CN109637835A - A kind of nitrogen-doped carbon nanometer pipe/cobaltosic oxide composite aerogel and preparation method thereof - Google Patents
A kind of nitrogen-doped carbon nanometer pipe/cobaltosic oxide composite aerogel and preparation method thereof Download PDFInfo
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
The invention discloses a kind of nitrogen-doped carbon nanometer pipe/cobaltosic oxide composite aerogels, nitrogen-doped carbon nanometer pipe aeroge is prepared first with polypyrrole aeroge, then it is impregnated in dopamine solution and carries out polymeric modification, and it is compounded to form nitrogen-doped carbon nanometer pipe/ZIF-67 composite aerogel with ZIF-67, finally it is fired.The present invention is using the polypyrrole aeroge containing nitrogen-atoms as the presoma of nitrogen-doped carbon nanometer pipe, and the effective compound of nitrogen-doped carbon nanometer pipe aeroge and cobaltosic oxide is realized using the auto polymerization characteristic of poly-dopamine, the preparation method being related to is simple, reaction condition is mild；Gained composite material can effectively keep the three-dimensional porous structure of aeroge, nitrogen-doped carbon nanometer pipe aeroge can effective dispersed cobalt oxide nano particle, it can realize that the electric double layer capacitance of nitrogen-doped carbon nanometer pipe and the fake capacitance of cobaltosic oxide be combined with each other simultaneously, be suitable for the fields such as supercapacitor.
Description
Technical field
The invention belongs to aerogel materials, technical field of material chemistry, and in particular to a kind of nitrogen-doped carbon nanometer pipe/tetra- oxidations three
Cobalt composite aerogel and preparation method thereof.
Background technique
Aerogel material is a kind of form of solid matter, is one of the smallest solid of world's upper density, has porous web
The features such as network structure, controllable huge specific surface area and meso-scale.Usual aerogel material is silica aerogel and carbon airsetting
Glue；Wherein carbon aerogels are unique conductive aeroges, can be used for the electrode material of double electric layers supercapacitor.
Currently, different according to the mechanism of storage electric energy, supercapacitor can be divided into double layer capacitor and pseudocapacitors.It is double
The electrode material that electric layer capacitor uses is mostly porous carbon materials (such as active carbon, carbon aerogels, carbon nanotube, graphene)；
Pseudocapacitors are also referred to as Faradic pseudo-capacitor, and generation mechanism is different from double layer capacitor, the electrode material of pseudocapacitors
Predominantly metal oxide and conducting polymer.The effective of these materials compound would be possible to obtain the super of excellent electrochemical performance
Grade capacitor electrode material.
The practical specific capacitance of research discovery metal oxide in recent years is much smaller than its theoretical specific capacitance, this be mainly because
Metal oxide for the lower electric conductivity of metal oxide, nano-scale is easy aggregation.At present by carbon nanotube and metal
Generally yield is dusty material for oxide compound.Recent research indicate that the electronic structure of carbon material, crystalline texture and hydrophilic
Property can be changed by Heteroatom doping.The specific capacitance of carbon material compared with undoped carbon material after chemical doping is usual
It can improve.The hydrophily of carbon material had not only can be improved in nitrogen-doping, but also can improve the chemical property of carbon material.However, mesh
The N doping of the preceding graphene for nano-lamellar structure itself and the carbon nanotube with nano tubular structure, usually
By additional nitrogenous compound, and carry out what high-temperature roasting or hydro-thermal reaction were realized.
Summary of the invention
It is a primary object of the present invention in view of the deficienciess of the prior art, providing a kind of nitrogen-doped carbon nanometer pipe/tetra-
Co 3 O composite aerogel, it utilizes the auto polymerization of dopamine using nitrogen-doped nanometer pipe aeroge and ZIF-67 as presoma
It is effective compound that effect realizes nitrogen-doped nanometer pipe aeroge and ZIF-67's, then is fired and to obtain nitrogen-doped carbon nanometer pipe/tetra- oxidations
Three cobalt composite aerogels；Gained polypyrrole/ZIF-67 composite aerogel can express excellent chemical property and stable circulation
Property, and the preparation method being related to is simple, easily-controllable, is suitble to promote and apply.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of nitrogen-doped carbon nanometer pipe/cobaltosic oxide composite aerogel, prepares nitrogen first with polypyrrole aeroge and mixes
Then miscellaneous carbon nanotube aerogel is impregnated in dopamine solution and carries out polymeric modification, then successively, be impregnated in nitric acid repeatedly
Nitrogen-doped carbon nanometer pipe/ZIF-67 composite aerogel is prepared in the methanol solution of cobalt and the methanol solution of 2-methylimidazole, finally
It is fired to obtain nitrogen-doped carbon nanometer pipe/cobaltosic oxide composite aerogel.
