material, because
This, the research of electrode material is also the emphasis that exploitation has the ultracapacitor of more dominance energy.Electrode material for super capacitor master
There is transition metal oxide (RuO2、MnO2、NiO、Co3O4Deng), conducting polymer (polyaniline, polypyrrole, polythiophene etc.) with
And carbon-based material (graphene, carbon nanotube etc.) three categories.Wherein transition metal oxide has higher theoretical specific capacitance, can
To generate capacitance by the redox reaction of Rapid reversible, energy is stored, but electric conductivity is poor to lead to its practical specific capacitance
It is not high, by itself and conducting polymer, compound its electric conductivity of raising of carbon-based material, this problem can be well solved.
In the research of electrode material, the nanocomposite with core shell heterojunction structure can combine different materials because of it
The advantages of material, shows good performance and attracts attention, becomes the hot spot of research.In transition metal oxide, RuO2Property
It can be preferably but expensive and have pollution to environment.
Invention content
For problems of the prior art, the present invention has selected that cost is relatively low, resourceful and free of contamination routine
Material C o3O4And MnO2, its polyaniline that is preferable with electric conductivity and being relatively less oxidized easily is compound, successfully devise
One seed nucleus-core-shell structure copolymer heterojunction structure.Using nickel foam as collector, by the Co of hydro-thermal method preparation3O4Nano-wire array as kernel, and
A part of capacitance is provided, in Co3O4Potentiostatic electrodeposition last layer polyaniline film stores a part of charge as outer core on skeleton
And the effective approach that provides quickly is transmitted for electronics, material conductivity is improved, manganese dioxide is as outer made from last hydro-thermal method
Shell further increases the capacitive property of material, to obtain may be used as the ternary nano composite material of electrode of super capacitor
Co3O4/PANI/MnO2。
The present invention is prepared for a kind of cobaltosic oxide prepared using hydro-thermal method as kernel, and constant potential electrodeposition process electrochemistry is poly-
The polyaniline of conjunction is outer core, and manganese dioxide prepared by hydro-thermal method is the ternary nano composite wood with core-nucleocapsid structure of shell
Material, method is simple, and cost is relatively low, and chemical property is good, is a kind of good electrode material for super capacitor.
Technical scheme is as follows：
A kind of ternary nano composite material Co as electrode of super capacitor3O4/PANI/MnO2Preparation method, specifically
Include the following steps：
(1) Co is grown in nickel foam3O4As kernel：
It using nickel foam as substrate, is dipped in precursor solution, is placed in reaction kettle and carries out hydro-thermal reaction, hydro-thermal reaction
After；Product is ultrasonic in deionized water, then deionized water, ethyl alcohol is used to rinse respectively, it is dry, it is calcined in Muffle furnace；
It obtains with Co3O4Nickel foam；
The precursor solution be cobalt nitrate hexahydrate, ammonium fluoride, urea and a certain amount of surfactant be dissolved in from
The mixed liquor of sub- water composition；
Cobalt nitrate hexahydrate in the precursor solution, ammonium fluoride, urea the ratio of substance withdrawl syndrome be 1：2：5, it is used
Surfactant is cetyl trimethylammonium bromide (CTAB), surfactant qualities used：The volume of deionized water is
0.15g：30mL.
(2) by step (1) obtain with Co3O4Nickel foam, be dipped in the deposition liquid being made of dilute sulfuric acid and aniline,
As outer core, product is rinsed with water one layer of polyaniline film of electrochemical deposition, is obtained with Co at room temperature3O4And polyaniline film
Nickel foam；
(3) by step (2) obtain with Co3O4Nickel foam with polyaniline film is substrate, is dipped in liquor potassic permanganate
In, it is placed in reaction kettle and carries out hydro-thermal reaction, prepare MnO2Shell, after hydro-thermal reaction；Product is surpassed in deionized water
Sound, then deionized water, ethyl alcohol is used to rinse respectively, drying for standby.
