CN107068423B - A kind of Preparation method and use of cobalt oxide/graphene/multi-stage porous carbon electrode material - Google Patents
A kind of Preparation method and use of cobalt oxide/graphene/multi-stage porous carbon electrode material Download PDFInfo
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- CN107068423B CN107068423B CN201710272592.6A CN201710272592A CN107068423B CN 107068423 B CN107068423 B CN 107068423B CN 201710272592 A CN201710272592 A CN 201710272592A CN 107068423 B CN107068423 B CN 107068423B
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Abstract
The present invention provides a kind of cobalt oxide/graphene/multi-stage porous carbon electrode material Preparation method and uses, and steps are as follows: 1, the preparation of graphene oxide；2, weigh graphene oxide, deionized water be added, make its it is fully dispersed obtain graphene oxide solution, then sequentially add EDTA-3K, cabaltous nitrate hexahydrate and urea, obtain mixed liquor, continue ultrasound after being vigorously stirred；Mixed liquor is transferred in reaction kettle, hydro-thermal reaction, is drawn off after its natural cooling, collects solid product, drying；It by the solid product after drying under inert gas inert gas shielding, is calcined, is calcined after it is cooled to room temperature, then in air, obtain calcined product；Cobalt oxide/graphene/multi-stage porous carbon electrode material is obtained after washing calcined product drying using hot water.Synthetic method of the present invention is simple and easy, and synthetic material is had excellent performance, and is suitable for promoting the use of.
Description
Technical field
The present invention relates to a kind of cobalt oxide/graphene/multi-stage porous carbon electrode material Preparation method and use, category is received
Meter Gong Neng multi-stage porous fabricating technology field.
Background technique
Supercapacitor (Supercapacitor) also known as electrochemical capacitor (Electrochemical
It Capacitor), is a kind of novel energy storage apparatus for relying primarily on electric double layer and redox fake capacitance charge storage electric energy.Its
As a kind of powerful energy storage device, fill up between battery and conventional capacitor (in terms of energy density and power density)
Blank, capacitance can reach farad grade.Electrode material is the deciding factor of performance of the supercapacitor quality, direct relation
To its chemical property.Active carbon becomes currently the only commercialized electric double layer since it is with a series of good characteristic
Capacitor electrode material.
But the chemical property of pure carbon electrode material is lower, how to further increase the chemical property of electrode material
Become key.Graphene because the good characteristic of its own such as: electronic conductivity, good mechanical and thermal stability and Gao Bi
Surface area makes it have very big application in terms of electrochemistry.Multi-stage porous has three-dimensional grapheme block materials and ordered mesopore carbon concurrently
The advantages of the two, not only possesses the three-dimensional channel for carrier high-speed transfer, high stability and high mechanical strength, while having huge
Big reaction interface and orderly adjustable meso-hole structure, the adjustable denaturation of these structures and composition are that exploitation graphene is order mesoporous
Carbon composite is stored in electrochemical energy and the application in the fields such as conversion, photocatalysis, absorption and separation provides wide put down
Platform.
Summary of the invention
The present invention prepares graphene oxide using Hummers method, is related to a kind of graphene oxide intercalation EDTA-3K multi-stage porous
The preparation and its application of carbon material.Firstly, being the preparation of graphene oxide, by doped metal ion in graphene, ultrasound.Then
It takes hydro-thermal method to prepare mixture, is dried after product is taken out.Then it is transferred in nickel crucible, carries out pyrocarbon under nitrogen protection
Change.
The technical solution adopted by the present invention is that:
A kind of preparation method of cobalt oxide/graphene/multi-stage porous carbon electrode material, steps are as follows:
The preparation of step 1, graphene oxide
Low-temp reaction: the concentrated sulfuric acid is fitted into three-necked flask, is placed in ice-water bath, and temperature is controlled.In stirring bar
Under part, it is slowly added to the mixture of graphite powder and sodium nitrate, continues to stir.It is slowly added to potassium permanganate several times again, stirring is anti-
It answers.
Medium temperature reaction: and then temperature is increased, continue to be stirred to react.It is then slowly added into deionized water, is stirred, repeats and adds
Enter water to be stirred to react.
