CN106783197B - A kind of ZIF-8 pyrolysis porous carbon-graphene composite material and its preparation method and application - Google Patents
A kind of ZIF-8 pyrolysis porous carbon-graphene composite material and its preparation method and application Download PDFInfo
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- CN106783197B CN106783197B CN201611008324.5A CN201611008324A CN106783197B CN 106783197 B CN106783197 B CN 106783197B CN 201611008324 A CN201611008324 A CN 201611008324A CN 106783197 B CN106783197 B CN 106783197B
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Abstract
The present invention relates to a kind of ZIF-8 pyrolysis porous carbon-graphene composite material and its preparation method and application, the structures of the composite material are as follows: graphene is wrapped in ZIF-8 and is pyrolyzed porous carbon surface.Preparation method includes: to mix zinc nitrate hexahydrate and 2-methylimidazole, is dissolved in solvent, stands 1~2h, obtains milk shape solution, is centrifuged, and is washed, and vacuum drying obtains ZIF-8 crystal；ZIF-8 crystal is mixed with potassium citrate, is ground, high temperature cabonization, pickling, it is dry to get.Preparation method of the invention is simple, it is at low cost, obtained ZIF-8 pyrolysis porous carbon-graphene composite material has many advantages, such as that chemical property is stable, capacitive character is good, specific surface area is high, it takes full advantage of multi-stage porous and three-dimensional conductive frame improves chemical property, its specific capacitance has reached 300F/g under the current density of 1A/g, is a kind of high performance electrode material of ideal supercapacitor.
Description
Technical field
The invention belongs to technical field of nano material, in particular to a kind of ZIF-8 is pyrolyzed porous carbon-graphene composite material
And its preparation method and application.
Background technique
Zeolite imidazole ester skeleton structure has excellent physical and chemical performance, such as higher porosity and specific surface area, good
Good chemical stability etc..These special natures make it be widely used in electrochemical field.
In the prior art, pure ZIF-8 pyrolysis porous carbon is by obtaining after ZIF-8 crystal direct carbonization；But pure ZIF-8
It is pyrolyzed porous carbon relative distribution, the electrode material specific capacity for being used as supercapacitor is low, again forthright difference.
Graphene is a kind of two dimensional crystal being made of carbon atom.Pure grapheme material is two-dimentional large pore material.System at present
The method of standby graphene is directly by the methods of organic carbon and graphene oxide reduction, and graphene is large pore material, easy shape
Reticulate structure；But pure graphene is as electrode material that often specific capacity is lower, forthright difference, energy density are low again.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of ZIF-8 pyrolysis porous carbon-graphene composite material and its
Preparation method and application, this method prepare ZIF-8 crystal by chemical synthesis, then by grinding ZIF-8 crystal and citric acid
Potassium is uniformly mixed, and graphene is wrapped in ZIF-8 and is pyrolyzed porous carbon surface by high temperature cabonization, obtains the ZIF- of electrochemical performance
8 pyrolysis porous carbon-graphene composite materials, preparation process environmental protection, simple process, preparation cost are cheap.
ZIF-8 pyrolysis porous carbon prepared by the present invention is carbonized to obtain by ZIF-8 crystal high-temperature, and the raw material sources of graphene are
Potassium citrate.The present invention is compound by graphene and the porous carbon phase of ZIF-8 pyrolysis, substantially increases the chemical property of material.
A kind of ZIF-8 of the invention is pyrolyzed porous carbon-graphene composite material, the structure of the composite material are as follows: graphite
Alkene is wrapped in ZIF-8 and is pyrolyzed porous carbon surface.
The raw material for preparing of the composite material includes: zinc nitrate hexahydrate, 2-methylimidazole, methanol, potassium citrate etc..
A kind of ZIF-8 of the invention is pyrolyzed porous carbon-graphene composite material preparation method, comprising:
(1) zinc nitrate hexahydrate and 2-methylimidazole are mixed, is dissolved in solvent, stood 1~2h, it is molten to obtain milk shape
Liquid is centrifuged, and is washed, and vacuum drying obtains ZIF-8 crystal；
It (2) is in mass ratio that 1:5~1:40 is mixed with potassium citrate by the ZIF-8 crystal in step (1), grinding obtains
Uniform white powder, high temperature cabonization, pickling is dry, obtains ZIF-8 pyrolysis porous carbon-graphene composite material；Wherein, high
The condition of temperature carbonization are as follows: 800 DEG C of heat preservation 2h.