In step (1), the temperature of the hydro-thermal reaction is 120 DEG C, time 10h；The product surpasses in deionized water
Sound 1min；The drying temperature is 60 DEG C；The calcination temperature is 350 DEG C, calcination time 3h.
In step (2), the composition of the deposition liquid of the electrochemical deposition polyaniline contains 0.25M sulfuric acid and 0.1M aniline；
The electrochemical deposition sedimentation time 120~300s, 0.6~1.0V of sedimentation potential；
In step (3), liquor potassic permanganate concentration used is 0.02M；The temperature of the hydro-thermal reaction is 120 DEG C, hydro-thermal
Reaction time is 4h；By product, ultrasound 1min, drying temperature are 60 DEG C in deionized water.
Beneficial effects of the present invention are：
(1) for the present invention using nickel foam as substrate, design has prepared one kind with Co made from hydro-thermal method3O4Nano-wire array
For kernel, the polyaniline film of electrochemical deposition is outer core, MnO made from hydro-thermal method2For core-core-shell structure copolymer heterojunction structure of shell,
Electro-chemical test is carried out to it, shows good capacitive property, high rate performance and stable circulation performance, is a kind of super well
Grade capacitor electrode material.
(2) preparation method provided by the invention is simple, and cost is relatively low.
Description of the drawings
Fig. 1：A is electronic scanner microscope (SEM) figure of step 1 in Examples 1 to 4, and b is step 2 in embodiment 2
SEM schemes, and c, d are the SEM figures of the different enlargement ratios of step 3 in embodiment 2.
Fig. 2 is transmission electron microscope (TEM) figure of step 3 in embodiment 2.
Specific implementation mode
With reference to specific implementation example, the present invention will be further described, so that those skilled in the art more fully understand
The present invention, but the invention is not limited in following embodiments.
Embodiment 1
1, using nickel foam as substrate, by cobalt nitrate hexahydrate, ammonium fluoride, urea according to substance withdrawl syndrome 1:2:5 ratio
It is dissolved in 30mL deionized waters, and 0.15g CTAB is added, be configured to precursor solution, in 120 DEG C of hydro-thermal reaction 10h, certainly
It so is cooled to room temperature, by product ultrasound 1min in deionized water, then deionized water, ethyl alcohol is used to rinse respectively, after 60 DEG C of dryings,
3h is calcined at 350 DEG C.Its scanning electron microscope is as shown in Figure 1a, aoxidizes the average diameter 50-80nm of cobalt nanowire, surface light
It is sliding, kernel can be used as.
2, with Co3O4Nickel foam be working electrode, platinum electrode be used as auxiliary electrode, saturated calomel electrode as join
Than electrode, in the deposition liquid containing 0.25M sulfuric acid and 0.1M aniline, electrochemical deposition polyaniline film, sedimentation potential
Product is used deionized water and ethyl alcohol to rinse by 0.6V, sedimentation time 300s respectively.
It 3, will be with Co3O4The potassium permanganate that the nickel foam of nano wire and polyaniline film is put into a concentration of 0.02M of 25mL is molten
In liquid, in 120 DEG C of hydro-thermal reaction 4h, by product ultrasound 1min in deionized water, then deionized water, ethyl alcohol is used to rinse respectively,
60 DEG C of dryings.
Embodiment 2
1, using nickel foam as substrate, by cobalt nitrate hexahydrate, ammonium fluoride, urea according to substance withdrawl syndrome 1:2:5 ratio
It is dissolved in 30mL deionized waters, and 0.15g CTAB is added, be configured to precursor solution, in 120 DEG C of hydro-thermal reaction 10h, certainly
It so is cooled to room temperature, by product ultrasound 1min in deionized water, then deionized water, ethyl alcohol is used to rinse respectively, after 60 DEG C of dryings,
3h is calcined at 350 DEG C.Its scanning electron microscope is as shown in Figure 1a.
