CN106865546B - A kind of mesoporous micro-pore carbon material and its preparation method and application - Google Patents
A kind of mesoporous micro-pore carbon material and its preparation method and application Download PDFInfo
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Abstract
This application discloses a kind of mesoporous micro-pore carbon materials and its preparation method and application.The mesoporous micro-pore carbon material of the application, pore diameter range are 0.3-20 nanometers, and porosity 50-90%, the mesoporous volume ratio with micropore is 2:1 or more, specific surface area 1500-3200m2/g.The mesoporous micro-pore carbon material of the application, while there is superhigh specific surface area and high mesoporous ratio, it is a kind of completely new carbon material.The preparation method of the application, mesoporous micro-pore carbon material is prepared by silicon oxide material, the creative highly basic using melting dissolves the silica in silicon oxide material, and carbon is activated, it avoids using chlorine or hydrofluoric acid, no toxic gas or liquid generate, and production equipment is more simple, more economical, safe and environment-friendly；In addition, this method is not required to be formed with template mesoporous, a kind of new approach is provided for the preparation of mesoporous micro-pore carbon material.
Description
Technical field
This application involves porous carbon materials fields, more particularly to a kind of mesoporous micro-pore carbon material and preparation method thereof and answer
With.
Background technique
Mesoporous material refers to that average pore size is 2-50 nanometers of porous material, and poromerics refers to that average pore size is received less than 2
The porous material of rice.Since poromerics has aperture more smaller than mesoporous material, bigger specific surface area can be provided；Cause
This, the micro-pore carbon material with high-specific surface area is widely used in absorption, catalysis, supercapacitor etc. and needs bigger serface
Occasion.Traditional high-specific surface area carbon material mainly forms active carbon by carrying out activation to carbon material and prepares, for hole
Diameter cannot be controlled accurately.In addition, traditional active carbon is based on micropore, and since aperture is too small, many target molecules or ion
It spreads very slow or even is unable in access aperture in hole, significant portion of specific surface, which is practically without, to be utilized, and material property cannot
It gives full play to.Such as using micro-pore carbon material as the electrode material of supercapacitor in use, organic bath tetrafluoro boric acid
The diameter of solvation anion/cation in triethylammonium tetrakis is 1.30 nanometers and 1.16 nanometers respectively, less than the size micropore due to
Electrolyte ion cannot be accommodated and electric double layer capacitance cannot be formed, the surface area inside micropore is invalid.
In order to improve the application performance of high-specific surface area carbon material, the mesoporous micropore carbon materials with classification aperture can be prepared
Material.Mesoporous to be interconnected with micropore in mesoporous micro-pore carbon material, since mesoporous aperture is greater than micropore, molecule and ion exist
Diffusion velocity in mesoporous is very fast, mesoporous to enter micropore inner surface for molecule or ion and provide express passway.Mesoporous microporous carbon
The high-specific surface area of material is available to be made full use of, therefore performance is better than simple micro-pore carbon material.But traditional activation
Technique can only prepare simple micro-pore carbon material.Introduce that mesoporous to become research hot in carbon material by template in recent years
Point.But the mould material in template is expendable consumed product, material cost is high, and complex technical process, it is difficult to realize and produce
Industry.Recently, high-specific surface area carbon material is prepared as a kind of new method by carbide material.High ratio is prepared by carbide
The advantages of surface area carbon material, is to make accommodate in hole at most by the chemical Composition Control aperture of carbide
Molecule or ion, to improve catalysis, absorption or capacitive property.In all carbide, silicon carbide or oxidation of coal
Silicon is lower-cost.Oxycarbide ceramic can be by being pyrolyzed to obtain to polysiloxanes.Silicon oxide material is microcosmic
On be the mutually interspersed nano composite structure formed of carbon and amorphous silicon oxide；Remove the amorphous in silicon oxide material
The carbon material with nano-pore can be obtained in silicon.The main method for the carbide preparation microporous carbon reported recently is at high temperature
Logical chlorine is corroded, or is corroded at room temperature using hydrofluoric acid.Both methods has certain risk, chlorine
It is a kind of toxic gas with intense irritation smell, a large amount of suckings can be fatal；Hydrofluoric acid has aggressive, and human body connects
Touching a small amount of hydrofluoric acid can be fatal, belongs to severe poisonous chemicals.And it will form environmentally harmful by-product, such as four chlorinations
Silicon, generate with vapor has corrosivity and irritating hydrogen chloride etc. in air.Simultaneously as introducing mesoporous, carbon materials
The specific surface area of material can be substantially reduced, and there is presently no a kind of i.e. with the specific surface area of superelevation, while having higher mesoporous ratio again
The carbon material of example.
