CN104591184A - Preparation method of shell-like mesoporous carbon material for super capacitors - Google Patents
Preparation method of shell-like mesoporous carbon material for super capacitors Download PDFInfo
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- CN104591184A CN104591184A CN201510055624.8A CN201510055624A CN104591184A CN 104591184 A CN104591184 A CN 104591184A CN 201510055624 A CN201510055624 A CN 201510055624A CN 104591184 A CN104591184 A CN 104591184A
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Abstract
The invention discloses a preparation method of shell-like mesoporous carbon material for super capacitors, belonging to the technical field of carbon material preparation. The method comprises the following steps of: grinding and uniformly mixing petroleum asphalt serving as carbon source, nano zinc oxide serving as a template and potassium hydroxide serving as an activator together and putting the mixture into a porcelain boat, placing the porcelain boat in a tube furnace and heating in an argon atmosphere, thus obtaining the shell-like mesoporous carbon material. The specific area of the shell-like mesoporous carbon material is in a range of 1766-2646m<2>/g, and mean pore size of the shell-like mesoporous carbon material is in a range of 2.05-2.25nm; when used as super capacitor electrode material, in 6mol/L KOH electrolyte, the shell-like mesoporous carbon material has the specific capacity high up to 296F/g under the condition of 0.05A/g current density. In the preparation method provided by the invention, cheap petroleum asphalt is used as carbon source, so that high value-added utilization of petroleum asphalt is realized. The obtained shell-like mesoporous carbon material is used as a super capacitor electrode material, has the advantages of good rate capability, high specific capacity, good cycling stability, and so on.
Description
Technical field
The invention belongs to technical field of carbon material preparation, be specifically related to a kind of preparation method of ultracapacitor shelly Mesoporous Carbon Materials.
Background technology
Ultracapacitor is a kind of novel energy-storage travelling wave tube, has the advantages such as charge-discharge velocity is fast, good rate capability, long service life, has broad application prospects in industrial power, telecommunications, military affairs etc.The chemical property of ultracapacitor depends on electrode materials to a great extent, and therefore exploitation has high performance electrode materials tool and is of great significance.Mesoporous carbon, due to advantages such as the electrochemical stabilities that has high specific surface area and become reconciled, becomes the most popular a kind of electrode materials of current ultracapacitor.The raw material preparing mesoporous carbon mainly contains coal, oil and biomass etc.Petroleum pitch is the residue after crude distillation, is in a liquid state at normal temperatures, semi-solid state or solid-state.Petroleum pitch contains unsaturated aromatic hydrocarbon, has low ash and inexpensive advantage.China's oil pitch major part is used for Road construction, if petroleum pitch can be utilized to prepare mesoporous carbon, can realize the high value added utilization of petroleum pitch.
The method preparing mesoporous carbon has template and chemical activation method etc.Template can on nanoscale the pore texture of modulation mesoporous carbon.Template generally has silicon sol, zeolite and some nano metal materials etc.But the inorganic template agent such as silicon sol need just can wash away with hydrofluoric acid, cause operation more complicated and seriously polluted.Adopt nano granular of zinc oxide as template, can wash away with dilute hydrochloric acid, simple to operate.In chemical activation method, conventional activator has acid, alkali and salt.What current application was more, more ripe has potassium hydroxide, phosphoric acid and zinc chloride etc.Potassium hydroxide, in reactivation process, can react with C and generate K
2cO
3, form hole.In addition, K
2cO
3also can react with C, generate potassium metal, when activation temperature exceedes potassium metal boiling point, potassium vapor can diffuse into the generation that carbon-coating promotes micropore, meanwhile, and K
2cO
3decompose the K produced
2o and CO
2also the generation of micropore is conducive to.Therefore nano-scale zinc oxide is worked in coordination with activation of potassium hydroxide petroleum pitch and is prepared mesoporous activated carbon for supercapacitors material tool and be of great significance.
