CN106744804B - A kind of preparation method and supercapacitor of multi-stage porous carbon material - Google Patents
A kind of preparation method and supercapacitor of multi-stage porous carbon material Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000010453 quartz Substances 0.000 claims description 25
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- 125000006850 spacer group Chemical group 0.000 claims description 11
- 239000007772 electrode material Substances 0.000 claims description 9
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 9
- 238000009413 insulation Methods 0.000 claims description 8
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- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
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- 238000000354 decomposition reaction Methods 0.000 abstract description 2
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- 229910052799 carbon Inorganic materials 0.000 description 11
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- 239000011799 hole material Substances 0.000 description 9
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- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
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- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
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- 229910052845 zircon Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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Abstract
本发明属于超级电容器技术领域，提供了一种多级孔碳材料的制备方法及超级电容器。该制备方法包括以下步骤：合成粒径为20‑200nm的ZIFs晶体材料；将ZIFs晶体材料置于微波加热炉中；在惰性氛围下，5min内将ZIFs晶体材料的温度升高至加热处理温度进行加热碳化处理，惰性氛围的压力值为20000‑80000Pa，加热碳化处理的温度为800‑1100℃，加热碳化处理的时间为5‑300min；冷却处理。本发明通过合成粒径为20‑200nm的ZIFs晶体材料，并在5min内迅速将温度升高到800℃以上进行碳化处理，促使ZIFs晶体材料迅速分解，随后又重新键合，最终生成多级孔碳材料。该制备方法制备工序简单快速，成本低，并且能够实现多级孔碳材料的有效控制。
The invention belongs to the technical field of supercapacitors, and provides a preparation method of a multi-level porous carbon material and a supercapacitor. The preparation method comprises the following steps: synthesizing a ZIFs crystal material with a particle size of 20-200 nm; placing the ZIFs crystal material in a microwave heating furnace; under an inert atmosphere, raising the temperature of the ZIFs crystal material to the heating treatment temperature within 5 minutes to carry out For the heating and carbonization treatment, the pressure value of the inert atmosphere is 20000-80000Pa, the temperature of the heating and carbonization treatment is 800-1100°C, and the time of the heating and carbonization treatment is 5-300min; the cooling treatment is performed. In the invention, the ZIFs crystal material with a particle size of 20-200 nm is synthesized, and the temperature is rapidly increased to more than 800° C. for carbonization treatment within 5 minutes, so as to promote the rapid decomposition of the ZIFs crystal material, and then re-bond to finally generate multi-level pores. carbon material. The preparation method has the advantages of simple and rapid preparation process, low cost, and can realize the effective control of the hierarchical porous carbon material.
Description
Technical field
The invention belongs to the preparation methods of supercapacitor technologies field more particularly to a kind of multi-stage porous carbon material and super
Capacitor.
Background technique
Supercapacitor is a kind of novel energy storage apparatus, have charge/discharge speed is fast, high-efficient, operating temperature range is wide,
The features such as having extended cycle life.Porous carbon materials are due to its flourishing cellular structure, high-ratio surface, satisfactory electrical conductivity, high chemistry
The advantages that stability is the preferred electrode material of supercapacitor.
Porous carbon materials can be divided into micropore (being less than 2nm), mesoporous (2-50nm) and macropore carbon materials according to its pore size
Material (is greater than 50nm).Although the carbon material in different ducts the exploration of structure, pattern in terms of have been achieved for it is very big
Progress, but as research is deeply with the continuous extension of practical application, single cellular structure, which being far from satisfying, to be showed
Real demand.In this case, multi-stage porous carbon material comes into being.Multi-stage porous carbon material is exactly by two or more hole
It is linked a kind of new carbon to form network structure, the carbon material for combining different pore structures not only has single-stage hole material
The excellent properties of material, and it makes it with big specific surface area, flourishing multistage pore structure and multi-stage porous synergistic effect
The characteristic better than other single pore structure carbon materials is provided in each application field.Particularly, in electrode of super capacitor
The different ducts of Material Field, multi-stage porous carbon material form good mutual supplement with each other's advantages in electrochemistry, are keeping electrode material
Under higher specific capacitance, moreover it is possible to which there is good high rate performance.