Summary of the invention
The purpose of the application is to provide a kind of new mesoporous micro-pore carbon material, and its preparation method and application.
The application uses following technical scheme:
The one side of the application discloses a kind of mesoporous micro-pore carbon material, and the pore diameter range of the mesoporous micro-pore carbon material is
0.3-20 nanometers, porosity 50-90%, the mesoporous volume ratio with micropore is 2:1 or more, specific surface area 1500-3200m2/
g。
The mesoporous micro-pore carbon material of the application can have simultaneously more than 3000m2The specific surface area of/g, also, it is mesoporous and
The volume ratio of micropore is more than 2:1, and pore volume is more than 2cm3/g.The mesoporous micro-pore carbon material of the application both has high-ratio surface
Product, but it is mesoporous with controlled quantity, so that mesoporous micro-pore carbon material has superior performance and wider purposes.This Shen
Please mesoporous micro-pore carbon material it is a kind of on the way, supercapacitor is used for, so that capacitive property surmounts using import activity
The capacitor of charcoal YP50.
It should be noted that existing high specific area carbon is based on traditional active carbon.Active carbon is a kind of simple
Poromerics.Although the specific surface area highest of active carbon can achieve 3000m2/ g, but mainly based on long and narrow micropore.
Molecule or ion are spread very slow in these long and narrow micropores；Even some big molecules and ion not can enter too small
Micropore.The dynamic performance for showing as material in the application is poor, while effective surface area is lower than actual surface area.Although now
It has been reported that have many high-specific surface area carbon materials for having and being classified mesoporous-microcellular structure, but these materials are mesoporous in introducing
Afterwards, specific surface area is all decreased obviously to 2000m2/ g is lower, while mesoporous ratio is not high, and pore volume is also little.And
The mesoporous micro-pore carbon material of the application can not only obtain 3000m2The specific surface area of/g or more, and mesoporous ratio can be very
It is high.
The another aspect of the application discloses the method for the mesoporous micro-pore carbon material of the application, including at high temperature using molten
The highly basic melted dissolves the silica in silicon oxide material, while activating to carbon, then uses pickling, is situated between
Hole micro-pore carbon material.
It should be noted that existing method is to form porous carbon materials using chlorine or hydrofluoric acid corrosion oxidation silicon；But
It is that there are certain risk for this method, and will cause environmental pollution.Therefore, what the application was creative uses melting
Highly basic dissolves silica, while activating to carbon, is classified mesoporous-micro-pore carbon material, i.e. Jie of the application to obtain
Hole micro-pore carbon material.It is appreciated that the key of the application be using melting highly basic, and under hot conditions use also for
Guarantee that highly basic is in a molten state, therefore, corresponding melting temperature is used according to different highly basic, does not do specific limit herein
It is fixed.First purpose of highly basic is fused silica, and second purpose is activated to carbon, wherein carrying out activation to carbon is
Refer to, the carbon in silicon oxide carbide is made to become active carbon.Highly basic in general chemistry definition may be used to the application, does not do have herein
Body limits.The purpose of pickling processes is to wash off the reaction product of remaining highly basic and highly basic and silica, therefore, as long as energy
It is enough to be reacted with alkali, and be not easy remaining inorganic acid and may be used to the application, it is not specifically limited herein.But in order to reach
Better effect, in the preferred embodiment of the application, the hot conditions of type and highly basic dissolution silica to highly basic are carried out
It is particularly limited to.
Preferably, in the preparation method of the mesoporous micro-pore carbon material of the application, silicon oxide material is by phenyl polysiloxane
High temperature pyrolysis is carried out in protective atmosphere to form.
It should be noted that phenyl polysiloxane, which is that one kind that application proposes is novel, is used to prepare mesoporous micro-pore carbon material
Presoma；, as presoma, mesoporous micropore can be regulated and controled by using with different silicon/carbon ratio example phenyl polysiloxane
The pore-size distribution of carbon material.
