CN107622880A - A kind of MnCoO2/ carbon nanotube electrode material and preparation method thereof - Google Patents
A kind of MnCoO2/ carbon nanotube electrode material and preparation method thereof Download PDFInfo
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- Electric Double-Layer Capacitors Or The Like (AREA)
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Abstract
The invention discloses a kind of MnCoO2/ carbon nanotube electrode material and preparation method thereof.The present invention includes following steps：Using potassium permanganate as manganese source, using cobaltous sulfate as cobalt source, dodecyl sodium sulfate (SDBS) is pattern controlling agent, and MnCoO is prepared by the method for Microwave-assisted firing2；Appropriate multi-walled carbon nanotube sample is immersed in activated carbon nano-tube in chromic acid lotion at room temperature；Finally by MnCoO2Mixed with activated carbon nano-tube, prepare MnCoO2/ carbon nanotube electrode material.The present invention is well mixed, as the electrode of ultracapacitor in mass ratio by after electrode material drying and grinding with carbon black, polytetrafluoroethylene (PTFE).The inventive method is environment-friendly, preparation method is simple, is easy to mass produce.
Description
Technical field
The invention belongs to electrochemistry and technical field of nano material, and in particular to a kind of MnCoO2/ carbon nanotube electrode material
Material and preparation method thereof.
Background technology
MnCoO2It is the manganese cobalt/cobalt oxide based on divalence manganese element and divalence cobalt element, in electrode material, magnetic material
Material, catalyst, environmental improvement etc. have extensive use, turn into research topic more popular in recent years, research emphasis bag
Include its synthesis technique and optimization.The synthetic method of manganese cobalt/cobalt oxide has a lot, mainly there is electrochemical process, hydro-thermal method, solid phase at present
Synthetic method, template etc..Synthesis manganese cobalt/cobalt oxide is aided in using conventional hydrothermal method, crystal nucleation process can preferentially occur in container
On inwall and powder dust particle, and due to particle disorder distribution and nonhomogen-ous nucleation the speed factor such as slowly so that seeded growth
Slowly, reaction process is influenceed.So in order to solve problems, the method that selection uses microwave radiation.The selection of microwave radiation
Property heat characteristic and body phase mode of heating from inside to outside so that the shortcomings that nucleation first occurs at chamber wall is resolved；And
Microwave heating has the characteristics of overall heating, therefore numerous " focus " can be produced in solvent, so that nucleation rate is shown
Write and improve, nanocrystalline aggregate velocity is accelerated, and improves W-response process.
Microwave synthesis is exactly there is the material of microware heating effect to be placed in microwave field some to be allowed to that chemistry occurs
Synthesis.Due to the interior principle of heating and absorption polarization of microwave so that microware heating is highly effective.Add micro-wave dielectric
The chemosynthesis reaction of fuel factor has many new features, the building-up process of microwave synthetic material and traditional high―temperature nuclei phase
Than reaction speed is fast, greatly shortens generated time, and the material of synthesis is more preferable, and quality is higher, more economical.Due to microwave action energy
It is enough that chemical effect, polarity effect and magnetic effect are produced to material, there is facilitation to the reaction of material internal physiochemical, so as to reach
To effect more more preferable than conventional heating methods.
The capacitive property of manganese material is mainly based upon structural parameters and determined, such as surface topography, particle size, polymorphism
Deng.The characteristics of electrochemical properties of cobalt material are excellent, charge-discharge velocity is fast, and capacitance is big, relative stability is preferable.But manganese cobalt
The electric conductivity of oxide is poor, cyclical stability is low, thus can not reach the basic demand of electrode of super capacitor, limits
Its practical application.In order to solve this problem, scientists are started with from the angle for improving electric conductivity, are added in manganese cobalt/cobalt oxide
Enter some electrically conductive materials, such as porous carbon, acetylene black, CNT, graphene etc., obtained composite has both two kinds of materials
Good characteristic.Selection loads other particles using it as base material using CNT as research object.CNT is as one
Dimension nano material, in light weight, hexagonal structure connection is perfect, has many abnormal mechanics, electricity and chemical properties, so can
To be greatly enhanced the charge transfer efficiency of active material, also enable the bigger contact area of electrode material to electrolyte,
The integral capacitor characteristic of raising system.
The content of the invention
For overcome the deficiencies in the prior art, it is an object of the invention to provide it is a kind of it is environment-friendly, preparation method is simple, greatly
It is big to shorten generated time, it is easy to mass produce the MnCoO of high-purity2/ carbon nanotube electrode material and preparation method thereof.