The method of traditional synthesis porous carbon materials is the high-temperature decomposition of carbon source presoma；And existing synthesis multi-stage porous
The method of carbon material is mainly template, by the material with special pore structure as template, is then filled into precursor
In die clearance, the multi-stage porous carbon material gone divided by acquisition reverse phase duplication formwork structure through precursor carbonization and template.Before
Person can only obtain the porous carbon materials of single cellular structure, although and the latter can prepare the porous carbon of multi-pore channel structure
Material, but preparation process has to pass through addition template, removes removing template, and process is tedious, and preparation time is long, higher cost.Most
Closely also have on a small quantity about using ZIFs (Zeolitic Imidazolate Frameworks, class zeolitic imidazolate framework material)
It is carbonized by high temperature pyrolysis and obtains the report of high-ratio surface porous carbon electrode material, however most of the porous carbon of this method preparation
Duct range is relatively narrow, and mostly single cellular structure cannot control the multipolarization in duct.
Therefore, the preparation method of existing multi-stage porous carbon material there are porous carbon duct narrow scope, preparation section it is cumbersome,
Time length and problem at high cost.
Summary of the invention
The purpose of the present invention is to provide the preparation methods and supercapacitor of a kind of multi-stage porous carbon material, it is intended to solve existing
With the presence of multi-stage porous carbon material preparation method porous carbon duct narrow scope, preparation section is cumbersome, the time is long and cost
High problem.
It is an object of that present invention to provide a kind of preparation method of multi-stage porous carbon material, which includes:
Synthesize the ZIFs crystalline material that partial size is 20-200nm；
The ZIFs crystalline material is placed in microwave oven；
In an inert atmosphere, the temperature of the ZIFs crystalline material heat treatment temperature is increased in 5min to heat
Carbonization treatment, the pressure value of the inert atmosphere are 20000-80000Pa, and the temperature of the heating carbonization treatment is 800-1100
DEG C, the time of the heating carbonization treatment is 5-300min；
Cooling treatment.
Another object of the present invention, which also resides in, provides a kind of supercapacitor, including electrode material, and the electrode material is
The preparation method of multi-stage porous carbon material, the multi-stage porous carbon material of the multi-stage porous carbon material from the above mentioned prepares.
The present invention is the ZIFs crystalline material of 20-200nm by synthesis partial size, and is rapidly increased to temperature in 5min
800 DEG C or more carry out carbonization treatment, promote ZIFs crystalline material to decompose rapidly, are then bonded again, ultimately generate multi-stage porous
Carbon material.The preparation method preparation section is simple and quick, at low cost, and can be realized effective control of multi-stage porous carbon material.
Detailed description of the invention
Fig. 1 is the flow diagram of the preparation method for the multi-stage porous carbon material that one embodiment of the present of invention provides；
Fig. 2 is the cross-sectional view of the structure for the device for preparing multi-stage porous carbon material that one embodiment of the present of invention provides；
Fig. 3 is the structure top view for the device for preparing multi-stage porous carbon material that one embodiment of the present of invention provides；
Fig. 4 is another structural profile for the device for preparing multi-stage porous carbon material that one embodiment of the present of invention provides
Figure.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot
It is interpreted as indication or suggestion relative importance or implicitly indicates the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include one or more of the features.In the description of the present invention,
The meaning of " plurality " is two or more, unless otherwise specifically defined.
As shown in Figure 1, one embodiment of the present of invention provides a kind of preparation method of multi-stage porous carbon material comprising:
Step S101: the ZIFs crystalline material that synthesis partial size is 20-200nm.
In embodiments of the present invention, be carbonized persursor material selection be the key that be made multi-stage porous carbon, it is more in order to prepare
Grade hole carbon must be by the size controlling of the ZIFs crystalline material of synthesis in 20-200nm, so that intergranular contact area to the greatest extent may be used
Can be big, guarantee between subsequent ZIFs crystalline material particle it is rapid decompose, be bonded again during keep the contact of large area, with
Increase the probability that multistage hole generates.In the concrete application of the embodiment of the present invention, the partial size of ZIFs crystalline material passes through ZIFs
Reaction temperature, reaction density and reaction time when crystalline material synthesizes etc. control.