It should also be noted that, the preparation method of the application, can be directly used the silicon oxide carbide material prepared for making
Standby mesoporous micro-pore carbon material can also use the raw material of silicon oxide material, i.e. phenyl polysiloxane, prepare mesoporous micropore
Carbon material.High temperature pyrolysis is carried out to phenyl polysiloxane specifically, being included in protective atmosphere, obtains silicon oxide material,
Then phenyl polysiloxane high temperature pyrolysis product is handled using the highly basic of melting at high temperature, then uses pickling, i.e.,
Obtain mesoporous micro-pore carbon material.
Preferably, phenyl polysiloxane is the silica column of polyphenyl methyl siloxane or the hydroxyl containing phenyl.
It should be noted that wherein polyphenyl methyl siloxane is using poly- second in a kind of implementation of the application
Alkenyl phenyl siloxane and polymethyl hydrogen siloxane are reacted and are obtained.
Preferably, the temperature for carrying out high temperature pyrolysis to phenyl polysiloxane is 1000-1200 DEG C, and protective atmosphere is nitrogen
Or argon gas.
Preferably, the high-temperature temperature that highly basic dissolves the silica in silicon oxide material is 700-900 DEG C.
Preferably, highly basic is sodium hydroxide or potassium hydroxide.
Preferably, the acid that pickling processes use is inorganic acid.
It is furthermore preferred that inorganic acid is hydrochloric acid, sulfuric acid or nitric acid.
It preferably, further include being dried after pickling processes using baking oven.
Preferably, for the temperature for using baking oven to dry for 80-120 DEG C, drying time is 3-5 hours.
It should be noted that the purpose of baking oven drying is removal liquid residual, therefore, as long as temperature is to mesoporous micropore carbon materials
Material does not damage itself, and the time dried, be also only required to effectively to remove liquid remains can.
Preferably, the present processes specifically include, by silicon oxide carbide and excessive highly basic mixed grinding, then in inertia
Heating melts highly basic under atmosphere, is dissolved using the highly basic of melting to the silica in silicon oxide material, while to carbon
It is activated, then carries out pickling again, obtain the mesoporous micro-pore carbon material of the application.
It should be noted that the preferred embodiment of the application, in advance mixes silicon oxide material with excessive strong basic solid
Grinding, is then uniformly heated again, melts highly basic, and operation in this way can be safer；It is of course also possible to which highly basic is melted in advance
Melt, then silicon oxide material is dispersed in the highly basic of melting and is reacted.
It should be noted that the preparation method of existing active carbon, is extremely difficult to accurately control aperture, it can not
It introduces mesoporous；And use the preparation method of the application that can prepare 3 nanometers of average pore size under the premise of not using template,
Pore volume 2.4cm3/ g, the volume ratio of mesoporous/micropore are 3.6:1, BET specific surface area 3200m2The mesoporous micro-pore carbon material of/g.
The another aspect of the application discloses the mesoporous micro-pore carbon material of the application in adsorbent material, catalysis material or surpasses
Application in grade capacitor.
It is appreciated that the mesoporous micro-pore carbon material of the application, not only specific surface area with higher, but also with larger proportion
It is mesoporous, therefore, it can be completely applied in adsorbent material, catalysis material or supercapacitor, high-specific surface area is able to maintain
Good imbibition and liquid-keeping property, and its high mesoporous ratio can have better percent of pass.
The another aspect of the application discloses a kind of supercapacitor of mesoporous micro-pore carbon material using the application, mesoporous
Water system specific capacitance of the micro-pore carbon material in supercapacitor is higher than 300F/g, and organic system specific capacitance is higher than 150F/g, and power is close
Degree energy density in 30kW/kg reaches 20Wh/kg, and power density energy density in 372W/kg reaches 40Wh/kg.
It should be noted that the mesoporous micro-pore carbon material due to the application has superhigh specific surface area, and capacitor and material
Specific surface area be positively correlated, to realize high specific capacitance.Since the mesoporous micro-pore carbon material of the application has big hole again
Volume and mesoporous ratio, ion spread the charge-discharge velocity for accelerating capacitor quickly in the material.To sum up, the application
Mesoporous micro-pore carbon material is the energy density for increasing supercapacitor, and increases the power density of supercapacitor.