Pyroreaction: continuously adding deionized water, is warming up to 98 DEG C, reaction.
Cooling, centrifugation, filtering: after reaction, it is 30% that reaction solution, which is cooled to room temperature, and appropriate mass fraction is added
Hydrogenperoxide steam generator until do not bubble.Finally, centrifugal filtration, is cleaned multiple times with dilute hydrochloric acid, and detected with barium chloride without white
Color flocculent deposit, it is neutrality that deionized water, which is washed to supernatant, and vacuum drying obtains graphene oxide for 24 hours.
The preparation of step 2, cobalt oxide/graphene/multi-stage porous carbon electrode material
The graphene oxide of the above-mentioned preparation of 30mg is weighed, 40mL deionized water is added, ultrasonic 30min keeps its fully dispersed
Graphene oxide solution is obtained, 10g EDTA-3K, 0.4g cabaltous nitrate hexahydrate and 0.1g urea is then sequentially added, is mixed
Liquid A is closed, continues ultrasound 1h after being vigorously stirred 5min；
The mixed liquor A of black is transferred in reaction kettle, hydro-thermal reaction 12h under 120 DEG C of hydrothermal conditions, after its natural cooling
It is drawn off, collects solid product, dried under the conditions of 80 DEG C；
Solid product after drying is transferred in nickel crucible, protects (airflow rate 150mL in inert nitrogen gas
min-1) under, with 3 DEG C of min-1Heating rate rise to 800 DEG C and calcined, 1h is maintained, after it is cooled to room temperature, then in sky
4h is calcined in gas, temperature is set as 250 DEG C, it is therefore an objective to which the cobalt simple substance of small part remaining is completely converted into Co3O4；
It is washed using 90 DEG C of hot water, removes the K in product2CO3Equal impurity obtain the four of black after 70 DEG C dry
Co 3 O/graphene/multi-stage porous carbon electrode material.
In step 2, in the mixed liquor A, used graphene oxide, EDTA-3K, cabaltous nitrate hexahydrate and urea exist
The ratio between mass concentration in deionized water is 0.75:250:10:2.5, it is described be vigorously stirred after continue ultrasound to be vigorously stirred
Continue ultrasound 1h after 5min.
In step 2, the temperature of the hydro-thermal reaction is 120 DEG C, reaction time 12h, and the temperature of the drying is 80 DEG C.
In step 2, the inert gas is nitrogen, and the calcination temperature is 800 DEG C, in 800 DEG C of holding 1h, rises to 800
DEG C rate be 3 DEG C of min-1；The temperature calcined in air is 250 DEG C, time 4h.
In step 2, the temperature of the hot water is 90 DEG C, and the drying temperature is 70 DEG C.
The cobalt oxide/graphene/multi-stage porous carbon electrode material is used as electrode material.
The utility model has the advantages that
(1) porous multi-stage porous have that large specific surface area, pore structure are flourishing, chemical stability is high, mechanical performance is strong and
The conditions such as cellular structure and aperture size are adjustable can satisfy this experiment low cost, high performance requirement.
(2) such multi-stage porous has both the performance and multistage pore structure prosperity and cooperative ability of single Porous materials, has excellent
Good comprehensive performance.
(3) synthetic method is simple and easy, and synthetic material is had excellent performance, and is suitable for promoting the use of.
Detailed description of the invention
Fig. 1 is the charging and discharging curve that cyclic voltammetry measures.
Fig. 2 is transmission electron microscope picture.
Specific embodiment
The invention will be further described below in conjunction with the accompanying drawings:
Embodiment 1:
Firstly, being placed in ice-water bath in the three-necked flask that a certain amount of concentrated sulfuric acid is fitted into, controlled at 0 DEG C
Left and right.Under agitation, it is slowly added to 3.0g graphite powder and 1.5g sodium nitrate, continues to stir 5min.Slowly add several times again
Enter 9.0g potassium permanganate, reacts 0.5h.Then temperature is increased to 35 DEG C of the reaction was continued 2h.It is then slowly added into 5mL deionized water,
After stirring 5min, 10mL deionized water is added, after reacting 10min, 100mL deionized water is continuously added, is warming up to 98 DEG C, instead
Answer 30min.After centrifugation, pickling, being washed to neutrality, then 45 DEG C of vacuum drying obtain graphite oxide for 24 hours.