In embodiments of the present invention, the corresponding pattern of particle that ZIFs crystalline material partial size is 20-200nm is globoid.
Other three-dimensional shapes of the surface area ratio of globoid are bigger, and particle and intergranular contact area are bigger, in this way the particle in carbonization
Between form link, the probability for generating hole is bigger.Wherein, globoid refer specifically to sphere or regular dodecahedron or cube
The polyhedron of the comparison rules such as body, in the concrete application of the embodiment of the present invention, ZIFs crystalline material can be in globoid
Any one or a combination thereof.If the pattern not instead of globoid of ZIFs crystalline material particle, other patterns are for example, elongated
It is rodlike or needle-shaped, then it is undesirable.
In embodiments of the present invention, ZIFs crystalline material specifically can be any one in class zeolitic imidazolate framework material
Kind, such as ZIF-8 (molecular formula C8H12N4Zn, structure are SOD topology), ZIF-67 (molecular formula C8H12N4Co, structure are opened up for SOD
Flutter) etc..Below by taking ZIF-8 and ZIF-67 as an example, illustrate preparation method.
The preparation method of ZIF-8, comprising the following steps:
Weigh 2.9328g Zn (NO3)2·6H2O and 6.4785g 2-methylimidazole is dissolved in respectively equipped with 200mL methanol
In beaker, above-mentioned solution is mixed after being uniformly dissolved, and places the beaker on magnetic stirring apparatus, gentle agitation is default at room temperature
By being centrifugally separating to obtain milky white precipitate after time, grinding obtains white powder after 80-180 DEG C of drying.By test, powder
The microstructure of particle is the globoid of rule, and particle diameter distribution is in 40-50nm.Wherein, preset time and reaction temperature can be with
The particle size of ZIFs crystalline material as needed is defined.Specifically, preset time can be within 0.5-48h, more
Specifically, it can be 1h.
The preparation method of ZIF-67, comprising the following steps:
Weigh 5.2492g Co (NO3)2·6H2O and 11.5942g 2-methylimidazole is dissolved in respectively equipped with 200mL methanol
In beaker, above-mentioned solution is mixed after being uniformly dissolved, and places the beaker on magnetic stirring apparatus, gentle agitation is default at room temperature
By being centrifugally separating to obtain milky white precipitate after time, grinding obtains white powder after 80-180 DEG C of drying.By test, powder
The microstructure of particle is the globoid of rule, and particle diameter distribution is in 80-110nm.Wherein, preset time and reaction temperature can be with
The particle size of ZIFs crystalline material as needed is defined, and specifically, preset time can be within 0.5-48h, more
Specifically, it can be 1h.
Step S102: ZIFs crystalline material is placed in microwave oven.
In one embodiment of the invention, step S102 is specifically included: by ZIFs crystalline material be placed in microwave by
In the device of body layer, and device is placed in microwave oven；Wherein, microwave receptive layers are made of microwave receptor.
In embodiments of the present invention, microwave receptor is specially and electromagnetic wave can be absorbed and project energy transmission heat to ZIFs
The substance of crystalline material can be at least one of silicon carbide, active carbon.When microwave receptor is the mixture of the two, mix
Composition and division in a proportion example is unrestricted.
In embodiments of the present invention, power >=1KW of microwave oven.Since microwave receptive layers 2 are to ZIFs crystalline material
Auxiliary heating, the power of microwave oven can be reduced, in a particular application, just as power >=1KW of microwave oven
It may be implemented to heat ZIFs crystalline material and be carbonized, it, can also be into more specifically, when the power of microwave oven is only 1KW
Row heating carbonization.Corresponding traditional microwave directly heats mode, can reduce more energy consumptions, reduce cost.
The present invention provides one be used for the ZIFs crystalline material microwave heating Installation practice, structural profile
Figure is as shown in Fig. 2, structure top view is as shown in Figure 3.Specifically, described device includes being prolonged by the central axial device outer wall of device
The direction stretched successively includes quartz ampoule 1, microwave receptive layers 2, wall 3 and the first insulating layer 4.