The beneficial effects of the present application are as follows:
The mesoporous micro-pore carbon material of the application, while there is superhigh specific surface area and high mesoporous ratio, this is one kind
The preceding new carbon not occurred.The preparation method of the mesoporous micro-pore carbon material of the application passes through silicon oxide material preparation point
Mesoporous-the micro-pore carbon material of grade, the creative highly basic using melting carry out dissolution and right to the silica in silicon oxide material
Carbon is activated, and the use of chlorine or hydrofluoric acid is avoided；Due to not needing to prevent the leakage of toxic gas or liquid, production is set
It is standby more simple, so that entire method process is more economical, safer, more environmentally friendly；In addition, this method does not need to be formed using template
It is mesoporous, the new environmental protection of one kind, safe, economic preparation way are provided to prepare mesoporous micro-pore carbon material by silicon oxide material
Diameter.Also, the supercapacitor of the mesoporous micro-pore carbon material using the application has higher energy density and power density.
Detailed description of the invention
Fig. 1 be in the embodiment of the present application one 1200 degrees Celsius of pyrolysis silicon oxide carbides of two-component silica gel at 800 degrees Celsius with hydrogen
Aoxidize the nitrogen physisorption isotherms of the mesoporous micro-pore carbon material of sodium corrosion preparation；
Fig. 2 be in the embodiment of the present application one 1200 degrees Celsius of pyrolysis silicon oxide carbides of two-component silica gel at 800 degrees Celsius with hydrogen
Aoxidize the graph of pore diameter distribution of the mesoporous micro-pore carbon material of sodium corrosion preparation；
Fig. 3 be in the embodiment of the present application two 1200 degrees Celsius of pyrolysis silicon oxide carbides of single component silica gel at 800 degrees Celsius with hydrogen
Aoxidize the nitrogen physisorption isotherms of the mesoporous micro-pore carbon material of sodium corrosion preparation；
Fig. 4 be in the embodiment of the present application two 1200 degrees Celsius of pyrolysis silicon oxide carbides of single component silica gel at 800 degrees Celsius with hydrogen
Aoxidize the graph of pore diameter distribution of the mesoporous micro-pore carbon material of sodium corrosion preparation；
Fig. 5 is the water system capacitor high rate performance figure of three intermediary hole micro-pore carbon material charcoal of the embodiment of the present application；
Fig. 6 is the organic system capacitor pair of four intermediary hole micro-pore carbon material of the embodiment of the present application and Japanese import YP50 active carbon
Than figure；
Fig. 7 is the energy density and function of four intermediary hole micro-pore carbon material of the embodiment of the present application and Japanese import YP50 active carbon
Rate density comparison diagram.
Specific embodiment
The preparation method of the porous carbon materials of existing more advanced controllable bore diameter is exactly to pass through silicon oxide material, molten
Silica therein is solved, porous carbon materials are formed；But existing method is all to carry out corrosion oxidation using chlorine logical under high temperature
Silicon, or hydrofluoric acid corrosion oxidation silicon is utilized at room temperature.These methods what is common is that, first, there are security risks；The
Two, the by-product of corrosion has pollution to environment.In this regard, present inventor passes through a large amount of practical studies, creative is mentioned
Out, highly basic is melted, silica is dissolved using the highly basic of melting, while carbon is activated, then used pickling, go
Except the reaction product of highly basic and highly basic and silica；Without hydrofluoric acid or chlorine, safety and environmental protection；And without using template.
The mesoporous micro-pore carbon material obtained by the preparation method of the application, compared with the mesoporous poromerics of existing method preparation, this Shen
Please can be controllable preparation specific surface area 1500-3200m2The mesoporous micro-pore carbon material of/g, that is to say, that the application's is mesoporous micro-
Hole carbon material, specific surface area can achieve 3000m2/ g or more has superhigh specific surface area, at the same time, Jie of the application
Hole micro-pore carbon material also has very high mesoporous ratio, and the mesoporous volume ratio with micropore is 2:1 or more, a kind of realization of the application
It is mesoporous to can achieve 4.4:1 with micropore volume ratio in mode.