The present invention is by the use of manganese cobalt binary metal oxide nanometer layer and CNT as elementary cell, by microwave radiation side
Method prepares MnCoO2/ carbon nano-tube combination electrode material.The good of carbon nanotube electrode material can be played in composite to lead
Electrical and enhancing prepares the cyclical stability of material, and manganese cobalt/cobalt oxide nanometer floor height fake capacitance can also play simultaneously, pass through
The cooperative effect of manganese cobalt binary metal oxide nanometer layer and CNT, obtain the electrode material with the two advantage.
In order to solve the above-mentioned technical problem, the present invention uses following technical scheme.
The present invention provides a kind of MnCoO2The preparation method of/carbon nanotube electrode material, it is by by MnCoO2And activated carbon
Nanotube is mixed to get；Wherein：The MnCoO2It is using potassium permanganate as manganese source, cobaltous sulfate is cobalt source, dodecyl sodium sulfate
SDBS is pattern controlling agent, is prepared using the method for Microwave-assisted firing；Activated carbon nano-tube is at room temperature by carbon nanometer
Pipe, which is immersed in chromic acid, carries out activation acquisition.
In the present invention, MnCoO2Mass ratio with activated carbon nano-tube is 1:1~1:8；Preferably, MnCoO2And activated carbon
The mass ratio of nanotube is 1:1,1:2,1:4 or 1:8.
In the present invention, CNT is multi-walled carbon nanotube.
In the present invention, the MnCoO2Preparation method it is as follows：By potassium permanganate, cobaltous sulfate and dodecyl sodium sulfate
SDBS is placed in microwave reaction instrument, and temperature control is 100~120 DEG C, and microwave power control is 70~110W, Microwave-assisted firing
Time is 15-45min.
In the present invention, temperature control is 110 DEG C, and microwave power control is 90~100W, and the Microwave-assisted firing time is 20-
30min。
In the present invention, it is 10~30min that CNT, which is immersed in the time activated in chromic acid,.
In the present invention, potassium permanganate, the mol ratio of cobaltous sulfate are 1:1~5:1；With 5mmolKMnO4On the basis of, dodecane
Base sodium sulfonate SDBS mass ranges are controlled in 0.04-0.05g.
The present invention also provides the MnCoO that a kind of above-mentioned preparation method obtains2/ carbon nanotube electrode material.Preferably, it is electric
The apparent form of pole material is flower ball-shaped, and particle diameter is in 400nm or so.
By MnCoO in the present invention2When/carbon nanotube electrode material is used to make electrode, by the way that electrode material addition is added
Appropriate glue is pressed together in foam nickel sheet (1cm × 1cm), and 9~11h is toasted at a temperature of 95~105 DEG C, is made.
The present invention compared with the existing technology, has advantages below and beneficial effect：
1st, the present invention synthesizes MnCoO by Microwave-assisted synthesis method2, generated time is substantially reduced, simplifies reaction step
Suddenly, reaction rate and efficiency are improved, improves some physics and chemical property of synthetic product.
2nd, MnCoO prepared by the present invention2Particle dispersion is more preferable, and without obvious cluster, such structure can improve
The electrochemical properties of material.
3rd, the present invention is using the method for chromic acid lotion room temperature activation multi-walled carbon nanotube, the CNT structure after room temperature activation
The ultracapacitor energy storage performance built has significant raising.Its surface texture is changed, what the CNT after activation was constructed
Ultracapacitor shows excellent capacitance characteristic.
Embodiment
The following examples can make those skilled in the art that the present invention be more fully understood, but not limit in any form
The present invention.
Embodiment 1
A kind of MnCoO2The preparation method and applications of/CNT, comprise the following steps：First by 5mmolKMnO4、
1mmolCoSO4、6mmolH2SO4It is put into 100ml deionized waters in three-neck flask, adds 0.05g SDBS, be stirred at room temperature
It is placed in microwave reaction instrument and is reacted after 30min, reaction temperature control is at 110 DEG C, reaction time 15min.Product is natural
Room temperature is cooled to, is filtered, resulting materials drying at room temperature 2d.Secondly the room temperature activation of CNT:Respectively by appropriate more wall carbon
Nanotube sample is soaked in chromic acid lotion at room temperature, and the heating of 2.5g potassium bichromates is dissolved in 5ml water, is slow added into
The 45ml98% concentrated sulfuric acids, stirring at low speed 10min, then with filtering and washing repeatedly after distilled water diluting, obtained product is at 150 DEG C
Processing is dried in heating 2h, finally obtains activated carbon nano-tube.Respectively by the MnCoO of microwave treatment2/ and activation after carbon receive
Mitron (1：1 mass ratio) sample vacuum freeze drying 48h, the surface texture of protection activity material.By dry active material
It is fully ground, with acetylene black, polytetrafluoroethylene (PTFE) in mass ratio 8:1:1 mixing, stirs, adds appropriate glue and be pressed together on foam
In nickel sheet (1cm × 1cm), working electrode (being designated as CNT-1) is made in 100 DEG C of baking 10h.