Patent 200910043229.2 discloses a kind of preparation method of porous carbon material used for storing energy.The method take mesophase pitch as carbon precursor, with silicon-dioxide or silica gel or SiO 2 molecular sieve for template.Reactant is obtained after first carbon precursor and template being mixed, then reacting by heating thing to 900 DEG C in a nitrogen atmosphere, after constant temperature 1 ~ 2h, template is washed away with 30% hydrofluoric acid, filter, wash filter residue to neutral, 110 DEG C of dryings obtained porous carbon material afterwards, the specific surface area of gained porous carbon material is up to 600m
2/ g, mean pore size is 5.0nm, and in the KOH electrolytic solution of 6mol/L, bulking value is 220F/g.Patent 201210522714.X discloses asphalt hard carbon material for lithium ion battery cathode preparation method.The method is that 200 ~ 280 DEG C of coal-tar pitches or petroleum pitch are for raw material with softening temperature, pulverizing is placed in tube furnace, in air atmosphere, be warming up to 250 ~ 350 DEG C to be cured, asphalt powder after solidification is placed in charring furnace, in a nitrogen atmosphere, is warming up to 700 ~ 1300 DEG C and carries out charing process, the median size of obtained hard carbon material is 5 ~ 10 μm, and its specific surface area is 100 ~ 300m
2/ g, class graphite microcrystal interlamellar spacing is 0.36 ~ 0.38nm.Patent 201110283711.0 discloses using magnesium oxide template and works in coordination with the method that activation of potassium hydroxide prepares porous carbon material.The method take coal-tar pitch as carbon source, nano magnesia is template, potassium hydroxide is activator, mixture after three's grinding is transferred in corundum crucible, be placed in microwave reactor and carry out a step microwave heating activation, obtained porous carbon material, the specific surface area of gained porous carbon material is between 439 ~ 1349m
2between/g, mean pore size is between 1.95 ~ 3.36nm.
Document " Synthesis of mesoporous carbons from bituminous coal tar pitch usingcombined nanosilica template and KOH activation " (Industrial & EngineeringChemistry Research, 50 (2011) 13825-13830) propose with coal-tar pitch to be carbon source, nano silicon is template, first two kinds of raw materials are carbonized at a certain temperature, obtained coal-tar pitch/silicon dioxide composite material; Then, after coal-tar pitch/silicon dioxide composite material being pulverized, add KOH and activate; Obtained Mesoporous Carbon Materials after above-mentioned charing and activation like this, the specific surface area of gained Mesoporous Carbon Materials is between 636 ~ 1366m
2between/g.
As can be seen from above-mentioned document, take mesophase pitch as carbon source, silicon-dioxide etc. are template, need template to be removed with hydrofluoric acid, operate more complicated and seriously polluted; Be that the hard carbon material specific surface area that carbon source obtains is lower with pitch, mean pore size is larger; Take coal-tar pitch as carbon source, magnesium oxide is template, saves time, operate more complicated, and the specific surface area of gained porous charcoal is lower although adopt microwave heating to prepare porous carbon material.
Summary of the invention
The present invention is directed to the deficiency that existing Mesoporous Carbon Materials technology of preparing exists, propose that a kind of specific surface area is large, high rate performance is excellent, specific storage is high, the preparation method of the shelly Mesoporous Carbon Materials of good cycling stability.
These preparation method's concrete steps are as follows:
(1) pre-treatment of reactant: petroleum pitch is put into mortar, add nano zine oxide ground and mixed even, add the potassium hydroxide of grind into powder again, the mixture of gained three is ground to and mixes, the quality of described petroleum pitch accounts for 7.4% ~ 11.1% of three's mixture total mass, and the quality of described nano zine oxide accounts for 66.7% ~ 70.4% of three's mixture total mass;
(2) preparation of shelly Mesoporous Carbon Materials: the mixture that step (1) obtains is put into porcelain boat, then described porcelain boat is placed in tube furnace, pass into argon gas in advance by the air emptying in tube furnace, argon gas speed is kept to be 60mL/min, with the temperature rise rate of 5 DEG C/min by diamond heating to 200 DEG C, constant temperature 30min, continue behind diamond heating to 800 ~ 900 DEG C with the temperature rise rate of 5 DEG C/min, constant temperature 60min, naturally cool to room temperature, the product obtained is taken out, beaker is put into after grinding, through pickling, ultracapacitor shelly Mesoporous Carbon Materials is obtained after washing and drying.
As one optimization, in step (1), the quality of described petroleum pitch accounts for 7.4% of three's mixture total mass, and the quality of described nano zine oxide accounts for 70.4% of mixture total mass.
The present invention take petroleum pitch as carbon source, and nano zine oxide is template, and potassium hydroxide is activator, and conventional heating activation obtains ultracapacitor shelly Mesoporous Carbon Materials.The specific surface area of this shelly Mesoporous Carbon Materials is between 1766 ~ 2646m
2between/g, mean pore size is between 2.05 ~ 2.25nm; As electrode for super capacitor material, in 6mol/L KOH electrolytic solution, under the current density of 0.05A/g, its specific volume is up to 296F/g.The present invention for carbon source, achieves the high value added utilization of petroleum pitch with the petroleum pitch of cheapness, and the shelly Mesoporous Carbon Materials of preparation, as electrode for super capacitor material, has the advantages such as the high and good cycling stability of good rate capability, specific storage.