2, with Co3O4Nickel foam be working electrode, platinum electrode be used as auxiliary electrode, saturated calomel electrode as join
Than electrode, in the deposition liquid containing 0.25M sulfuric acid and 0.1M aniline, electrochemical deposition polyaniline film, sedimentation potential
Product is used deionized water and ethyl alcohol to rinse by 0.8V, sedimentation time 240s respectively.Its scanning electron microscope is as shown in Figure 1 b.
After electrochemical deposition, nanowire diameter becomes larger in figure, and more layer of transparent shape films illustrate that polyaniline outer core deposits successfully, but
It does not have configuration of surface not have significant change.
It 3, will be with Co3O4The potassium permanganate that the nickel foam of nano wire and polyaniline film is put into a concentration of 0.02M of 25mL is molten
In liquid, in 120 DEG C of hydro-thermal reaction 4h, by product ultrasound 1min in deionized water, then deionized water, ethyl alcohol is used to rinse respectively,
60 DEG C of dryings.Its scanning electron microscope flower ball-shaped substance as shown in Fig. 1 c, d generates on nano wire, illustrates outside manganese dioxide
Shell is successfully prepared, and transmission electron microscope shows core-core-shell structure copolymer knot as shown in Fig. 2, consistent with scanning electron microscope result
Structure design is successfully prepared.
Embodiment 3
1, using nickel foam as substrate, by cobalt nitrate hexahydrate, ammonium fluoride, urea according to substance withdrawl syndrome 1:2:5 ratio
It is dissolved in 30mL deionized waters, and 0.15g CTAB is added, be configured to precursor solution, in 120 DEG C of hydro-thermal reaction 10h, certainly
It so is cooled to room temperature, by product ultrasound 1min in deionized water, then deionized water, ethyl alcohol is used to rinse respectively, after 60 DEG C of dryings,
3h is calcined at 350 DEG C.Its scanning electron microscope is as shown in Figure 1a.
2, with Co3O4Nickel foam be working electrode, platinum electrode be used as auxiliary electrode, saturated calomel electrode as join
Than electrode, in the deposition liquid containing 0.25M sulfuric acid and 0.1M aniline, electrochemical deposition polyaniline film, sedimentation potential
Product is used deionized water and ethyl alcohol to rinse by 1.0V, sedimentation time 240s respectively.
It 3, will be with Co3O4The potassium permanganate that the nickel foam of nano wire and polyaniline film is put into a concentration of 0.02M of 25mL is molten
In liquid, in 120 DEG C of hydro-thermal reaction 4h, by product ultrasound 1min in deionized water, then deionized water, ethyl alcohol is used to rinse respectively,
60 DEG C of dryings.
Embodiment 4
1, using nickel foam as substrate, by cobalt nitrate hexahydrate, ammonium fluoride, urea according to substance withdrawl syndrome 1:2:5 ratio
It is dissolved in 30mL deionized waters, and 0.15g CTAB is added, be configured to precursor solution, in 120 DEG C of hydro-thermal reaction 10h, certainly
It so is cooled to room temperature, by product ultrasound 1min in deionized water, then deionized water, ethyl alcohol is used to rinse respectively, after 60 DEG C of dryings,
3h is calcined at 350 DEG C.Its scanning electron microscope is as shown in Figure 1a.
2, with Co3O4Nickel foam be working electrode, platinum electrode be used as auxiliary electrode, saturated calomel electrode as join
Than electrode, in the deposition liquid containing 0.25M sulfuric acid and 0.1M aniline, electrochemical deposition polyaniline film, sedimentation potential
Product is used deionized water and ethyl alcohol to rinse by 1.0V, sedimentation time 120s respectively.
