CN104150481B - A kind of method simultaneously being prepared mesoporous activated carbon for supercapacitors material by two kinds of carbon sources - Google Patents
A kind of method simultaneously being prepared mesoporous activated carbon for supercapacitors material by two kinds of carbon sources Download PDFInfo
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- CN104150481B CN104150481B CN201410421358.1A CN201410421358A CN104150481B CN 104150481 B CN104150481 B CN 104150481B CN 201410421358 A CN201410421358 A CN 201410421358A CN 104150481 B CN104150481 B CN 104150481B
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Abstract
The present invention discloses a kind of method simultaneously being prepared mesoporous activated carbon for supercapacitors material by two kinds of carbon sources, belongs to technical field of carbon material preparation.The method be with deliming after rice husk and sucrose be carbon source simultaneously, take phosphoric acid as activator, reaction mixture rice husk and sucrose are mixed with phosphoric acid, obtained after drying is placed in microwave reaction device, heats in a nitrogen atmosphere, obtained mesoporous activated carbon for supercapacitors material.The specific surface area of gained Mesoporous Carbon Materials is between 1146 ~ 1399m
2between/g, total hole pore volume is between 0.79 ~ 1.29cm
3between/g, mean pore size is between 2.58 ~ 3.77nm.The method that the present invention adopts phosphoric acid to activate rice husk and sucrose to prepare mesoporous activated carbon for supercapacitors material simultaneously, have preparation technology simple, low production cost, can realize the advantages such as the high value added utilization of biomass.
Description
Technical field
The invention belongs to technical field of carbon material preparation, be specifically related to a kind of preparation method of mesoporous activated carbon for supercapacitors material.
Background technology
Ultracapacitor have power density high, have extended cycle life and the advantage such as charge-discharge velocity is fast, be a kind of novel energy-storing element.The electrode that ultracapacitor is formed primarily of the supported porous material of collector, be placed in two interelectrode barrier films and electrolytic solution composition.At present, the electrode materials carbon-based material that mainly specific surface area is larger of ultracapacitor, comprising: porous charcoal, charcoal-aero gel and carbon nanotube etc.Compared with micropore carbon material, Mesoporous Carbon Materials, owing to having larger aperture, can guarantee that ultracapacitor has good rate capability.Exploitation aperture and pore volume modulation, cheap Mesoporous Carbon Materials can receive the extensive concern of people, choose the key that cheap raw material and efficient preparation method are preparation low cost Mesoporous Carbon Materials.The raw material preparing Mesoporous Carbon Materials mainly contains coal, oil, biomass and other carbon raw material.Wherein, coal and oil are disposable ore resource, non-renewable.Biomass are timber and various shell mainly.Timber to cut down forest, welding is cost, and shell is renewable.
Rice husk is a kind of common agricultural wastes.The whole world is annual produces about 50,000,000,000 tons of paddy, and rice husk accounts for 20% of paddy total mass.China, as populous nation, produces a large amount of rice husks every year.But China's rice husk overall utilization is lower, major part is directly burned in rural area, both pollutes environment like this, wastes resource again.Be that carbon source is prepared porous carbon material and can be turned waste into wealth with rice husk, realize the high value added utilization of reproducible biomass resource.
Adopt physically activated or chemical activation can prepare Mesoporous Carbon Materials by rice husk.Traditional chemical activation method mainly with zinc chloride, phosphoric acid etc. for activator, the common drawback of these methods is all heat with traditional tube furnace, and its heat-up time is longer, and activating process is complicated, and activation temperature is higher, and cost is high.Exploring with rice husk is carbon source, and the effective ways fast, efficiently preparing mesoporous activated carbon for supercapacitors material are significant.Sucrose (C
12h
22o
11) be a kind of common carbonaceous organic material, the Carbon Materials performance separately with sucrose prepared by carbon source is general, but preparing Mesoporous Carbon Materials as carbon source rarely has report simultaneously using both rice husk and sucrose.
Patent 98114553.1 discloses the preparation method of activated carbon with high specific surface area.In the method, rice husk first carbonization 3 ~ 5 hours at 400 ~ 600 DEG C; Subsequently, be 1/3 to mix by weight by gained carbide and potassium hydroxide, at 400 DEG C of thermal treatment 30min, finally, be heated to 750 DEG C and constant temperature 60min, obtained active carbon with high specific surface area.Paper " Productionofactivatedcarbonfrombagassesandricehuskbyasin gle-stagechemicalactivationmethodatlowretentiontimes " (BioresourceTechnology, 99 (2008) 6809-6816) to propose with rice husk be raw material, in carbon dioxide atmosphere, when the mass ratio of zinc chloride and rice husk is 1/1, when activation temperature is 700 DEG C, the specific surface area of obtained activation charcoal reaches 750m
2/ g.Paper " Characteristicsofmicroporous/mesoporouscarbonspreparedfr omricehuskunderbase-andacid-treatedconditions " (JournalofHazardousMaterials, 171 (2009) 693-703) adopts conventional heating methods to prepare activation charcoal from rice husk; Wen Zhong, first carries out pre-treatment with sodium hydroxide solution to rice husk, subsequently, with pretreated rice husk for carbon source, when the mass ratio of phosphoric acid or zinc chloride and rice husk is 2/1, activates 60min, can obtain active carbon with high specific surface area at 500 DEG C.