It should be noted that the specific surface area (abbreviation S) of material is inversely proportional with aperture (abbreviation d), and therefore, existing carbon materials
Material specific surface area when introducing mesoporous can be substantially reduced；And find after study, specific surface area and pore volume (abbreviation V) at
Direct ratio, i.e. S=4V/d, the mesoporous micro-pore carbon material of the application improve pore volume, therefore this Shen while introducing mesoporous
It please can obtain the mesoporous micro-pore carbon material of high mesoporous ratio and high-specific surface area.
The application is described in further detail below by specific embodiment.Following embodiment only to the application carry out into
One step explanation, should not be construed as the limitation to the application.
Embodiment one
This example forms silicon oxide carbide in 1200 degree of pyrolysis using double-component silicon, and the highly basic of melting is then recycled to dissolve carbon
Silica in silica forms the mesoporous micro-pore carbon material of this example.The highly basic of this example uses sodium hydroxide, the acid of pickling processes
Using hydrochloric acid.It is specific the preparation method is as follows:
15 microlitres of platinum catalyst is dissolved in 20 grams of polyvinyl phenyl siloxane, then adds 1 gram of poly- methyl hydrogen
Siloxanes stirs 5 minutes, and solid silicone, i.e. polyphenyl methyl siloxane is made in hybrid reaction, solid silicone is shredded, in pipe
1200 DEG C of obtained silicon oxide carbide powder are fired to the heating rate of 5 DEG C/min in formula furnace nitrogen atmosphere.
The silicon oxide carbide of preparation and sodium hydroxide 1:4 in mass ratio are ground, it should be noted that sodium hydroxide
Purpose is dissolution silica and activates to carbon.Specifically 1:4 in mass ratio is added this example, that is, is added and is four times in silicon oxide carbide
Sodium hydroxide；800 DEG C are fired in tube furnace nitrogen atmosphere after mixing to be reacted, keeps the temperature 3 hours, after reaction
Reactant is transferred in the hydrochloric acid of 2mol/L, washing is sufficiently stirred, then filtered, washed filter 23 time repeatedly, product is placed
It is 4 hours dry at 100 DEG C in vacuum drying oven, obtain the mesoporous micro-pore carbon material of this example.
Using specific surface area, porosity and the aperture of the mesoporous micro-pore carbon material that nitrogen physisorption method prepares this example
It is tested.
Test results are shown in figure 1, the results show that the mesoporous micro-pore carbon material of this example preparation, BET specific surface area are
3120m2/ g, pore volume 2.4cm3/ g, mesoporous and micro pore volume ratio are 3.6:1, and average pore size is 3 nanometers.This example preparation
The pore-size distribution of mesoporous micro-pore carbon material is as shown in Figure 2, it is seen that the mesoporous micro-pore carbon material of this example, aperture is mainly distributed on 2-
The small macropore range in 10 nanometers of sections, distributed area is narrow, and aperture is more uniform.
Embodiment two
This example forms silicon oxide carbide in 1200 degree of pyrolysis using single component silica gel, and the highly basic of melting is then recycled to dissolve carbon
Silica in silica forms mesoporous micro-pore carbon material.The highly basic of this example uses sodium hydroxide, and the acid of pickling processes uses salt
Acid.It is specific the preparation method is as follows:
By the silica column powder of 20 grams of hydroxyls containing phenyl, with the heating rate of 5 DEG C/min in tube furnace argon atmosphere
It is fired to 1200 DEG C of obtained silicon oxide carbide powder.
The silicon oxide carbide of this example preparation and excessive sodium hydroxide 1:4 in mass ratio are ground, existed after mixing
It is fired to 800 DEG C in tube furnace argon atmosphere to be reacted, keeps the temperature 3 hours, reactant is transferred to 2mol/L after reaction
Hydrochloric acid in washing is sufficiently stirred, filter, wash filter 23 time repeatedly, product is placed in vacuum drying oven at 100 DEG C dry
4 hours, obtain the mesoporous micro-pore carbon material of this example.
Using specific surface area, porosity and the aperture of the mesoporous micro-pore carbon material that nitrogen physisorption method prepares this example
It is tested.