Quartz ampoule 1 includes being connected as the hollow spheres bottom of ZIFs crystalline material carbonizing zone and with hollow spheres bottom
Tubing string, and hollow spheres bottom and tubing string coaxially communicate.
Microwave receptive layers 2, wall 3 and the first insulating layer 4 are tubular structure, and microwave receptive layers 2 are set in quartz
The surface of pipe 1, wall 3 are set in the surface of microwave receptive layers 2, and the first insulating layer 4 is set in the surface of wall 3, and micro-
Wave receptive layers 2, wall 3 form sealing in one end of hollow spheres bottom.
In embodiments of the present invention, the hollow spheres bottom of quartz ampoule 1 is as carbonizing zone, for placing ZIFs crystalline material
And heating carbonization treatment is carried out to ZIFs crystalline material.Due to 1 bottom of quartz ampoule be hollow spheres, hollow spheres bottom it is close
The opening bore on its head is small and the bore close to its tail portion is big, and ZIFs crystalline material can be made to be evenly distributed in carbonizing zone,
It can be avoided ZIFs crystalline material simultaneously to be scattered due to the influence of air-flow to quartz ampoule 1, and then influence ZIFs crystal material
The heating of material, or even the device of the external offer heat source of pollution.
Further, in embodiments of the present invention, the connection type of hollow spheres bottom and tubing string can be flexible connection,
It is also possible to integrated molding.When the connection type of hollow spheres bottom and tubing string is to be flexibly connected, user can be according to stone
The service condition of English pipe 1 carries out any replacement or cleaning so that quartz ampoule 1 can be multiple to hollow spheres bottom and/or tubing string
It uses, has saved cost, can also be adapted to according to the tubing string of the demand replacement different length or different inner diameters that use more
Carbonization Conditions or more ZIFs crystalline materials；When the connection type of hollow spheres bottom and tubing string is integrated molding,
Integral replacing or cleaning can also will be carried out to quartz ampoule according to the service condition of device.
Further, in embodiments of the present invention, the internal diameter of hollow spheres bottom can be the interior of 3-5cm and/or tubing string
Diameter can be 15-30mm.Specifically, the internal diameter of hollow spheres bottom can be limited as a certain specific value conduct in 3-5cm
Then the inner diameter size of hollow spheres bottom changes the internal diameter numerical value of tubing string according to the practical carbonization situation of ZIFs crystalline material；
The internal diameter of tubing string can also be limited as inner diameter size of a certain specific value as hollow spheres bottom in 15-30mm, then
The internal diameter numerical value of hollow spheres bottom is changed according to the practical carbonization situation of ZIFs crystalline material.Such as the ZIFs for needing to be carbonized
When crystalline material quality increases, there can be the quartz ampoule 1 of larger inner diameter hollow spheres bottom by replacing to increase ZIFs crystalline substance
The carbonizing zone of body material；When the gas flow for needing to be passed through is bigger, there can be the quartz of larger inner diameter tubing string by replacing
Pipe 1 is to increase the contact surface of ZIFs crystalline material and gas.
Further, in embodiments of the present invention, the thickness of quartz ampoule 1 can be 1.5-5mm.1 thickness of quartz ampoule is closing
Increase in suitable range can play the effect of heat preservation to a certain extent, i.e., in suitable thickness range, when the thickness of quartz ampoule 1
When degree increases, quartz ampoule 1 is better to the heat insulation effect of ZIFs crystalline material.
In embodiments of the present invention, microwave receptive layers 2 are set in the surface of quartz ampoule 1, and microwave receptive layers 2 are that auxiliary is heated
Body layer makes ZIFs crystalline material short for carrying out auxiliary heating to ZIFs crystalline material in the case where outside provides heat source
The target temperature for reaching carbonization in time is conducive to the heating carbonization speed for improving ZIFs crystalline material.Specifically, microwave receptor
Layer 2 can be it is powdered make 1 thermally equivalent of quartz ampoule preferably to contact with quartz ampoule 1, more specifically, microwave receptive layers 2 can
To be made of single carbofrax material, it is also possible to that microwave heat source can be absorbed by other to carry out ZIFs crystalline material
Other substances of auxiliary heating collectively constitute, for example, it may be being made of the mixture of silicon carbide and active carbon.When microwave receptor
When layer is the mixture of the two, mixed proportion is unrestricted.