The graphite oxide of the above-mentioned preparation of 30mg is weighed, 40mL deionized water is added, after ultrasonic disperse is uniform, sequentially adds
10g EDTA-3K, 0.4g cabaltous nitrate hexahydrate and 0.1g urea are simultaneously sufficiently mixed.Then it is transferred in reaction kettle, 120 DEG C of hydro-thermal items
After reacting 12h under part, take out, and dried under the conditions of 70 DEG C.Then it is transferred in nickel crucible, under nitrogen protection, with 3-5 DEG C
min-1Heating rate rise to 800 DEG C, maintain 1h, calcine 4h after it is cooled to room temperature, then in air at 250 DEG C.Then
Hot water washs repeatedly, obtains graphene oxide intercalation EDTA-3K multi-stage porous after dry.
Fig. 1 is that EDTA-3K multi-stage porous carbon material does the obtained charging and discharging curve figure of electrode material；
Fig. 2 is Co3O4The transmission electron microscope picture of/GNS/EPCs.
Embodiment 1:
Firstly, being placed in ice-water bath in the three-necked flask that a certain amount of concentrated sulfuric acid is fitted into, controlled at 0 DEG C
Left and right.Under agitation, it is slowly added to the mixture of 3.0g graphite powder (325 mesh) and 1.5g sodium nitrate, continues to stir 5min.
It is slowly added to 9.0g potassium permanganate several times again, pays attention to controlling reaction temperature no more than 20 DEG C, be stirred to react 0.5h.Then it rises
High-temperature continues to be stirred to react 2h to 35 DEG C.It is then slowly added into 5mL deionized water, after stirring 5min, is slow added into 10mL
Deionized water continuously adds 100mL deionized water after reacting 10min, is warming up to 98 DEG C, reacts 30min.After reaction will
Reaction solution is cooled to room temperature and is added the hydrogenperoxide steam generator that appropriate mass fraction is 30% until not bubbling.Finally, centrifugation
Filtering, the metal ion removed in solution is cleaned multiple times in dilute hydrochloric acid successively, and is detected with barium chloride without white flock precipitate,
It is neutrality that deionized water, which is washed to supernatant, and 60 DEG C of vacuum drying obtain graphite oxide for 24 hours.
It weighs the graphite oxide of the above-mentioned preparation of 30mg, is added 40mL deionized water, ultrasonic 30min, keep its fully dispersed
To graphene oxide, 10g EDTA-3K, 1.2g cabaltous nitrate hexahydrate and 0.3g urea are then sequentially added, 5min is vigorously stirred
Continue ultrasound 1h afterwards.Then the mixed liquor of black is transferred in reaction kettle, reacts 12h under 120 DEG C of hydrothermal conditions, it is naturally cold to it
But it is drawn off, is dried under the conditions of 80 DEG C afterwards.Then it is transferred in nickel crucible, in nitrogen protection (airflow rate 150mL
min-1) under, with 3 DEG C of min-1Heating rate rise to 800 DEG C, maintain 1h, calcined after it is cooled to room temperature, then in air
4h, temperature are set as 250 DEG C, it is therefore an objective to which the cobalt simple substance of small part remaining is completely converted into Co3O4.Then 90 DEG C of hot water are utilized
It washs repeatedly, removes the K in product2CO3Equal impurity obtain the sample of black after 70 DEG C dry.
The charging and discharging curve figure of EDTA-3K multi-stage porous in Fig. 1, charge and discharge are the process that charge collection is deposited and scattered and disappeared, charge and discharge
The curve reaction quantity of electric charge changes with time rule.Charge and discharge are the process that charge collection is deposited and scattered and disappeared, charging and discharging curve reaction electricity
Lotus amount changes with time rule.Show that cell potential is sharply increased with the extension in charging time in figure, then tends to
Steady to increase, when charging is complete, current potential reaches maximum, and electric discharge initial stage current potential sharply declines, and variation is obvious, then tends to be slow again
It is slow to reduce, in electric discharge latter stage, sparks and finish, current potential moment is reduced to 0.