A kind of preparation method of above-mentioned nitrogen-doped carbon nanometer pipe/cobaltosic oxide composite aerogel, comprising the following steps:
1) it carries out calcining under an argon using polypyrrole aeroge and prepares nitrogen-doped carbon nanometer pipe aeroge；
2) nitrogen-doped carbon nanometer pipe aeroge is soaked in dopamine solution, adjust the pH value of gained mixed liquor to 8~
9, polymeric modification is carried out to nitrogen-doped carbon nanometer pipe aeroge；
3) methanol solution and 2- of cobalt nitrate will be sequentially placed into through the modified nitrogen-doped carbon nanometer pipe aeroge of step 2)
Immersion treatment is carried out in the methanol solution of methylimidazole, repeats above-mentioned soaking step, products therefrom is washed, is dried, is obtained
Nitrogen-doped carbon nanometer pipe/ZIF-67 composite aerogel；
4) nitrogen-doped carbon nanometer pipe/ZIF-67 composite aerogel is roasted under protective atmosphere, obtains nitrogen-doped carbon and receives
Mitron/cobaltosic oxide composite aerogel.
In above scheme, the concentration of dopamine is 3~5mg/mL in the dopamine solution.
In above scheme, polymeric modification temperature described in step 2) be room temperature, the time be 18~for 24 hours.
In above scheme, each raw material used in step 3) is by weight are as follows: modified polypyrrole aeroge 4~6
Part, 300~600 parts of the methanol solution of cobalt nitrate, 300~600 parts of the methanol solution of 2-methylimidazole；Wherein weight shared by cobalt nitrate
Measuring number is 10~30 parts, and parts by weight shared by 2-methylimidazole are 30~60 parts.
In above scheme, immersion treatment time described in step 3) is 1~3h.
In above scheme, number of repetition described in step 3) is 6~10 times.
In above scheme, the protective atmosphere is argon gas or nitrogen.
In above scheme, the maturing temperature is 700~900 DEG C, and the time is 2~4h.
Compared with prior art, the invention has the benefit that
1) present invention is organic with metal using the polypyrrole aeroge containing nitrogen-atoms as the presoma of nitrogen-doped carbon nanometer pipe
Frame compound ZIF-67 is the presoma of cobaltosic oxide, and realizes that nitrogen-doped carbon is received using the auto polymerization characteristic of poly-dopamine
Abundant compound (the utilizing the amino and the effective Coordination Adsorption cobalt ions of hydroxyl of poly-dopamine) of mitron aeroge and ZIF-67, then pass through
Simple calcination process realizes effective compound, the preparation method letter being related to of nitrogen-doped carbon nanometer pipe aeroge and cobaltosic oxide
List, reaction condition are mild, product composition is controllable, are suitble to popularization and application；
2) present invention directly using the polypyrrole aeroge containing nitrogen-atoms as the presoma of nitrogen-doped carbon nanometer pipe, by its with
Gained product of roasting can effectively keep the three-dimensional porous structure of aeroge after ZIF-67 is compound；
3) in present invention gained composite material, nitrogen-doped carbon nanometer pipe aeroge can effective dispersed cobalt oxide nanometer
Grain, and the electric double layer capacitance of nitrogen-doped carbon nanometer pipe and the fake capacitance of cobaltosic oxide be combined with each other, be conducive to electron-transport with
Energy-storage property can effectively promote the electrochemical cycle stability of cobaltosic oxide, make that it is suitable for the fields such as supercapacitor.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
In following embodiment, by pass sequentially through self assembly, freeze-drying, pyrolysis and etc. prepare nitrogen-doped carbon nanometer pipe airsetting
Glue, specific preparation step are shown in document Applied Surface Science 2017,414,218-223.
