CN108557797A - A kind of cobalt doped porous carbon materials and preparation method thereof - Google Patents
A kind of cobalt doped porous carbon materials and preparation method thereof Download PDFInfo
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- CN108557797A CN108557797A CN201810517042.0A CN201810517042A CN108557797A CN 108557797 A CN108557797 A CN 108557797A CN 201810517042 A CN201810517042 A CN 201810517042A CN 108557797 A CN108557797 A CN 108557797A
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Abstract
The invention discloses a kind of cobalt doped porous carbon materials and preparation method thereof.The preparation method of the present invention includes following steps：(1) first that four hydration cobalt acetates, dicyandiamide and absolute ethyl alcohol and stirring is uniform；It after stirring evenly, is heated to 70 75 DEG C and solvent is allowed to volatilize, obtain complexing sample；(2) the complexing sample for obtaining step (1) pours into surface plate be dried in vacuo later with ammonium acetate and Gelatin in 85 95 DEG C of deionized water；(3) it by the high temperature cabonization under an inert atmosphere of sample after the vacuum drying of step (2), after high temperature cabonization, is etched with salt acid soak, obtains cobalt doped porous carbon materials.The method of the present invention is environmental-friendly, preparation method is simple, convenient for large-scale production.Cobalt doped porous carbon materials nitrogen content prepared by the present invention is high, has high specific surface area and relatively uniform pore-size distribution, has a good application prospect in toxic gas absorption and electrochemical field.
Description
Technical field
The invention belongs to technical field of nano material, it particularly relates to a kind of cobalt doped porous carbon materials and its preparation
Method.
Background technology
Carbon material, which is widely used, does the electrode of ultracapacitor, this is because carbon material easily obtains, easy processing, big table
Area and porosity, low-resistivity, good surface chemistry environment and physical and chemical performance and low cost etc..The storage of energy
Mainly charge is carried out in carbon material electrode and bath surface.Porous carbon materials due to peculiar property, synthesis material
Abundant and easy acquisition, therefore there are universal applications in modern science.Porous carbon materials have chemical stability high, acidproof
A series of features such as alkali, high temperature resistant, conduction, heat conduction, this kind of material usually have flourishing hole, high specific surface area, high
Chemical stability, excellent heat-resisting, acid and alkali-resistance and unique electronic conductivity matter, are indispensable important materials in modern industry
One of material.
In recent years, in order to further improve application of the porous carbon materials in terms of ultracapacitor, usually by hetero atom (example
Such as N, B, S) or (amino, nitro, sulfonic group etc.) containing heteroatomic group be doped in surface or the structure of porous carbon materials,
The performance of the various aspects of porous carbon materials is set to be upgraded and improved.Material with fake capacitance performance promotes ultracapacitor
Development, this material can improve the energy storage capacity of capacitor.However, most of fake capacitances are from electrode material surface
Redox reaction, during faraday's reaction, only one layer of very thin surface has participated in reaction.Moreover, being filled in faraday
In electric process, simple transition metal oxide such as MnO2Electric conductivity is very poor, and conducting polymer is easy mechanical degradation, hinders it
Application on electrode material.Therefore, structure carbon-based composite electrode material can not only improve the utilization rate of active material, together
When can also improve the electric conductivity and mechanical strength of composite material.
It includes amido carbohydrate, melamine, benzene to prepare the most common nitrogenous precursor of nitrogenous electrode material for super capacitor
Methylamine etc..Although the porous carbon of high nitrogen-containing can be obtained by the method for nitrating in situ, there is also many problems, than
Such as：Preparation process needs to use many organic chemical reagents, and price is relatively expensive；Introduce metal is combined preparation to have with carbon material
The ultracapacitor of better performance is also worth people further to explore.
Invention content
The object of the present invention is to provide it is a kind of it is environmental-friendly, preparation method is simple, convenient for large-scale production, high nitrogen content cobalt
Doped porous carbon material and preparation method thereof.
In order to solve the above-mentioned technical problem, the present invention uses following technical scheme：
A kind of preparation method of cobalt doped porous carbon materials, is as follows：
(1) first that four hydration cobalt acetates, dicyandiamide and absolute ethyl alcohol and stirring is uniform；After stirring evenly, it is heated to 70 DEG C
It allows solvent to volatilize, obtains complexing sample；
(2) the complexing sample for obtaining step (1) and ammonium acetate and Gelatin be in 85-95 DEG C of deionized water, it
After pour into surface plate and be dried in vacuo；
(3) by the high temperature cabonization under an inert atmosphere of sample after the vacuum drying of step (2), after high temperature cabonization, with salt acidleach
Bubble etching, obtains cobalt doped porous carbon materials.
In the present invention, four mass ratioes for being hydrated cobalt acetates, Ammoniom-Acetate, dicyandiamide and gelatin are (0.25-0.75)：(1-2)：
(1-1.5)：(1-2).