Test results are shown in figure 3, the results show that this example preparation classification it is mesoporous-micro-pore carbon material, BET specific surface
Product is 1549m2/ g, pore volume 1.8cm3/ g, mesoporous and micropore ratio are 4.4:1, and average pore size is 4.5 nanometers.This example preparation
Mesoporous micro-pore carbon material pore-size distribution it is as shown in Figure 4, it is seen that the mesoporous micro-pore carbon material of this example, aperture is mainly distributed on
The macropore range in 2-50 nanometers of sections, distributed area is wider, and pore-size distribution relatively disperses.Although the mesoporous microporous carbon of this example preparation
Material, specific surface area is lower, but has still maintained very high mesoporous and micropore ratio, while in the preparation method of this example,
Used single component silica gel, cost is lower, and preparation method is simpler.
Embodiment three
The mesoporous micro-pore carbon material that will be prepared in embodiment one, conductive agent Super P carbon black, mass fraction be 60% it is viscous
Knot agent polytetrafluoroethylene (PTFE) (abbreviation PTFE) weighs in mass ratio for the ratio of 80:10:10, is transferred in mortar, is added suitable
Ethyl alcohol carries out being fully ground mixing, with the volatilization of ethyl alcohol, slurry gradually retrogradation, then stirs compacting repeatedly, make slurry finally at
The slurry-mud of semi-solid state.Roll squeezer suitable distance is adjusted, roll-in slurry-mud is so that it becomes 100-150 microns of thick, superficial compactions
Electrode film is finally struck out the round pole piece that diameter is 10mm with sheet-punching machine, is placed in vacuum oven by smooth electrode film
In 80 DEG C of dryings for 24 hours.Length about 50mm, width about 15mm are cut, with a thickness of afflux of the nickel foam as working electrode of 1mm
Body.Round pole piece is placed in foamed nickel current collector, and with roll squeezer that it is integral with collector roll-in, work electricity is made
Pole.Working electrode, mercury oxide reference electrode, platinum are placed in three-necked flask electrode, addition 6M KOH solution as electrolyte,
Capacity measurement is carried out in 0-1V voltage range, test results are shown in figure 5.
The results show that specific capacitance has reached 320F/g when current density is 0.5A/g；Even if current density reaches
When 50A/g, specific capacitance still has 170F/g.As it can be seen that the mesoporous micro-pore carbon material using embodiment one prepares capacitor, can obtain
Very high specific capacitance is able to maintain high specific capacitance under high current, illustrates that the high rate performance of capacitor is superior.Capacitor be by
Zwitterion is generated since electrostatic interaction is adsorbed on conductor material surface formation electric double layer.It is common, conductor material surface
Product is bigger, and the electric double layer capacitance that can be generated is higher.Mesoporous micro-pore carbon material prepared by embodiment one has very high specific surface
Product, therefore very high specific capacitance can be generated.In addition, it is different from traditional micro-pore carbon material, it is mesoporous prepared by embodiment one
Micro-pore carbon material has a high proportion of mesoporous.The size of zwitterion is respectively less than mesopore size, is not in due to ion size
The phenomenon that cannot be introduced into very much micropore greatly, and migration resistance of the ion in mesoporous is small, and material can be rapidly achieved under high current
Expect that surface forms electric double layer, shows as superior high rate performance.As it can be seen that the mesoporous high ratio of micro-pore carbon material prepared by embodiment one
The characteristics of surface area and high mesoporous ratio, be the key that realize superior capacitive property.
Example IV
The energy density of supercapacitor is directly proportional to specific capacitance, square directly proportional to voltage range.Improve energy
Density should increase voltage range as much as possible.Therefore, practical supercapacitor is broader organic molten usually using voltage range
Liquid is as electrolyte.This example demonstrates mesoporous micro-pore carbon material answering in the supercapacitor using organic solution as electrolyte
With.