Embodiment 1
A kind of nitrogen-doped carbon nanometer pipe/cobaltosic oxide composite aerogel, preparation method include the following steps:
1) it carries out calcining under an argon using polypyrrole aeroge and prepares nitrogen-doped carbon nanometer pipe aeroge；
2) gained nitrogen-doped carbon nanometer pipe aeroge is soaked in the dopamine solution that concentration is 3mg/mL, and uses Tris
Buffer solution adjusts the pH value of gained mixed liquor to 8.0, carries out polymeric modification (room temperature reaction to nitrogen-doped carbon nanometer pipe aeroge
18h)；
3) methanol solution and 2- first of cobalt nitrate will be sequentially placed into through the modified nitrogen-doped carbon nanometer pipe aeroge of step 2)
Immersion treatment in the methanol solution of base imidazoles repeats above-mentioned soaking step, products therefrom is washed, is dried, N doping is obtained
Carbon nanotube/ZIF-67 composite aerogel；Each raw material used in this step is calculated by weight as: modified nitrogen-doped carbon
4 parts of nanotube aeroge, 300 parts of the methanol solution (wherein 10 parts of cobalt nitrate) of cobalt nitrate, the methanol solution 500 of 2-methylimidazole
Part (wherein 32 parts of 2-methylimidazole)；The time impregnated every time is 1.5h, and number of repetition is 6 times；
4) gained nitrogen-doped carbon nanometer pipe/ZIF-67 composite aerogel is placed in tube furnace in a nitrogen atmosphere, heating
To 800 DEG C of roasting 2h, nitrogen-doped carbon nanometer pipe/cobaltosic oxide composite aerogel is obtained.
Nitrogen-doped carbon nanometer pipe obtained by the present embodiment/cobaltosic oxide composite aerogel is subjected to Electrochemical Detection, in 1A/
The capacity retention that g current density cycle charge-discharge is 3000 times is 94.5%.
Embodiment 2
A kind of nitrogen-doped carbon nanometer pipe/cobaltosic oxide composite aerogel, preparation method include the following steps:
1) it carries out calcining under an argon using polypyrrole aeroge and prepares nitrogen-doped carbon nanometer pipe aeroge；
2) gained nitrogen-doped carbon nanometer pipe aeroge is soaked in the dopamine solution that concentration is 4mg/mL, and uses Tris
Buffer solution adjusts the pH value of gained mixed liquor to 9.0, carries out polymeric modification (room temperature reaction to nitrogen-doped carbon nanometer pipe aeroge
24h)；
3) methanol solution and 2- first of cobalt nitrate will be sequentially placed into through the modified nitrogen-doped carbon nanometer pipe aeroge of step 2)
Immersion treatment in the methanol solution of base imidazoles repeats above-mentioned soaking step, products therefrom is washed, is dried, N doping is obtained
Carbon nanotube/ZIF-67 composite aerogel；Each raw material used in this step is calculated by weight as: modified nitrogen-doped carbon
6 parts of nanotube aeroge, 400 parts of the methanol solution (wherein 25 parts of cobalt nitrate) of cobalt nitrate, the methanol solution 600 of 2-methylimidazole
Part (wherein 50 parts of 2-methylimidazole)；The time impregnated every time is 2h, repeats to impregnate number to be 8 times；
4) gained nitrogen-doped carbon nanometer pipe/ZIF-67 composite aerogel is placed in tube furnace under an argon atmosphere, heating
To 900 DEG C of roasting 2h, nitrogen-doped carbon nanometer pipe/cobaltosic oxide composite aerogel is obtained.
Nitrogen-doped carbon nanometer pipe obtained by the present embodiment/cobaltosic oxide composite aerogel is subjected to Electrochemical Detection, in 1A/
The capacity retention that g current density cycle charge-discharge is 3000 times is 94.1%.
Embodiment 3
A kind of nitrogen-doped carbon nanometer pipe/cobaltosic oxide composite aerogel, preparation method include the following steps:
1) it carries out calcining under an argon using polypyrrole aeroge and prepares nitrogen-doped carbon nanometer pipe aeroge；
2) gained nitrogen-doped carbon nanometer pipe aeroge is soaked in the dopamine solution that concentration is 5mg/mL, and uses Tris
Buffer solution adjusts the pH value of gained mixed liquor to 8.5, carries out polymeric modification (room temperature reaction to nitrogen-doped carbon nanometer pipe aeroge
20h)；
3) methanol solution and 2- first of cobalt nitrate will be sequentially placed into through the modified nitrogen-doped carbon nanometer pipe aeroge of step 2)
Immersion treatment in the methanol solution of base imidazoles repeats above-mentioned soaking step, products therefrom is washed, is dried, N doping is obtained
Carbon nanotube/ZIF-67 composite aerogel；Each raw material used in this step is calculated by weight as: modified nitrogen-doped carbon
5 parts of nanotube aeroge, 300 parts of the methanol solution (wherein 12 parts of cobalt nitrate) of cobalt nitrate, the methanol solution 400 of 2-methylimidazole
Part (wherein 35 parts of 2-methylimidazole)；The time impregnated every time is 2.5h, repeats to impregnate number to be 9 times；
4) gained nitrogen-doped carbon nanometer pipe/ZIF-67 composite aerogel is placed in tube furnace in a nitrogen atmosphere, heating
To 700 DEG C of roasting 4h, nitrogen-doped carbon nanometer pipe/cobaltosic oxide composite aerogel is obtained.