In the present invention, in step (2), vacuum drying temperature is 55-65 DEG C.
In the present invention, in step (3), the heating schedule of high temperature cabonization is as follows：With heating rate for 5 DEG C/min, from room temperature
600-950 DEG C is heated to be kept the temperature again as 1-5h.
In the present invention, in step (3), concentration of hydrochloric acid 0.1-2mol/L.
In the present invention, in step (3), immersion etch period is 2-3h.
The present invention further provides cobalt doped porous carbon materials made from a kind of above-mentioned preparation method.
The present invention compared with the existing technology, has the following advantages and beneficial effect：
1, cobalt and dicyandiamide are played the role of complexing by the present invention using gelatin as the carbon template of material, by cobalt and dicyandiamide with
It can not only make the mixing of raw material evenly among the form incorporation gelatin of complexing, moreover it is possible to so that the nitrogen content of material is increased, to carry
Rise the performance of material.
2, the present invention prepares porous carbon materials by carbon source of gelatin, and raw material sources are extensive, of low cost.
3, the super capacitor material that method of the invention is prepared is to be made material by thermal decomposition release ammonia due to ammonium acetate
There is bulk multi-hole structure in material, and this structure pore-size distribution is uniform, has high specific surface area, in absorption, ultracapacitor, very
It is with a wide range of applications to the fields such as catalysis and fuel cell.
Description of the drawings
Fig. 1 is the adsorption desorption curve graph that embodiment 1 obtains cobalt doped porous carbon materials.
Fig. 2 is the SEM figures that embodiment 2 obtains cobalt doped porous carbon materials.
Fig. 3 is the graph of pore diameter distribution that embodiment 2 obtains cobalt doped porous carbon materials.
Specific implementation mode
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
The content and constituent of cobalt doped porous carbon materials are as follows：
A kind of preparation method of cobalt doped porous carbon materials, includes the following steps：
It is first that four hydration cobalt acetates, dicyandiamide and absolute ethyl alcohol and stirring is uniform, it is heated to 70 DEG C and solvent is allowed to volatilize；Then
By the sample of complexing and ammonium acetate and Gelatin in 90 DEG C of deionized water, liquid is poured into surface plate after solvent is uniform,
It is dried in vacuo at 60 DEG C.Xerogel is then put into quartz boat, quartz boat is placed in tube furnace and is carried out in a nitrogen atmosphere
Heating, nitrogen flow rate 50ml/min, heating rate are 5 DEG C/min, are heated slowly to 600 DEG C from room temperature, carbonization time 2h；
Then hydrochloric acid is configured to 0.1M solution etches 3h and cleans the material after carbonization, be dried in vacuo, obtain at 60 DEG C after suction filtration
Cobalt doped porous carbon materials.Obtained material aperture is 4nm, and it is 0.6ml/g, specific surface area 273m to add up pore volume2/ g,
Main element group becomes Co, N, C and O, and Fig. 1 is the adsorption desorption curve graph that embodiment 1 obtains cobalt doped porous carbon materials.
Application Example 1
8mg is weighed after the material of embodiment 1 is ground, and then weighs poly- the four of 1mg carbon blacks and 0.1ml 10mg/ml
Vinyl fluoride is dried after mixing, is applied in nickel foam after taking 3mg mixtures to soak, is then dried again；Hydroxide with 6M
Potassium 200ml takes 10ml infiltrations to be coated with the nickel foam 2h of sample, to be surveyed under the current density of 1A/g in the potassium hydroxide solution of 6M
The specific capacitance for obtaining material is 308F/g.
Embodiment 2
The content and constituent of cobalt doped porous carbon materials are as follows：
A kind of preparation method of cobalt doped porous carbon materials, includes the following steps：
It is first that four hydration cobalt acetates, dicyandiamide and absolute ethyl alcohol and stirring is uniform, it is heated to 80 DEG C and solvent is allowed to volatilize；Then
By the sample of complexing and ammonium acetate and Gelatin in 80 DEG C of deionized water, liquid is poured into surface plate after solvent is uniform,
It is dried in vacuo at 60 DEG C.Xerogel is then put into quartz boat, quartz boat is placed in tube furnace and is carried out in a nitrogen atmosphere
Heating, nitrogen flow rate 50ml/min, heating rate are 5 DEG C/min, are heated slowly to 750 DEG C from room temperature, carbonization time 2h；
Then hydrochloric acid is configured to 0.3M solution etches 2.5h and cleans the material after carbonization, be dried in vacuo, obtain at 60 DEG C after suction filtration
To cobalt doped porous carbon materials.Obtained material aperture is 4.0nm, and it is 0.65ml/g to add up pore volume, and specific surface area is
239m2/ g, main element group become Co, N, C and O, and Fig. 2 is the SEM figures that embodiment 2 obtains cobalt doped porous carbon materials.Fig. 3
It is the graph of pore diameter distribution that embodiment 2 obtains cobalt doped porous carbon materials.