The mesoporous micro-pore carbon material that will be prepared in embodiment one, conductive agent Super P carbon black, mass fraction be 60% it is viscous
Knot agent polytetrafluoroethylene (PTFE) (abbreviation PTFE) weighs in mass ratio for the ratio of 80:10:10, is transferred in mortar, is added suitable
Ethyl alcohol carries out being fully ground mixing, with the volatilization of ethyl alcohol, slurry gradually retrogradation, then stirs compacting repeatedly, make slurry finally at
The slurry-mud of semi-solid state.Roll squeezer suitable distance is adjusted, roll-in slurry-mud is so that it becomes 100-150 microns of thick, superficial compactions
Electrode film is finally struck out the round pole piece that diameter is 10mm with sheet-punching machine, is placed in vacuum oven by smooth electrode film
In 80 DEG C of dryings for 24 hours.Assemble supercapacitor using CR2032 button cell component, two panels pole piece respectively as positive and negative anodes, in
Between separated by polyethylene battery diaphragm, electrolyte be 1M concentration ttraethylammonium tetrafluoroborate/acetonitrile solution.It comprises the concrete steps that: will
Smooth pole piece is placed in the center of negative electrode casing, and 40 μ L electrolyte are added dropwise, are put into polyethylene battery diaphragm, then 40 μ L electrolysis is added dropwise
Liquid makes diaphragm complete wetting, then another pole piece is placed on diaphragm, and adjustment good position is located at center, then by gasket and
Elastic slice is successively placed on above pole piece, to enhance the smooth export of inside battery contact tight type and electric current, finally covers anode cover,
It is sealed with sealing machine, completes the assembling of supercapacitor.Using the nickel foam of adhesive electrodes material as electrode assembling at button electricity
Pond.Capacity measurement is carried out in 0-2.5V voltage range.
Test result is as shown in A curve in Fig. 6.The results show that specific capacitance reaches when current density is 0.5A/g
162F/g.Even if current density has reached 50A/g, specific capacitance still has 100F/g.As it can be seen that using the mesoporous micropore of embodiment one
Carbon material prepares capacitor, can obtain very high specific capacitance, is able to maintain high specific capacitance under high current, illustrates electricity
The high rate performance of appearance is superior.Zwitterion size of the zwitterion of ttraethylammonium tetrafluoroborate than KOH is big, so in unit plane
The number of ions that can be adsorbed in product reduces, and shows as specific capacitance and is less than example using KOH aqueous solution as the specific capacitance of electrolyte.
Even so, since the voltage range in ttraethylammonium tetrafluoroborate/acetonitrile is 0-2.5V, much higher than the 0-1V of KOH aqueous solution, institute
It is higher with energy density.Since the size of ttraethylammonium tetrafluoroborate zwitterion is larger, it is too small more likely to cannot be introduced into aperture
Micropore, or the migration velocity in hole is very slow.It is different from traditional micro-pore carbon material, it is mesoporous micro- prepared by embodiment one
Hole carbon material has a high proportion of mesoporous.The size of ttraethylammonium tetrafluoroborate zwitterion be less than mesopore size, be not in by
In ion size cannot be introduced into micropore greatly very much the phenomenon that, and migration resistance of the ion in mesoporous is small, can be under high current
It is rapidly achieved material surface and forms electric double layer, show as superior high rate performance.As it can be seen that mesoporous micropore prepared by embodiment one
The characteristics of carbon material high-specific surface area and high mesoporous ratio, be the key that realize superior capacitive property.
At the same time, this example using the YP50 alternative embodiment one of Japanese import mesoporous micro-pore carbon material as a comparison into
Row test.Wherein, the YP50 of Japanese import is a kind of high grade activated carbon for being widely used in supercapacitor in industry, YP50
Specific surface area be 1750m2/ g, pore volume 1.3cm3/ g, mesoporous and micropore ratio are 0.8:1.It can be seen that YP50 is still with micropore
Main, mesoporous is secondary.
Japanese import YP50 active carbon is assembled into supercapacitor using CR2032 button cell component with same method, is used
Same method testing capacitor.Test result is as shown in B curve in Fig. 6.The results show that when current density is 0.5A/g, than electricity
Hold and there was only 97F/g.More obviously, when current density has reached 50A/g, specific capacitance drops to only 10F/g.Performance is much low
In mesoporous micro-pore carbon material prepared by the embodiment one of curve A.Since the specific surface area of YP50 is more mesoporous than prepared by embodiment one
Micro-pore carbon material specific surface area is small, so specific capacitance also accordingly reduces.In addition, due to the ruler of ttraethylammonium tetrafluoroborate zwitterion
It is very little larger, and YP50 causes ion to cannot be introduced into too small micropore based on 2 nanometers of micropores below, or migrates in hole
It is very slow, it is presented as under high current that clearly, high rate performance is poor for capacitor decline.It is compared from this, prepared by embodiment one
Mesoporous micro-pore carbon material there is high-specific surface area and high mesoporous ratio to embody the electricity for being much better than the carbon material based on micropore
Capacitive energy.