Nitrogen-doped carbon nanometer pipe obtained by the present embodiment/cobaltosic oxide composite aerogel is subjected to Electrochemical Detection, in 1A/
The capacity retention that g current density cycle charge-discharge is 3000 times is 95.2%.
Embodiment 4
A kind of nitrogen-doped carbon nanometer pipe/cobaltosic oxide composite aerogel, preparation method include the following steps:
1) it carries out calcining under an argon using polypyrrole aeroge and prepares nitrogen-doped carbon nanometer pipe aeroge；
2) gained nitrogen-doped carbon nanometer pipe aeroge is soaked in the dopamine solution that concentration is 3mg/mL, and uses Tris
Buffer solution adjusts the pH value of gained mixed liquor to 8.5, carries out polymeric modification (room temperature reaction to nitrogen-doped carbon nanometer pipe aeroge
21h)；
3) methanol solution and 2- first of cobalt nitrate will be sequentially placed into through the modified nitrogen-doped carbon nanometer pipe aeroge of step 2)
Immersion treatment in the methanol solution of base imidazoles repeats above-mentioned soaking step, products therefrom is washed, is dried, N doping is obtained
Carbon nanotube/ZIF-67 composite aerogel；Each raw material used in this step is calculated by weight as: modified nitrogen-doped carbon
4 parts of nanotube aeroge, 300 parts of the methanol solution (wherein 20 parts of cobalt nitrate) of cobalt nitrate, the methanol solution 400 of 2-methylimidazole
Part (wherein 50 parts of 2-methylimidazole)；The time impregnated every time is 1h, repeats to impregnate number to be 10 times；
4) gained nitrogen-doped carbon nanometer pipe/ZIF-67 composite aerogel is placed in tube furnace under an argon atmosphere, heating
To 800 DEG C of roasting 2.5h, nitrogen-doped carbon nanometer pipe/cobaltosic oxide composite aerogel is obtained.
Nitrogen-doped carbon nanometer pipe obtained by the present embodiment/cobaltosic oxide composite aerogel is subjected to Electrochemical Detection, in 1A/
The capacity retention that g current density cycle charge-discharge is 3000 times is 94.6%.
Embodiment 5
A kind of nitrogen-doped carbon nanometer pipe/cobaltosic oxide composite aerogel, preparation method include the following steps:
1) it carries out calcining under an argon using polypyrrole aeroge and prepares nitrogen-doped carbon nanometer pipe aeroge；
2) gained nitrogen-doped carbon nanometer pipe aeroge is soaked in the dopamine solution that concentration is 4mg/mL, and uses Tris
Buffer solution adjusts the pH value of gained mixed liquor to 8.0, carries out polymeric modification (room temperature reaction to nitrogen-doped carbon nanometer pipe aeroge
20h)；
3) methanol solution and 2- first of cobalt nitrate will be sequentially placed into through the modified nitrogen-doped carbon nanometer pipe aeroge of step 2)
Immersion treatment in the methanol solution of base imidazoles repeats above-mentioned soaking step, products therefrom is washed, is dried, N doping is obtained
Carbon nanotube/ZIF-67 composite aerogel；Each raw material used in this step is calculated by weight as: modified nitrogen-doped carbon
5 parts of nanotube aeroge, 450 parts of the methanol solution (wherein 25 parts of cobalt nitrate) of cobalt nitrate, the methanol solution 550 of 2-methylimidazole
Part (wherein 60 parts of 2-methylimidazole)；The time impregnated every time is 1.5h, repeats to impregnate number to be 7 times；
4) gained nitrogen-doped carbon nanometer pipe/ZIF-67 composite aerogel is placed in tube furnace in a nitrogen atmosphere, heating
To 800 DEG C of roasting 3h, nitrogen-doped carbon nanometer pipe/cobaltosic oxide composite aerogel is obtained.
Nitrogen-doped carbon nanometer pipe obtained by the present embodiment/cobaltosic oxide composite aerogel is subjected to Electrochemical Detection, in 1A/
The capacity retention that g current density cycle charge-discharge is 3000 times is 95.0%.