In the step (1) mass ratio of zinc nitrate hexahydrate, 2-methylimidazole and solvent be 1~5:8~10:700~
800,
The solvent is methanol.
The condition being centrifuged in the step (1) are as follows: 8000~10000 revs/min, be centrifuged 5~10 minutes.
Washing is methanol or ethanol washing 2~3 times in the step (1).
Dry temperature is 50~60 DEG C in the step (1), and vacuum degree is -0.1~-0.08MPa.
The mass ratio of ZIF-8 crystal and potassium citrate is 1:20 in the step (2).
The atmosphere of step (2) the high temperature carbonisation is nitrogen and argon gas gaseous mixture or argon gas；The rate of heating is 2
~5 DEG C/min.
The condition of pickling is 6~8h of hydrochloric acid agitator treating of 0.5~1.0mol/L in the step (2).
The composite material is applied to the electrode material field of supercapacitor.
Novel ZIF-8 pyrolysis porous carbon-graphene composite wood is prepared by simple technological design in the present invention
Material.The composite material has the advantage that graphene is wrapped in ZIF-8 and is pyrolyzed porous carbon surface, forms three-dimensional conductive frame.It is multiple
Condensation material is hierarchical porous structure, improves the specific capacity of material entirety and forthright again.Therefore, ZIF-8 is pyrolyzed porous carbon and graphite
Alkene progress is effective compound, can achieve good chemiluminescence, to prepare the composite material haveing excellent performance.
Beneficial effect
(1) method preparation process of the invention is simple and environmentally-friendly, easily operated, is a kind of Green Chemistry preparation method；
(2) experimental design is ingenious in the present invention, by high temperature cabonization technology, is simply and effectively wrapped in graphene sheet layer
ZIF-8 pyrolysis porous carbon-graphene composite material is prepared in the surface ZIF-8；
(3) ZIF-8 prepared by the present invention is pyrolyzed porous carbon-graphene composite material specific capacitance with higher, compared with
Good is forthright again, is the ideal electrode material of supercapacitor；
(4) ZIF-8 pyrolysis porous carbon-graphene composite material prepared by the present invention has forthright good again, power density
The advantages that height, energy density is big, and capacitive character is good, chemical property is stable, specific surface area is high, takes full advantage of multi-stage porous and three-dimensional is led
Electric frame improves chemical property, its specific capacitance has reached 300F/g under the current density of 1A/g.
Detailed description of the invention
Fig. 1 is that (A) ZIF-8 is pyrolyzed porous carbon, (B) pure graphene nano lamella in embodiment 1, and (C) ZIF-8 is pyrolyzed porous
The SEM of carbon-graphite alkene composite material schemes；
Fig. 2 is that ZIF-8 is pyrolyzed porous carbon, graphene in embodiment 1, and ZIF-8 is pyrolyzed porous carbon-graphene composite material
Multiplying power figure；
Fig. 3 is that ZIF-8 is pyrolyzed porous carbon, graphene in embodiment 1, and ZIF-8 is pyrolyzed porous carbon-graphene composite material
Power density and energy density profile；
Fig. 4 is the SEM figure that ZIF-8 is pyrolyzed porous carbon-graphene composite material (ZIF-8-G-1) in embodiment 2.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
(1) zinc nitrate hexahydrate and 2-methylimidazole are mixed, is dissolved in methanol, zinc nitrate hexahydrate, 2- methyl miaow
The mass ratio of azoles and methanol is 1:8:700.
(2) by solution left standstill 1h, milk shape solution is obtained.
(3) obtained solution is centrifuged 10min under 10000 revs/min of speed, after washed three times with methanol, obtain
ZIF-8 crystal.