It 3, will be with Co3O4The potassium permanganate that the nickel foam of nano wire and polyaniline film is put into a concentration of 0.02M of 25mL is molten
In liquid, in 120 DEG C of hydro-thermal reaction 4h, by product ultrasound 1min in deionized water, then deionized water, ethyl alcohol is used to rinse respectively,
60 DEG C of dryings.
Claims (5)
1. a kind of MnO2It is the preparation method of tri compound electrode material for super capacitor, which is characterized in that use hydro-thermal method and perseverance
Current potential electrodeposition process prepares the ternary nano composite material with core-core-shell structure copolymer heterojunction structure, specifically comprises the following steps：
(1) Co is grown in nickel foam3O4As kernel：
It using nickel foam as substrate, is dipped in presoma liquid solution, is placed in reaction kettle and carries out hydro-thermal reaction, hydro-thermal reaction
After；Product is ultrasonic in deionized water, then deionized water, ethyl alcohol is used to rinse respectively, it is dry, it is calcined in Muffle furnace；
It obtains with Co3O4Nickel foam；
The precursor solution is that cobalt nitrate hexahydrate, ammonium fluoride, urea and a certain amount of surfactant are dissolved in deionized water
The mixed liquor of composition；
(2) by step (1) obtain with Co3O4Nickel foam, be dipped in the deposition liquid being made of dilute sulfuric acid and aniline, room temperature
As outer core, product is rinsed with water one layer of polyaniline film of lower electrochemical deposition, is obtained with Co3O4With the bubble of polyaniline film
Foam nickel；
(3) by step (2) obtain with Co3O4Nickel foam with polyaniline film is substrate, is dipped in liquor potassic permanganate,
It is placed in reaction kettle and carries out hydro-thermal reaction, prepare MnO2Shell, after hydro-thermal reaction；Product is ultrasonic in deionized water,
Deionized water, ethyl alcohol is used to rinse respectively again, drying for standby.
2. MnO according to claim 12It is the preparation method of tri compound electrode material for super capacitor, feature exists
In in step (1), the temperature of the hydro-thermal reaction is 120 DEG C, time 10h；The product is ultrasonic in deionized water
1min；Drying temperature is 60 DEG C；Calcination temperature is 350 DEG C, calcination time 3h.
3. MnO according to claim 12It is the preparation method of tri compound electrode material for super capacitor, feature exists
In the ratio of substance withdrawl syndrome of, cobalt nitrate hexahydrate in the precursor solution, ammonium fluoride, urea be 1：2：5, surface used is lived
Property agent be cetyl trimethylammonium bromide (CTAB), surfactant qualities used：The volume of deionized water is 0.15g：
30mL。
4. MnO according to claim 12It is the preparation method of tri compound electrode material for super capacitor, feature exists
In in step (2), the composition of the deposition liquid of one layer of polyaniline film of the electrochemical deposition contains 0.25M sulfuric acid and 0.1M benzene
Amine；120~300s of time of the electrochemical deposition, 0.6~1.0V of sedimentation potential.
5. MnO according to claim 12It is the preparation method of tri compound electrode material for super capacitor, feature exists
In in step (3), liquor potassic permanganate concentration used is 0.02M；The temperature of the hydro-thermal reaction is 120 DEG C, when hydro-thermal reaction
Between be 4h；By product, ultrasound 1min, drying temperature are 60 DEG C in deionized water.
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| CN110797201B (en) * | 2018-08-01 | 2021-11-23 | 天津大学 | Polyaniline-manganese dioxide composite material, preparation method thereof and application thereof in electrochemical energy storage field |
| CN110970228A (en) * | 2018-09-30 | 2020-04-07 | 天津大学 | Asymmetric super capacitor |
| CN110136993B (en) * | 2019-05-08 | 2020-04-10 | 武汉大学 | Method for preparing electrode plate of supercapacitor by hydrothermal method |
| CN111009422B (en) * | 2019-12-10 | 2021-10-08 | 中北大学 | Nickel-based NiCo with core-shell structure2O4Preparation method of polyaniline nano material |
| CN111986929A (en) * | 2020-07-31 | 2020-11-24 | 江苏大学 | Preparation method of cobalt manganate/nickel sulfide core-shell array structure electrode material |
| CN112216528A (en) * | 2020-10-12 | 2021-01-12 | 多助科技(武汉)有限公司 | Method for preparing electrode plate of high-voltage water-system supercapacitor by hydrothermal method |
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