According to the test result of Fig. 6, the corresponding power density-energy density figure of two materials (Ragone Plot) is drawn,
As shown in Figure 7.As it can be seen that mesoporous micro-pore carbon material prepared by embodiment one reaches the maximum energy-density of 30Wh/kg, or
The maximum power density of 40kW/kg.And Japanese import YP50 active carbon only reaches the maximum energy-density of 20Wh/kg, or
The maximum power density of 8kW/kg.The maximum energy-density ratio YP50 high 50% of mesoporous micro-pore carbon material prepared by embodiment one,
Maximum power density is 5 times of YP50.Also, mesoporous micro-pore carbon material prepared by embodiment one is in the power density of 30kW/kg
Under, it still is able to reach the energy density of 20Wh/kg；Under the power density of 372W/kg, it may be possible to reach 40Wh/kg's
Energy density；This is that YP50 active carbon can not be reached.
On the basis of above embodiments, the application further tests the acid of highly basic and pickling processes.As a result
It has been shown that, other than sodium hydroxide, potassium hydroxide also can achieve the effect of identical dissolution silica；Also, sodium hydroxide
It is all relatively common, cheap highly basic with potassium hydroxide；For the temperature of high temperature, primarily to make highly basic melt or
Melting is kept, therefore, temperature all may be used at 700-900 DEG C.In terms of pickling, other than hydrochloric acid, sulfuric acid and nitric acid can also be used
In the application, the reaction product of remaining highly basic and highly basic and silica also can be effectively removed.As for being dried after pickling
Temperature and drying time, according to the difference for the mesoporous micro-pore carbon material being finally made, 80-120 DEG C of temperature, time 3-5 hour
Substantially mesoporous micro-pore carbon material can effectively be dried.
The foregoing is a further detailed description of the present application in conjunction with specific implementation manners, and it cannot be said that this Shen
Specific implementation please is only limited to these instructions.For those of ordinary skill in the art to which this application belongs, it is not taking off
Under the premise of from the application design, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to the protection of the application
Range.
Claims (8)
1. a kind of method for preparing mesoporous micro-pore carbon material, it is characterised in that: including at high temperature using the highly basic of melting to carbon
Silica in silica material is dissolved, while being activated to carbon, and pickling is then used, and obtains the mesoporous microporous carbon
Material.
2. according to the method described in claim 1, it is characterized by: the silicon oxide material is being protected by phenyl polysiloxane
Property atmosphere in carry out high temperature pyrolysis form.
3. according to the method described in claim 2, it is characterized by: the phenyl polysiloxane be polyphenyl methyl siloxane or
The silica column of the hydroxyl containing phenyl.
4. the method for mesoporous micro-pore carbon material according to claim 2, it is characterised in that: the temperature of the high temperature pyrolysis is
1000-1200 DEG C, the protective atmosphere is nitrogen or argon gas.
5. according to the method described in claim 1, it is characterized by: the temperature of the high temperature is 700-900 DEG C.
6. according to the method described in claim 1, it is characterized by: the highly basic is sodium hydroxide or potassium hydroxide, the acid
Washing the acid used is hydrochloric acid, sulfuric acid or nitric acid.
7. method according to claim 1-6, it is characterised in that: the method specifically includes, by silicon oxide carbide
With excessive highly basic mixed grinding, then heating melts highly basic under an inert atmosphere, using the highly basic of melting to silicon oxide carbide
Silica in material is dissolved, while being activated to carbon, then carries out pickling again, obtains the mesoporous micropore carbon materials
Material.
8. the mesoporous micro-pore carbon material of method preparation according to claim 1-7, it is characterised in that: described mesoporous
The pore diameter range of micro-pore carbon material is 0.3-20 nanometers, and porosity 50-90%, the mesoporous volume ratio with micropore is 2:1 or more,
Specific surface area is 1500-3200m2/g。
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