(4) obtained ZIF-8 crystal is dry；Wherein, dry temperature is 60 DEG C, and vacuum degree is -0.1MPa.
It (5) is in mass ratio that 1:20 is mixed with potassium citrate by the ZIF-8 crystal being prepared, grinding obtains uniform white
Color powder.
(6) under nitrogen atmosphere by obtained white powder, 5 DEG C/min is warming up to 800 DEG C, keeps 2h, and carbonization is prepared
ZIF-8 is pyrolyzed porous carbon-graphene composite material.
(7) ZIF-8 of preparation is pyrolyzed porous carbon-graphene composite material 0.5mol/L salt pickling 6h, it is dry, it obtains
ZIF-8 is pyrolyzed porous carbon-graphene composite material.
It is porous that preparation-obtained ZIF-8 pyrolysis is characterized using scanning electron microscope (SEM), electrochemical workstation
The pattern and structure of carbon-graphite alkene composite material and the chemical property as electrode material for super capacitor.
SEM test result shows: prepared ZIF-8 pyrolysis porous carbon-graphene composite material has in the present embodiment
Three-dimensional structure, graphene nanometer sheet are wrapped in ZIF-8 and are pyrolyzed porous carbon surface.Referring to Fig. 1.Electrochemical results show:
ZIF-8 is pyrolyzed porous carbon-graphene composite material specific capacitance with higher and preferable forthright again, and quality specific capacitance reaches
300F/g, referring to fig. 2；Higher power density has reached 10000W/kg, higher energy density, 40Wh/kg, referring to figure
3.Wherein, the preparation method that ZIF-8 is pyrolyzed porous carbon is shown in comparative example 1.The preparation method of graphene is shown in comparative example 2.
Embodiment 2
(1) zinc nitrate hexahydrate and 2-methylimidazole are mixed, is dissolved in methanol, zinc nitrate hexahydrate, 2- methyl miaow
The mass ratio of azoles and methanol is 1:8:700.
(2) by solution left standstill 1h, milk shape solution is obtained.
(3) obtained solution is centrifuged 10min under 10000 revs/min of speed, after washed three times with methanol, obtain
ZIF-8 crystal.
(4) obtained ZIF-8 crystal is dry；Wherein, dry temperature is 60 DEG C, and vacuum degree is -0.1MPa.
It (5) is in mass ratio that 1:5 is mixed with potassium citrate by the ZIF-8 crystal being prepared, grinding obtains uniform white
Powder.
(6) under nitrogen atmosphere by obtained white powder, 5 DEG C/min is warming up to 800 DEG C, keeps 2h, and carbonization is prepared
ZIF-8 is pyrolyzed porous carbon-graphene composite material.
(7) ZIF-8 of preparation is pyrolyzed porous carbon-graphene composite material 0.5mol/L salt pickling 6h, it is dry, acquisition
Composite material is denoted as ZIF-8-G-1.Its SEM figure is as shown in Figure 4.
Embodiment 3
(1) zinc nitrate hexahydrate and 2-methylimidazole are mixed, is dissolved in methanol, zinc nitrate hexahydrate, 2- methyl miaow
The mass ratio of azoles and methanol is 1:8:700.
(2) by solution left standstill 1h, milk shape solution is obtained.
(3) obtained solution is centrifuged 10min under 10000 revs/min of speed, after washed three times with methanol, obtain
ZIF-8 crystal.
(4) obtained ZIF-8 crystal is dry；Wherein, dry temperature is 60 DEG C, and vacuum degree is -0.1MPa.
It (5) is in mass ratio that 1:40 is mixed with potassium citrate by the ZIF-8 crystal being prepared, grinding obtains uniform white
Color powder.
(6) under nitrogen atmosphere by obtained white powder, 5 DEG C/min is warming up to 800 DEG C, keeps 2h, and carbonization is prepared
ZIF-8 is pyrolyzed porous carbon-graphene composite material.
(7) ZIF-8 of preparation is pyrolyzed porous carbon-graphene composite material 0.5mol/L salt pickling 6h, it is dry, acquisition
Composite material is denoted as ZIF-8-G-2.