As can be seen from above-mentioned document, prepare the technique of gac or mesoporous carbon with conventional heating methods, its complex process, soak time is long, and energy consumption is high, adds the production cost of gac or mesoporous carbon.Conventional heating has come according to thermal conduction, radiation, convection current three kinds of heat transfer types, and be heat from the outside ecto-entad of material, the motivating force of heating is temperature head.The inner rate of heating of most of granule materials is slow, and granule materials internal and external temperature field is uneven, and it is very long that granule materials reaches the even required time of bulk temperature, needs just can complete activation poration process through the long period.And will obtain high specific surface area gac, only have after the top layer hole of granule materials is collapsed by activation, granule materials central porisity could be formed.Thus cause Conventional activation methods length consuming time, consume energy high.
Summary of the invention
The present invention is directed to the deficiency of existing mesoporous carbon technology of preparing, propose a kind of method simultaneously being prepared mesoporous activated carbon for supercapacitors material by two kinds of carbon sources, to realize simplifying preparation technology, reduce the object of production cost.
Concrete steps of the present invention are as follows:
(1) pre-treatment of reactant: get a certain amount of phosphoric acid and be dissolved in distilled water, add a certain amount of sucrose after stirring, obtain mixture A after ultrasonic vibration 30min; Getting a certain amount of phosphoric acid is again dissolved in distilled water, adds pretreated rice husk after stirring, and ultrasonic vibration 30min obtains mixture B; Above-mentioned two kinds of mixtures are mixed together, after sonic oscillation, after 100 DEG C of forced air dryings, obtain reactant; Wherein, the mass ratio of phosphoric acid and rice husk is between 2.5/1 ~ 3.5/1, and the mass ratio of sucrose and rice husk is between 0.5/1 ~ 1.5/1.
(2) preparation of Mesoporous Carbon Materials: the reactant that step (1) obtains is put into corundum crucible; described corundum crucible is put in quartzy protector; described quartzy protector is placed in microwave reaction device; under the nitrogen protection of flowing; arranging microwave power is 600W, and microwave heating time is that 20min prepares Mesoporous Carbon Materials.Reaction terminate after, naturally be down to room temperature, then by the product obtained take out, grind after put into beaker, through pickling, distilled water wash to neutrality, obtain mesoporous activated carbon for supercapacitors material after drying.
The inventive method be simultaneously with the rice husk after sucrose and deliming for carbon source, take phosphoric acid as activator, carry out microwave heating under nitrogen protection, obtained mesoporous activated carbon for supercapacitors material.The specific surface area of gained Mesoporous Carbon Materials is between 1146 ~ 1399m
2between/g, total hole pore volume is between 0.79 ~ 1.29cm
3between/g, mean pore size is between 2.58 ~ 3.77nm.
As one optimization, in described step (1): the mass ratio of phosphoric acid and rice husk is 3/1, the mass ratio of sucrose and rice husk is 1/1.Mesoporous Carbon Materials prepared under this kind of condition, in 6MKOH electrolytic solution, under 100mA/g current density, electrode specific volume can reach 163F/g, and the energy density of ultracapacitor can reach 5.58Wh/g.
Compared with prior art, the present invention has the following advantages:
1, with rice husk and sucrose for carbon source, abundant raw material source, inexpensive, be easy to get;
2, adopt phosphoric acid to activate rice husk and sucrose simultaneously, effectively can reduce the usage quantity of activator;
3, in the KOH electrolytic solution of 6M, under the current density of 100mA/g, the specific volume of mesoporous carbon electrode prepared by the present invention can reach 163F/g.
Accompanying drawing explanation
Fig. 1 is N2 adsorption and the desorption isotherm of Mesoporous Carbon Materials prepared by the embodiment of the present invention 1,2,3.
Fig. 2 is the pore size distribution of Mesoporous Carbon Materials prepared by the embodiment of the present invention 1,2,3.
Fig. 3 is the specific volume histogram of mesoporous carbon electrode materials under the current density of 100mA/g prepared by the embodiment of the present invention 1,2,3.
Fig. 4 is the energy density histogram of mesoporous carbon ultracapacitor under the current density of 100mA/g prepared by the embodiment of the present invention 1,2,3.
Embodiment
Below in conjunction with specific embodiment in detail the present invention is described in detail, but the present invention is not limited to following embodiment.