Comparative example 1
1) nitrogen-doped carbon nanometer pipe aeroge is prepared using polypyrrole aeroge；
2) gained nitrogen-doped carbon nanometer pipe aeroge is soaked in the dopamine solution that concentration is 4mg/mL, and uses Tris
Buffer solution adjusts the pH value of gained mixed liquor to 8.0, carries out polymeric modification (room temperature reaction to nitrogen-doped carbon nanometer pipe aeroge
20h)；
Nitrogen-doped carbon nanometer pipe aeroge obtained by this comparative example is subjected to Electrochemical Detection, is filled in 1A/g current density circulation
The capacity retention that electric discharge is 3000 times is 85.1%.
Comparative example 2
1) after mixing by the methanol solution of the methanol solution of cobalt nitrate and 2-methylimidazole, reaction is stood for 24 hours, by institute
It obtains product to be washed, dried, obtains ZIF-67 powder；Each raw material used in this step is calculated by weight as: cobalt nitrate
300 parts of methanol solution (wherein 20 parts of cobalt nitrate), 400 parts of (wherein 2-methylimidazole 50 of methanol solution of 2-methylimidazole
Part)；
2) gained ZIF-67 powder is placed in tube furnace under an argon atmosphere, is heated to 800 DEG C of roasting 2.5h, obtains four oxygen
Change three cobalt dusts.
Cobaltosic oxide obtained by this comparative example is subjected to Electrochemical Detection, at 1A/g current density cycle charge-discharge 3000 times
Capacity retention be 84.2%.
Each raw material cited by the present invention can realize that the bound value of the present invention and each raw material, interval value can
Realize the present invention；Embodiment numerous to list herein.The bound value of technological parameter of the invention, interval value can realize this
Invention, embodiment numerous to list herein.
Claims (8)
1. a kind of nitrogen-doped carbon nanometer pipe/cobaltosic oxide composite aerogel prepares N doping first with polypyrrole aeroge
Then carbon nanotube aerogel is impregnated in dopamine solution and carries out polymeric modification, then successively, be impregnated in cobalt nitrate repeatedly
Methanol solution and 2-methylimidazole methanol solution in prepare nitrogen-doped carbon nanometer pipe/ZIF-67 composite aerogel, most pass through afterwards
Roasting obtains nitrogen-doped carbon nanometer pipe/cobaltosic oxide composite aerogel.
2. a kind of nitrogen-doped carbon nanometer pipe described in claim 1/cobaltosic oxide composite aerogel preparation method, feature exist
In, comprising the following steps:
1) nitrogen-doped carbon nanometer pipe aeroge is prepared using polypyrrole aeroge；
2) nitrogen-doped carbon nanometer pipe aeroge is soaked in dopamine solution, the pH value of adjusting gained mixed liquor is right to 8~9
Nitrogen-doped carbon nanometer pipe aeroge carries out polymeric modification；
3) methanol solution and 2- methyl of cobalt nitrate will be sequentially placed into through the modified nitrogen-doped carbon nanometer pipe aeroge of step 2)
Immersion treatment is carried out in the methanol solution of imidazoles, repeats above-mentioned soaking step, products therefrom is washed, is dried, nitrogen is obtained and mixes
Miscellaneous carbon nanotube/ZIF-67 composite aerogel；
4) nitrogen-doped carbon nanometer pipe/ZIF-67 composite aerogel is roasted under protective atmosphere, obtain nitrogen-doped carbon nanometer pipe/
Cobaltosic oxide composite aerogel.
3. preparation method according to claim 2, which is characterized in that the concentration of dopamine is 3 in the dopamine solution
~5mg/mL.
4. preparation method according to claim 2, which is characterized in that polymeric modification temperature described in step 2) is room temperature,
Time be 18~for 24 hours.
5. preparation method according to claim 2, which is characterized in that each raw material used in step 3) is by weight
Are as follows: 4~6 parts of modified polypyrrole aeroge, 300~600 parts of the methanol solution of cobalt nitrate, the methanol solution of 2-methylimidazole
300~600 parts；Wherein parts by weight shared by cobalt nitrate are 10~30 parts, and parts by weight shared by 2-methylimidazole are 30~60 parts.
6. preparation method according to claim 2, which is characterized in that immersion treatment time described in step 3) is 1~3h.
7. preparation method according to claim 2, which is characterized in that number of repetition described in step 3) is 6~10 times.
8. preparation method according to claim 2, which is characterized in that the maturing temperature is 700~900 DEG C, the time 2
~4h.
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| CN110729476A (en) * | 2019-10-22 | 2020-01-24 | 中国科学院宁波材料技术与工程研究所 | Pseudo-capacitance composite high-capacity lithium manganate positive electrode material and preparation method thereof, and lithium ion battery |
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