Wherein, ZIFs crystalline material is the substance of weak absorbing microwave, i.e. the substance of nonpolar molecule.ZIFs crystalline material exists
Faint heating under directly the acting on of microwave, but since around microwave receptive layers 2 are brought rapidly up in microwave field and are ZIFs crystal
Material provides heat source from outside to inside, and the heating temperature of ZIFs crystalline material is made to rise rapidly and facilitate it further in microwave
It is heated and is carbonized in, reinforce the speed that ZIFs crystalline material absorbs microwave and own temperature is made to increase from inside to outside, reach fast
The effect of speed auxiliary heating.Meanwhile the heating in conjunction with ZIFs crystalline material under the auxiliary heating of microwave receptive layers 2 from outside to inside
And heating in microwave field from inside to outside and the heating that makes ZIFs crystalline material more uniform while being rapidly heated
Carbonization.
Further, in embodiments of the present invention, the internal diameter of microwave receptive layers 2 can be 1.5-5cm；Microwave receptive layers 2
Thickness can be 1-3cm.The internal diameter and thickness of microwave receptive layers 2 can be defined simultaneously, can also individually limit internal diameter
For 1.5-5cm a certain specific value and change the thickness sizes of microwave receptive layers 2, or individually limit with a thickness of 1-3cm's
A certain specific value and the inner diameter size for changing microwave receptive layers 2.
In embodiments of the present invention, wall 3 is set in the surface of microwave receptive layers 2, for completely cutting off 2 He of microwave receptive layers
First insulating layer 4, prevent microwave receptive layers 2 heat up when temperature it is excessively high caused by the first insulating layer 4 hot-spot and ablation.
When microwave receptive layers 2 are made of silicon carbide powder, wall 3 is also as the device for containing silicon carbide powder.Wall 3 can be with
By it is resistant to high temperature and not with the material composition of silicon carbide reactor, more specifically, wall 3 can be alumina layer.
Further, in embodiments of the present invention, the internal diameter of wall 3 is 4-10cm；And/or wall 3 with a thickness of
2-5mm.Such as summarize in specific embodiment, internal diameter 6cm, with a thickness of 3mm.
In embodiments of the present invention, the first insulating layer 4 is set in the surface of wall 3.Wherein, the first insulating layer 4 is uniform
Be distributed on the outer surface of the central axis away from device of wall 3, enable wall 3 uniformly by the first insulating layer
4 are covered, to keep the temperature to wall 3 and by the inside microwave receptive layers 2 and quartz ampoule 1 that wall 3 wraps up.
Further, in embodiments of the present invention, the first insulating layer 4 with a thickness of 3-8cm, such as specific embodiment converge
Always, with a thickness of 6cm.By the control to 4 thickness of the first insulating layer, so that effectively playing insulation effect to wall 3
Meanwhile reduction is to the consumption of the first insulating layer 4.In another embodiment, the material of first insulating layer 4 can with but not only
Select any one of common asbestos, high alumina asbestos, cotton containing zircon, mullite fiber blanket.Certainly, as long as being that by heat preservation
Other heat preservation heat-resisting materials of effect may be incorporated for preparing the first insulating layer 4 of the invention.
In embodiments of the present invention, microwave receptive layers 2, wall 3 and the first insulating layer 4 are tubular structure, and micro-
Wave receptive layers 2, wall 3 form sealing in one end of hollow spheres bottom.The present apparatus by microwave receptive layers 2, wall 3 with
And first insulating layer 4 be disposed as tubular structure, can effectively control microwave receptive layers 2, wall 3 and the first insulating layer
4 adjacent two layers, adjacent three layers of distance value can also effectively control each layer at a distance from device central axis, therefore, microwave receptor
Layer 2, wall 3 and the first heat preservation can with uniform heat temperature raising carried out to internal corresponding each layer and uniform protect
Temperature, heating carbonization that can be more uniform to ZIFs crystalline material are kept the temperature.The present apparatus is by microwave receptive layers 2, wall 3 in
One end of empty spherical bottom forms sealing, can effectively wrap up hollow spheres bottom comprehensively, plays the effect for promoting heating comprehensively
Fruit.