Embodiment 1
Mesoporous Carbon Materials MC
5-2-3concrete preparation process as follows:
(1) pre-treatment of reactant: the phosphoric acid getting 8.1g15mol/L is dissolved in 25mL distilled water, adds 8.1g sucrose, obtain a kind of mixture after ultrasonic vibration 30min after stirring; 5.4g15mol/L phosphoric acid is dissolved in after stirring in 115mL distilled water, adds the pretreated rice husk of 5.4g, after ultrasonic vibration 30min, obtain another kind of mixture; Above-mentioned two kinds of mixtures are mixed together, after ultrasonic vibration 30min, after 100 DEG C of forced air dryings, obtain reactant.
(2) preparation of Mesoporous Carbon Materials: the reactant that step (1) obtains is put into corundum crucible; described corundum crucible is put in quartzy protector; described quartzy protector is placed in microwave reaction device; under the nitrogen protection of flowing; arranging microwave power is 600W, and microwave heating time is that 20min prepares Mesoporous Carbon Materials.After reaction terminates, naturally be down to room temperature, then the product obtained taken out, grind after put into beaker, after 2M salt acid elution, then through distilled water wash to neutral, after 110 DEG C of dry 24h, 325 mesh sieves, obtain mesoporous activated carbon for supercapacitors material.Gained porous carbon material is labeled as MC
5-2-3.In 6MKOH electrolytic solution, under 100mA/g current density, MC
5-2-3the specific volume of electrode reaches 143F/g, MC
5-2-3the energy density of ultracapacitor reaches 4.88Wh/g.
Embodiment 2
Mesoporous Carbon Materials MC
6-2-2concrete preparation process as follows:
(1) pre-treatment of reactant: the phosphoric acid getting 5.4g15mol/L is dissolved in 25mL distilled water, adds 5.4g sucrose, obtain a kind of mixture after ultrasonic vibration 30min after stirring; 10.8g15mol/L phosphoric acid is dissolved in after stirring in 115mL distilled water, adds the pretreated rice husk of 5.4g, after ultrasonic vibration 30min, obtain another kind of mixture; Subsequently, implement according to the method same with the step (1) in embodiment 1.
(2) implement according to the method same with the step (2) in embodiment 1, gained Mesoporous Carbon Materials mark MC
6-2-2.In 6MKOH electrolytic solution, under 100mA/g current density, MC
6-2-2the specific volume of electrode reaches 163F/g, MC
6-2-2the energy density of ultracapacitor reaches 5.58Wh/g.
Embodiment 3
Mesoporous Carbon Materials MC
7-2-1concrete preparation process as follows:
(1) pre-treatment of reactant: the phosphoric acid getting 2.7g15mol/L is dissolved in 25mL distilled water, adds 2.7g sucrose, obtain a kind of mixture after ultrasonic vibration 30min after stirring; 16.2g15mol/L phosphoric acid is dissolved in after stirring in 115mL distilled water, adds the pretreated rice husk of 5.4g, after ultrasonic vibration 30min, obtain another kind of mixture; Subsequently, implement according to the method same with the step (1) in embodiment 1.
(2) implement according to the method same with the step (2) in embodiment 1, gained Mesoporous Carbon Materials mark MC
7-2-1.In 6MKOH electrolytic solution, under 100mA/g current density, MC
7-2-1the specific volume of electrode reaches 145F/g, MC
7-2-1the energy density of ultracapacitor reaches 5.01Wh/g.
Pore structure analysis result and the productive rate of embodiment 1-3 gained Mesoporous Carbon Materials are listed in table 1.
The pore structure analysis result of table 1 embodiment 1-3 gained Mesoporous Carbon Materials and productive rate
Claims (2)
1. prepared a method for mesoporous activated carbon for supercapacitors material by two kinds of carbon sources, it is characterized in that, the method concrete steps are as follows simultaneously:
(1) pre-treatment of reactant: be dissolved in by phosphoric acid in distilled water, add sucrose after stirring, obtains mixture A after ultrasonic vibration 30min; Be dissolved in distilled water by phosphoric acid again, add pretreated rice husk after stirring, ultrasonic vibration 30min obtains mixture B; Above-mentioned two kinds of mixtures are mixed together, after sonic oscillation, after 100 DEG C of forced air dryings, obtain reactant;
Wherein, the mass ratio of phosphoric acid and rice husk is between 2.5/1 ~ 3.5/1, and the mass ratio of sucrose and rice husk is between 0.5/1 ~ 1.5/1;
(2) preparation of Mesoporous Carbon Materials: the reactant that step (1) obtains is put into corundum crucible, described corundum crucible is put in quartzy protector, described quartzy protector is placed in microwave reaction device, under the nitrogen protection of flowing, arranging microwave power is 600W, and microwave heating time is that 20min prepares Mesoporous Carbon Materials; Reaction terminate after, naturally be down to room temperature, then by the product obtained take out, grind after put into beaker, through pickling, distilled water wash to neutrality, obtain mesoporous activated carbon for supercapacitors material after drying.
2. prepare the method for mesoporous activated carbon for supercapacitors material as claimed in claim 1, it is characterized in that, in described step (1): the mass ratio of phosphoric acid and rice husk is 3/1, the mass ratio of sucrose and rice husk is 1/1.
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