Application Example 1
Through occasion China CHI760e electrochemical workstations using cyclic voltammetry and the method for constant current charge-discharge, using three electrodes
System：With 1mol/L H2SO4Make electrolyte, CNT-1 foam nickel sheet is as working electrode, using Ag/AgCl as reference electrode,
Pt silks are made to electrode.Detect the specific capacitance of the material and the performance of cyclical stability, cyclic voltammetry test, it is shown that material has
Standby excellent redox ability, capability retention is 85.3% after 5000 circulations under 5A/g high current densities.Utilize electricity
Sub- flying-spot microscope (surface microstructure for characterizing the electrode material) stratiform manganese oxide is the uneven bouquet of granularity size
Pattern, size distribution is in 400nm or so, and crystallinity is poor.In 1mol/L H2SO4Current density in solution and in 0.5A/g
Under, the specific capacitance of electrode material of the present invention has reached 332.7F/g.
Embodiment 2
A kind of MnCoO2The preparation method and applications of/CNT, comprise the following steps：First by 5mmolKMnO4、
5mmolCoSO4、6mmolH2SO4It is put into 100ml deionized waters in three-neck flask, adds 0.1g SDBS, 30min is stirred at room temperature
After be placed in microwave reaction instrument and reacted, reaction temperature control is at 110 DEG C, reaction time 30min.Product naturally cools to
Room temperature, filter, resulting materials drying at room temperature 2d.Secondly the room temperature activation of CNT:Respectively by appropriate multi-walled carbon nanotube
Sample is soaked in 2.5g potassium bichromates heating in chromic acid lotion and is dissolved in 5ml water at room temperature, is slow added into the dense sulphur of 45ml98%
Acid, stirring at low speed 20min, then with filtering and washing, obtained product heat 2h at 150 DEG C and done repeatedly after distilled water diluting
Dry processing, finally obtains activated carbon nano-tube.Respectively by the MnCoO of microwave treatment2And the CNT (1 after activation：2 matter
Measure ratio) sample vacuum freeze drying 48h, the surface texture of protection activity material.Dry active material is fully ground, with second
Acetylene black, polytetrafluoroethylene (PTFE) in mass ratio 8:1:1 mixing, stir, add appropriate glue be pressed together on foam nickel sheet (1cm ×
On 1cm), working electrode (being designated as CNT-2) is made in 100 DEG C of baking 10h.
Application Example 2
Through occasion China CHI760e electrochemical workstations using cyclic voltammetry and the method for constant current charge-discharge, using three electrodes
System：With 1mol/L H2SO4Make electrolyte, CNT-2 foam nickel sheet is as working electrode, using Ag/AgCl as reference electrode,
Pt silks are made to electrode.Detect the specific capacitance of the material and the performance of cyclical stability, cyclic voltammetry test, it is shown that material has
Standby excellent redox ability, capability retention is 88.7% after 5000 circulations under 5A/g high current densities.Utilize electricity
Sub- flying-spot microscope (surface microstructure for characterizing the electrode material) stratiform manganese oxide is granularity bouquet shape of uniform size
Looks, size distribution is in 400nm or so, and good crystallinity.In 1mol/L H2SO4In solution and under 0.5A/g current density,
The specific capacitance of electrode material of the present invention has reached 384.2F/g.
Embodiment 3
A kind of MnCoO2The preparation method and applications of/CNT, comprise the following steps：First by 5mmolKMnO4、
1mmolCoSO4、6mmolH2SO4It is put into 100ml deionized waters in three-neck flask, adds 0.2g SDBS, 30min is stirred at room temperature
After be placed in microwave reaction instrument and reacted, reaction temperature control is at 110 DEG C, reaction time 45min.Product naturally cools to
Room temperature, filter, resulting materials drying at room temperature 2d.Secondly the room temperature activation of CNT：Respectively by appropriate multi-walled carbon nanotube
Sample be soaked at room temperature in chromic acid lotion (2.5g potassium bichromates heating is dissolved in 5ml water, be slow added into the dense sulphur of 45ml98%
Acid, stirring at low speed 30min) and then with filtering and washing, obtained product heat 2h at 150 DEG C and done repeatedly after distilled water diluting
Dry processing, finally obtains activated carbon nano-tube.Respectively by the MnCoO of microwave treatment2And the CNT (1 after activation:4 matter
Measure ratio) sample vacuum freeze drying 48h, the surface texture of protection activity material.Dry active material is fully ground, with second
Acetylene black, polytetrafluoroethylene (PTFE) in mass ratio 8:1:1 mixing, stir, add appropriate glue be pressed together on foam nickel sheet (1cm ×
On 1cm), working electrode (being designated as CNT-3) is made in 100 DEG C of baking 10h.