Application Example 2
8mg is weighed after the material of embodiment 2 is ground, and then weighs poly- the four of 1mg carbon blacks and 0.1ml 10mg/ml
Vinyl fluoride is dried after mixing, is applied in nickel foam after taking 5mg mixtures to soak, is then dried again；Hydroxide with 6M
Potassium 200ml is taken 10ml infiltrations to be coated with the nickel foam 2h of sample, is measured for 1A/g with current density in the potassium hydroxide solution of 6M
The specific capacitance of material is 462F/g.
Embodiment 3
The content and constituent of cobalt doped porous carbon materials are as follows：
A kind of preparation method of cobalt doped porous carbon materials, includes the following steps：
It is first that four hydration cobalt acetates, dicyandiamide and absolute ethyl alcohol and stirring is uniform, it is heated to 80 DEG C and solvent is allowed to volatilize；Then
By the sample of complexing and ammonium acetate and Gelatin in 80 DEG C of deionized water, liquid is poured into surface plate after solvent is uniform,
It is dried in vacuo at 60 DEG C.Xerogel is then put into quartz boat, quartz boat is placed in tube furnace and is carried out in a nitrogen atmosphere
Heating, nitrogen flow rate 50ml/min, heating rate are 5 DEG C/min, are heated slowly to 850 DEG C from room temperature, carbonization time 2h；
Then hydrochloric acid is configured to 1M solution etches 2h and cleans the material after carbonization, be dried in vacuo at 60 DEG C after suction filtration, obtain cobalt
Doped porous carbon material.Obtained material aperture is 5.0nm, and it is 0.49ml/g, specific surface area 239m to add up pore volume2/
G, main element group become Co, N, C and O.
Application Example 3
8mg is weighed after the material of embodiment 3 is ground, and then weighs poly- the four of 1mg carbon blacks and 0.1ml 10mg/ml
Vinyl fluoride is dried after mixing, is applied in nickel foam after taking 4mg mixtures to soak, is then dried again；Hydroxide with 6M
Potassium 200ml is taken 10ml infiltrations to be coated with the nickel foam 2h of sample, is measured for 1A/g with current density in the potassium hydroxide solution of 6M
The specific capacitance of material is 294F/g.
Claims (7)
1. a kind of preparation method of cobalt doped porous carbon materials, which is characterized in that be as follows：
(1) first that four hydration cobalt acetates, dicyandiamide and absolute ethyl alcohol and stirring is uniform；After stirring evenly, it is heated to 70-80 DEG C and allows
Solvent volatilizees, and obtains complexing sample；
(2) the complexing sample for obtaining step (1) falls later with ammonium acetate and Gelatin in 80-95 DEG C of deionized water
Enter in surface plate and is dried in vacuo；
(3) it by the high temperature cabonization under an inert atmosphere of sample after the vacuum drying of step (2), after high temperature cabonization, is carved with salt acid soak
Erosion, obtains cobalt doped porous carbon materials.
2. preparation method according to claim 1, which is characterized in that four hydration cobalt acetates, Ammoniom-Acetate, dicyandiamide and gelatin
Mass ratio be (0.25-0.75)：(1-2)：(1-1.5)：(1-2).
3. preparation method according to claim 1, which is characterized in that in step (2), vacuum drying temperature is 55-65 DEG C.
4. preparation method according to claim 1, which is characterized in that in step (3), the heating schedule of high temperature cabonization is such as
Under：With heating rate for 5 DEG C/min, it is heated to 600-950 DEG C from room temperature and is kept the temperature again as 1-5h.
5. preparation method according to claim 1, which is characterized in that in step (3), concentration of hydrochloric acid 0.1-2mol/L.
6. preparation method according to claim 1, which is characterized in that in step (3), immersion etch period is 2-3h.
7. cobalt doped porous carbon materials made from a kind of preparation method according to one of claim 1-6.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014201463A (en) * | 2013-04-02 | 2014-10-27 | 旭化成ケミカルズ株式会社 | Nitrogen-containing carbon material and method for producing the same, and electrode for fuel cell |
| CN105845915A (en) * | 2016-05-31 | 2016-08-10 | 陕西科技大学 | Method for preparing anode material of three-dimensional porous carbon skeleton/CoO composite structured lithium ion battery |
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- 2018-05-25 CN CN201810517042.0A patent/CN108557797B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014201463A (en) * | 2013-04-02 | 2014-10-27 | 旭化成ケミカルズ株式会社 | Nitrogen-containing carbon material and method for producing the same, and electrode for fuel cell |
| CN105845915A (en) * | 2016-05-31 | 2016-08-10 | 陕西科技大学 | Method for preparing anode material of three-dimensional porous carbon skeleton/CoO composite structured lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| 葛余俊: "钴、氮掺杂多孔碳作为氧还原催化剂的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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