Further, in embodiments of the present invention, as shown in figure 4, in order to further so that the present apparatus is reached better guarantor
Temp effect, device further include the second insulating layer 5 for having the end that the nearly hollow spheres bottom of the first insulating layer 4 is arranged in, for pair
Microwave receptive layers 2, wall 3 further are kept the temperature in the sealing that one end of hollow spheres bottom is formed.In specific embodiment
In, the material of second insulating layer 5 can with but not only select common asbestos, high alumina asbestos, cotton containing zircon, mullite fiber blanket
Any one of, it can also select but not just for asbestos brick.
In embodiments of the present invention, the device with microwave receptive layers makes ZIFs crystalline material in a short time in carbonizing zone
Reach target temperature, heat it is more uniform it is quick, high-efficient, low energy consumption, operation is convenient, while avoiding ZIFs crystalline material pair
The pollution of microwave cavity.
Step S103: in an inert atmosphere, in 5min by the temperature of ZIFs crystalline material be increased to heat treatment temperature into
Row heating carbonization treatment, the pressure value of inert atmosphere are 20000-80000Pa, and the temperature for heating carbonization treatment is 800-1100
DEG C, the time for heating carbonization treatment is 5-300min.
In embodiments of the present invention, the temperature of ZIFs crystalline material is increased to target heat-treatment temperature in 5min, it is fast
Violent heating can generate fulminant heat and act on ZIFs crystalline material, promote C-H, C- of ZIFs crystalline material molecule
The keys such as O and C-N are largely broken rapidly, bond together to form H again2O, CO2, NO2Equal gases evolution, thus realize carbonization, but due to
The speed for forming gas evolution is far smaller than the speed decomposed, and can also be mutually bonded between ZIFs particle, eventually form mutual chain
The hole network structure connect.
In embodiments of the present invention, oxygen or the presence of other gases make to send out in ZIFs crystalline material carbonisation in order to prevent
Other reactions, the carbonization treatments of ZIFs crystalline material such as raw oxidation carry out in an inert atmosphere.Inert atmosphere includes but is not limited to
Vacuum nitrogen environment.As a preferred embodiment, inert atmosphere vacuumizes-nitrogen charging gas disposal realization by repeating, and vacuumizes-nitrogen charging
The number of gas disposal is at least 3 times.Specifically, ZIFs crystalline material is placed in after microwave oven, vacuumize, stops vacuumizing
It is then vacuumized again with purged with nitrogen flow afterwards, nitrogen stream is replaced more than three times.
In embodiments of the present invention, in order to prevent air remaining in microwave oven can under high temperature rough vacuum ion
Change, form ion beam to generate vacuum arc, is unfavorable for the electromagnetism carbonization of ZIFs crystalline material, needing will be in microwave oven
Vacuum degree control in appropriate range.It specifically, can be by the vacuum degree control in microwave oven in 20000-
In the range of 80000Pa, more specifically, the vacuum degree in microwave oven can be the range arbitrary number of 20000-80000Pa
Value can choose integer value corresponding with microwave oven vacuum meter in order to facilitate reading, can also exist according to actual needs
It is chosen within the scope of 20000-80000Pa.
In embodiments of the present invention, during the heating carbonization treatment of ZIFs crystalline material, the temperature of carbonization treatment is heated
There are stringent control in degree, time.Heating temperature is excessively high or heating time is too long, since vaporization is stronger in activation process, holds
Unformed porous contraction is easily led to, hole is eventually led to and collapses to form macropore, is unfavorable for gas storage；And heating temperature is too low or adds
The hot time is too short, cannot achieve preferable carbonization effect, is equally unfavorable for obtaining multi-stage porous carbon material.In view of this, of the invention
The temperature that embodiment heats carbonization treatment is 800-1100 DEG C, time 5-300min.