Compared with prior art, the present invention has the following advantages:
1. petroleum pitch is the residue after crude distillation, the advantage such as have low ash, cheapness, be easy to get;
2. nano zine oxide is as template, can remove with dilute hydrochloric acid;
3. raw material adopts dry state hybrid system, simple to operate;
4. the specific surface area of obtained shelly Mesoporous Carbon Materials reaches 2646m
2/ g, its specific volume, up to 296F/g, has good rate capability and cyclical stability.
Accompanying drawing explanation
Fig. 1 is the nitrogen Adsorption and desorption isotherms of shelly mesoporous carbon prepared by the embodiment of the present invention 1,2,3,4.
Fig. 2 is the graph of pore diameter distribution of shelly mesoporous carbon prepared by the embodiment of the present invention 1,2,3,4.
Fig. 3 is the field emission scanning electron microscope photo of shelly Mesoporous Carbon Materials prepared by the embodiment of the present invention 4.
Fig. 4 is that the specific volume of shelly mesoporous carbon electrode materials in 6mol/L KOH electrolytic solution prepared of the embodiment of the present invention 1,2,3,4 is with current density change figure.
Fig. 5 is that the specific volume of shelly mesoporous carbon electrode materials under 1A/g current density prepared of the embodiment of the present invention 1,2,3,4 is with cycle index variation diagram.
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: shelly mesoporous carbon SMPC
2-19-6-850concrete preparation process as follows:
(1) pre-treatment of reactant: take 2g petroleum pitch and put into mortar, adds 19g nano zine oxide (particle diameter is between 100 ~ 150nm), then adds 6g potassium hydroxide, and the grinding of gained three mixture evenly obtains reactant.
(2) preparation of shelly Mesoporous Carbon Materials: the reactant that step (1) obtains is put into porcelain boat, then described porcelain boat is placed in tube furnace, first pass into argon gas by the air emptying in tube furnace, argon gas speed is kept to be 60mL/min, with the temperature rise rate of 5 DEG C/min by diamond heating to 200 DEG C, constant temperature 30min, continues after diamond heating to 850 DEG C with the temperature rise rate of 5 DEG C/min, constant temperature 60min, naturally cools to room temperature.Beaker is put into after being ground by the product obtained, ultrasonic vibration after a certain amount of 2mol/L dilute hydrochloric acid is added in beaker, magnetic agitation 2h, after leaving standstill under room temperature condition, with distilled water wash product to neutral, be placed in loft drier dry, ground 325 mesh standard sieves, obtain ultracapacitor shelly Mesoporous Carbon Materials.Gained shelly Mesoporous Carbon Materials is labeled as SMPC
2-19-6-850.SMPC
2-19-6-850as electrode material for super capacitor in 6mol/L KOH electrolytic solution, under the current density of 0.05A/g, its specific volume is up to 296F/g; After current density increases to 20A/g, its specific volume conservation rate is 80.1%.
Embodiment 2: shelly mesoporous carbon SMPC
3-18-6-800concrete preparation process as follows:
(1) pre-treatment of reactant: implement according to the method same with the step (1) in embodiment 1, difference is that the petroleum pitch taken is 3g, and nano zine oxide is 18g.
(2) implement according to the method same with the step (2) in embodiment 1, difference is diamond heating to 800 DEG C.Gained shelly mesoporous carbon is labeled as SMPC
3-18-6-800.SMPC
3-18-6-800as electrode material for super capacitor in the KOH electrolytic solution of 6mol/L, under the current density of 0.05A/g, its specific volume reaches 237F/g.
Embodiment 3: shelly mesoporous carbon SMPC
3-18-6-850concrete preparation process as follows:
(1) pre-treatment of reactant: implement according to the method same with the step (1) in embodiment 1, difference is that the petroleum pitch taken is 3g, and nano zine oxide is 18g.
(2) implement according to the method same with the step (2) in embodiment 1.Gained shelly Mesoporous Carbon Materials is labeled as SMPC
3-18-6-850.SMPC
3-18-6-850as electrode material for super capacitor in 6mol/L KOH electrolytic solution, under the current density of 0.05A/g, its specific volume reaches 263F/g.
Embodiment 4: shelly mesoporous carbon SMPC
3-18-6-900concrete preparation process as follows:
(1) pre-treatment of reactant: implement according to the method same with the step (1) in embodiment 1, difference is that the petroleum pitch taken is 3g, and nano zine oxide is 18g.