Comparative example 1
(1) zinc nitrate hexahydrate and 2-methylimidazole are mixed, is dissolved in methanol, zinc nitrate hexahydrate, 2- methyl miaow
The mass ratio of azoles and methanol is 1:8:700.
(2) by solution left standstill 1h, milk shape solution is obtained.
(3) obtained solution is centrifuged 10min under 10000 revs/min of speed, after washed three times with methanol, obtain
ZIF-8 crystal.
(4) obtained ZIF-8 crystal is dry；Wherein, dry temperature is 60 DEG C, and vacuum degree is -0.1MPa.
(5) the ZIF-8 crystal being prepared is ground, obtains uniform white powder.
(6) under nitrogen atmosphere by obtained white powder, 5 DEG C/min is warming up to 800 DEG C, keeps 2h, and carbonization is prepared
ZIF-8 is pyrolyzed porous carbon.
(7) ZIF-8 of preparation is pyrolyzed porous carbon 0.5mol/L salt pickling 6h, it is dry to get.
Comparative example 2
(1) under nitrogen atmosphere by potassium citrate, 5 DEG C/min is warming up to 800 DEG C, keeps 2h, and graphite is prepared in carbonization
Alkene.
(2) by the graphene of preparation 0.5mol/L salt pickling 6h, it is dry to get.
Claims (6)
1. a kind of ZIF-8 is pyrolyzed porous carbon-graphene composite material preparation method, the structure of the composite material are as follows: graphite
Alkene is wrapped in ZIF-8 and is pyrolyzed porous carbon surface, and wherein the raw material sources of graphene are potassium citrate, and the composite material is applied to
The electrode material field of supercapacitor, comprising the following steps:
(1) zinc nitrate hexahydrate and 2-methylimidazole are mixed, are dissolved in solvent, stood 1~2h, obtain milk shape solution,
Centrifugation is washed, and vacuum drying obtains ZIF-8 crystal, and wherein the mass ratio of zinc nitrate hexahydrate, 2-methylimidazole and solvent is 1
~5:8~10:700~800；
It (2) is in mass ratio that 1:5~1:40 is mixed with potassium citrate by the ZIF-8 crystal in step (1), grinding, high temperature cabonization,
Pickling, it is dry, obtain ZIF-8 pyrolysis porous carbon-graphene composite material；Wherein, the condition of high temperature cabonization are as follows: with 2~5 DEG C/
The heating rate of min is warming up to 800 DEG C, 800 DEG C of heat preservation 2h；The atmosphere of high temperature cabonization process is nitrogen and argon gas gaseous mixture or argon
Gas.
2. a kind of ZIF-8 according to claim 1 is pyrolyzed porous carbon-graphene composite material preparation method, feature
It is, solvent is methanol in the step (1).
3. a kind of ZIF-8 according to claim 1 is pyrolyzed porous carbon-graphene composite material preparation method, feature
It is, the condition being centrifuged in the step (1) are as follows: 8000~10000 revs/min, be centrifuged 5~10 minutes.
4. a kind of ZIF-8 according to claim 1 is pyrolyzed porous carbon-graphene composite material preparation method, feature
It is, washing is methanol or ethyl alcohol in the step (1), is washed 2~3 times.
5. a kind of ZIF-8 according to claim 1 is pyrolyzed porous carbon-graphene composite material preparation method, feature
It is, vacuum drying temperature is 50~60 DEG C in the step (1), and vacuum degree is -0.1~-0.08MPa.
6. a kind of ZIF-8 according to claim 1 is pyrolyzed porous carbon-graphene composite material preparation method, feature
It is, the condition of pickling is 6~8h of hydrochloric acid agitator treating of 0.5~1.0mol/L in the step (2).
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| CN108545712A (en) * | 2018-04-17 | 2018-09-18 | 东华大学 | A method of synthesizing multi-stage porous carbon material with salt template carbonization ZIF-8 |
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| CN113716546B (en) * | 2021-08-31 | 2023-03-28 | 青岛海洋科技中心 | Graphene/mesoporous carbon/ZIF-derived carbon composite three-dimensional graded porous carbon material, and preparation method and application thereof |
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