Application Example 3
Through occasion China CHI760e electrochemical workstations using cyclic voltammetry and the method for constant current charge-discharge, using three electrodes
System：With 1mol/L H2SO4Make electrolyte, CNT-3 foam nickel sheet is as working electrode, using Ag/AgCl as reference electrode,
Pt silks are made to electrode.Detect the specific capacitance of the material and the performance of cyclical stability, cyclic voltammetry test, it is shown that material has
Standby excellent redox ability, capability retention is 82.1% after 5000 circulations under 5A/g high current densities.Utilize electricity
Sub- flying-spot microscope (surface microstructure for characterizing the electrode material) material is still flower spherical structure, in the further micro- of material
Make dispersed variation there occurs a certain degree of reunion in ripple course of reaction.In 1mol/L H2SO4In solution and in 0.5A/g
Current density under, the specific capacitance of electrode material of the present invention has reached 312.8F/g.
Claims (9)
- A kind of 1. MnCoO2The preparation method of/carbon nanotube electrode material, it is characterised in that by by MnCoO2Received with activated carbon Mitron is mixed to get；Wherein：The MnCoO2It is using potassium permanganate as manganese source, cobaltous sulfate is cobalt source, dodecyl sodium sulfate SDBS is pattern controlling agent, is prepared using the method for Microwave-assisted firing；Activated carbon nano-tube is soaked by CNT Carry out activation acquisition at room temperature in chromic acid.
- 2. preparation method according to claim 1, it is characterised in that MnCoO2Mass ratio with activated carbon nano-tube is 1:1 ~1:8.
- 3. preparation method according to claim 1, it is characterised in that MnCoO2Mass ratio with activated carbon nano-tube is 1: 1,1:2,1:4 or 1:8.
- 4. preparation method according to claim 1, it is characterised in that CNT is multi-walled carbon nanotube.
- 5. preparation method according to claim 1, it is characterised in that the MnCoO2Preparation method it is as follows：By permanganic acid Potassium, cobaltous sulfate and dodecyl sodium sulfate SDBS are placed in microwave reaction instrument, and temperature control is 100~120 DEG C, microwave power control 70~110W is made as, the Microwave-assisted firing time is 15-45min.
- 6. preparation method according to claim 1, it is characterised in that temperature control is 110 DEG C, and microwave power control is 90 ~100W, Microwave-assisted firing time are 20-30min.
- 7. preparation method according to claim 1, it is characterised in that CNT is immersed in the time activated in chromic acid and is 10~30min.
- 8. preparation method according to claim 1, it is characterised in that potassium permanganate, the mol ratio of cobaltous sulfate are 1:1~5: 1；With 5mmolKMnO4On the basis of, dodecyl sodium sulfate SDBS mass range is controlled in 0.05-0.2g.
- A kind of 9. MnCoO that preparation method according to one of claim 1~8 obtains2/ carbon nanotube electrode material.
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| CN109603889A (en) * | 2018-12-17 | 2019-04-12 | 上海应用技术大学 | A kind of catalyst and preparation method thereof for formaldehyde low-temperature catalytic oxidation |
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| CN103050701A (en) * | 2011-10-17 | 2013-04-17 | 中国科学院大连化学物理研究所 | Electrode material for lithium-air battery and preparation method of electrode material |
| CN103943838A (en) * | 2014-04-21 | 2014-07-23 | 西安交通大学 | Preparation method of metal oxide nanosheet and carbon nanotube composite energy-storage material |
| CN106693985A (en) * | 2016-11-24 | 2017-05-24 | 上海交通大学 | Preparation method of sheet spinel structure cobalt-manganese composite oxide |
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| CN103050701A (en) * | 2011-10-17 | 2013-04-17 | 中国科学院大连化学物理研究所 | Electrode material for lithium-air battery and preparation method of electrode material |
| CN103943838A (en) * | 2014-04-21 | 2014-07-23 | 西安交通大学 | Preparation method of metal oxide nanosheet and carbon nanotube composite energy-storage material |
| CN106693985A (en) * | 2016-11-24 | 2017-05-24 | 上海交通大学 | Preparation method of sheet spinel structure cobalt-manganese composite oxide |
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| 张治安等: ""锂空气电池用碳纳米管/钴锰氧化物复合电极材料的制备及电化学性能"", 《无机材料学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109603889A (en) * | 2018-12-17 | 2019-04-12 | 上海应用技术大学 | A kind of catalyst and preparation method thereof for formaldehyde low-temperature catalytic oxidation |
| CN109603889B (en) * | 2018-12-17 | 2021-07-20 | 上海应用技术大学 | Catalyst for low-temperature catalytic oxidation of formaldehyde and preparation method thereof |
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