(2) implement according to the method same with the step (2) in embodiment 1, difference is diamond heating to 900 DEG C.Gained shelly mesoporous carbon is labeled as SMPC
3-18-6-900.SMPC
3-18-6-900as electrode material for super capacitor in 6mol/L KOH electrolytic solution, under the current density of 0.05A/g, its specific volume reaches 226F/g.
Embodiment 1 – 4 gained shelly Mesoporous Carbon Materials pore structure parameter and productive rate analytical results list in table 1.
Table 1 embodiment 1 – 4 gained shelly Mesoporous Carbon Materials pore structure parameter and productive rate analytical results
Claims (2)
1. a ultracapacitor preparation method for shelly Mesoporous Carbon Materials, is characterized in that the method concrete steps are as follows:
(1) pre-treatment of reactant: petroleum pitch is put into mortar, add nano zine oxide ground and mixed even, add the potassium hydroxide of grind into powder again, the mixture of gained three is ground to and mixes, the quality of described petroleum pitch accounts for 7.4% ~ 11.1% of three's mixture total mass, and the quality of described nano zine oxide accounts for 66.7% ~ 70.4% of three's mixture total mass;
(2) preparation of shelly Mesoporous Carbon Materials: the mixture that step (1) obtains is put into porcelain boat, then described porcelain boat is placed in tube furnace, in argon gas atmosphere, with the temperature rise rate of 5 DEG C/min by diamond heating to 200 DEG C, constant temperature 30min, continue behind diamond heating to 800 ~ 900 DEG C with the temperature rise rate of 5 DEG C/min, constant temperature 60min, naturally cool to room temperature, the product obtained is taken out, put into beaker after grinding, after pickling, washing and drying, obtain ultracapacitor shelly Mesoporous Carbon Materials.
2. the preparation method of a kind of ultracapacitor shelly Mesoporous Carbon Materials as claimed in claim 1, it is characterized in that, in step (1), the quality of described petroleum pitch accounts for 7.4% of three's mixture total mass, and the quality of described nano zine oxide accounts for 70.4% of mixture total mass.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105502363A (en) * | 2015-12-25 | 2016-04-20 | 安徽工业大学 | Method for preparing corrugated graphene nanosheets for supercapacitor |
| CN107188172A (en) * | 2017-06-28 | 2017-09-22 | 中国科学院山西煤炭化学研究所 | A kind of preparation method rich in mesopore pitch super active carbon |
| CN108630454A (en) * | 2018-04-28 | 2018-10-09 | 辽宁大学 | A kind of method that combined techniques prepare super capacitor carbon electrode material |
| CN109205622A (en) * | 2018-09-20 | 2019-01-15 | 中国科学院广州能源研究所 | A kind of preparation method of the derivative porous carbon materials of biomass coke tar |
| CN110683541A (en) * | 2019-11-27 | 2020-01-14 | 天津合众汇能科技有限公司 | Method for preparing double electric layer capacitor activated carbon by template method |
| CN115020121A (en) * | 2022-06-08 | 2022-09-06 | 中国矿业大学 | Lignite residue based porous carbon material and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102431992A (en) * | 2011-09-22 | 2012-05-02 | 安徽工业大学 | Method for preparing porous carbon material by using magnesium oxide template in cooperation with activation of potassium hydroxide |
-
2015
- 2015-02-03 CN CN201510055624.8A patent/CN104591184A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102431992A (en) * | 2011-09-22 | 2012-05-02 | 安徽工业大学 | Method for preparing porous carbon material by using magnesium oxide template in cooperation with activation of potassium hydroxide |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105502363A (en) * | 2015-12-25 | 2016-04-20 | 安徽工业大学 | Method for preparing corrugated graphene nanosheets for supercapacitor |
| CN105502363B (en) * | 2015-12-25 | 2018-02-09 | 安徽工业大学 | A kind of preparation method of the graphene nanometer sheet of ultracapacitor fold |
| CN107188172A (en) * | 2017-06-28 | 2017-09-22 | 中国科学院山西煤炭化学研究所 | A kind of preparation method rich in mesopore pitch super active carbon |
| CN108630454A (en) * | 2018-04-28 | 2018-10-09 | 辽宁大学 | A kind of method that combined techniques prepare super capacitor carbon electrode material |
| CN109205622A (en) * | 2018-09-20 | 2019-01-15 | 中国科学院广州能源研究所 | A kind of preparation method of the derivative porous carbon materials of biomass coke tar |
| CN110683541A (en) * | 2019-11-27 | 2020-01-14 | 天津合众汇能科技有限公司 | Method for preparing double electric layer capacitor activated carbon by template method |
| CN115020121A (en) * | 2022-06-08 | 2022-09-06 | 中国矿业大学 | Lignite residue based porous carbon material and preparation method and application thereof |
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