This pore structure characteristic again may be by TEM figure to characterize, from Co in Fig. 23O4In the TEM figure of/GNS/EPCs
It can be seen that pore structure size distribution is between a few nanometers to tens of nanometers in the presence of a large amount of unordered nest cavernous structures.
Claims (6)
1. a kind of cobalt oxide/graphene/multi-stage porous carbon electrode material preparation method, which is characterized in that steps are as follows:
The preparation of step 1, graphene oxide；
The preparation of step 2, cobalt oxide/graphene/multi-stage porous carbon electrode material:
Weigh graphene oxide, deionized water be added, make its it is fully dispersed obtain graphene oxide solution, then sequentially add
EDTA-3K, cabaltous nitrate hexahydrate and urea, obtain mixed liquor A, continue ultrasound after being vigorously stirred；
Mixed liquor A is transferred in reaction kettle, hydro-thermal reaction, is drawn off after its natural cooling, collects solid product, drying；
Under nitrogen protection by the solid product after drying, it is calcined, is calcined after it is cooled to room temperature, then in air,
Obtain calcined product；
Cobalt oxide/graphene/multi-stage porous carbon electrode material is obtained after washing calcined product drying using hot water；
In step 2, in the mixed liquor A, used graphene oxide, EDTA-3K, cabaltous nitrate hexahydrate and urea go from
The ratio between mass concentration in sub- water is 0.75:250:10:2.5.
2. a kind of preparation method of cobalt oxide/graphene/multi-stage porous carbon electrode material according to claim 1,
Be characterized in that, in step 2, it is described be vigorously stirred after continue ultrasound and continue ultrasound 1h to be vigorously stirred after 5min.
3. a kind of preparation method of cobalt oxide/graphene/multi-stage porous carbon electrode material according to claim 1,
It is characterized in that, in step 2, the temperature of the hydro-thermal reaction is 120 DEG C, reaction time 12h, and the temperature of the drying is 80
℃。
4. a kind of preparation method of cobalt oxide/graphene/multi-stage porous carbon electrode material according to claim 1,
It is characterized in that, in step 2, the calcination temperature is 800 DEG C, and in 800 DEG C of holding 1h, the rate for rising to 800 DEG C is 3 DEG C of min-1；
The temperature calcined in air is 250 DEG C, time 4h.
5. a kind of preparation method of cobalt oxide/graphene/multi-stage porous carbon electrode material according to claim 1,
It is characterized in that, in step 2, the temperature of the hot water is 90 DEG C, and the drying temperature is 70 DEG C.
6. cobalt oxide/graphene/multi-stage porous carbon electrode material of the preparation of method described in Claims 1 to 5 any one
Purposes as electrode material.
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| CN105161318A (en) * | 2015-07-07 | 2015-12-16 | 上海应用技术学院 | Three-dimensional graphite alkene/cobaltosic oxide composite material, preparation method thereof and application |
| CN105845457A (en) * | 2016-05-26 | 2016-08-10 | 江苏大学 | Preparation method and application of porous carbon material |
| CN105854801A (en) * | 2016-05-10 | 2016-08-17 | 江苏大学 | Nitrogen-doped porous carbon material and preparation method and application thereof |
| CN105914048A (en) * | 2016-07-07 | 2016-08-31 | 西华大学 | Porous carbon-graphene-metal oxide composite material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105161318A (en) * | 2015-07-07 | 2015-12-16 | 上海应用技术学院 | Three-dimensional graphite alkene/cobaltosic oxide composite material, preparation method thereof and application |
| CN105854801A (en) * | 2016-05-10 | 2016-08-17 | 江苏大学 | Nitrogen-doped porous carbon material and preparation method and application thereof |
| CN105845457A (en) * | 2016-05-26 | 2016-08-10 | 江苏大学 | Preparation method and application of porous carbon material |
| CN105914048A (en) * | 2016-07-07 | 2016-08-31 | 西华大学 | Porous carbon-graphene-metal oxide composite material and preparation method and application thereof |
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