The embodiment of the present invention is prepared in porous carbon materials method, and the temperature control of carbonization treatment process also affects multistage
The carbonizing degree and carbonization quality of hole carbon material.Further preferred 900-1050 DEG C of the embodiment of the present invention is used as activation temperature.This
The temperature that inventive embodiments heat carbonization treatment is still more preferably 980 DEG C or so, at this point, prepared porous carbon materials
Porosity is preferable, and preparation cost, time are all relatively inexpensive.
Step S104: cooling treatment.
In embodiments of the present invention, cooling treatment carries out in an inert atmosphere.Terminate when heating is carbonized, stops microwave, i.e.,
Stop heating at once, cooling rapidly, the time required to can shortening cooling, effectively improves efficiency, reduces cost.Therefore, cooling
The decline natural cooling that handling can be with furnace temperature certainly, can also be lazy in order to accelerate cooling rate again on the original basis
Property air-flow, as cooled under nitrogen stream to be cooled to room temperature obtained porous carbon materials.
The present invention is the ZIFs crystalline material of 20-200nm by synthesis partial size, and is rapidly increased to temperature in 5min
800 DEG C or more carry out carbonization treatment, promote ZIFs crystalline material to decompose rapidly, are then bonded again, ultimately generate multi-stage porous
Carbon material.The preparation method preparation section is simple and quick, at low cost, and can be realized effective control of multi-stage porous carbon material.
It is illustrated below in conjunction with specific embodiment.
Embodiment 1
Step S1011: the ZIF-8 that synthesis partial size is 45nm.
The ZIF-8: being sent into the hollow spheres bottom of quartz ampoule 1 by step S1021, and being placed into package has carborundum powder
End alumina spacer layer in, and with cut out regular asbestos by alumina spacer layer package it is regular be placed in microwave oven,
The alumina spacer layer with silicon carbide powder and quartz ampoule position are adjusted, ZIF-8 in infrared temperature sensor alignment pipe is made.
Step S1031: closing fire door, closes vacuum release valve, presses and vacuumize button, after furnace chamber is evacuated to vacuum, closes
It closes and vacuumizes button, and being filled with nitrogen to cavity air pressure in cavity is 60kPa, repeats vacuum nitrogen gas twice, finally
It is 20kPa that nitrogen, which is charged to air pressure,.Microwave heating is opened, adjustment microwave power is 2.5kW, rises to temperature in 5mins
1000 DEG C, then adjusting microwave power makes temperature in 1000 DEG C of holding 120mins.
Step S1041: closing microwave, and fire door is opened after temperature drops to room temperature, and collecting good material and numbering can be obtained
Multi-stage porous carbon material.
Embodiment 2
Step S1012: the ZIF-67 that synthesis partial size is 90nm.
The ZIF-67: being sent into the hollow spheres bottom of quartz ampoule 1 by step S1022, and being placed into package has silicon carbide
In the alumina spacer layer of powder, and alumina spacer layer package regular is placed in microwave oven with regular asbestos are cut out
In, the alumina spacer layer with silicon carbide powder and quartz ampoule position are adjusted, ZIF- in infrared temperature sensor alignment pipe is made
67。
Step S1032: closing fire door, closes vacuum release valve, presses and vacuumize button, after furnace chamber is evacuated to vacuum, closes
It closes and vacuumizes button, and being filled with nitrogen to cavity air pressure in cavity is 60kPa, repeats vacuum nitrogen gas twice, finally
It is 30kPa that nitrogen, which is charged to air pressure,.Microwave heating is opened, adjustment microwave power is 3kW, and temperature is made to rise to 900 in 3mins
DEG C, then adjusting microwave power makes temperature in 900 DEG C of holding 180mins.
Step S1042: closing microwave, and fire door is opened after temperature drops to room temperature, and collecting good material and numbering can be obtained
Multi-stage porous carbon material.
The present invention also provides a kind of supercapacitor, including electrode material, electrode material is multi-stage porous carbon material, multistage
The preparation method of the multi-stage porous carbon material of hole carbon material from the above mentioned prepares.
The above is merely preferred embodiments of the present invention, be not intended to limit the invention, it is all in spirit of the invention and
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within principle.
Claims (7)
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