CN102013335B - Preparation method of super capacitor electrode material - Google Patents
Preparation method of super capacitor electrode material Download PDFInfo
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- CN102013335B CN102013335B CN2009101872425A CN200910187242A CN102013335B CN 102013335 B CN102013335 B CN 102013335B CN 2009101872425 A CN2009101872425 A CN 2009101872425A CN 200910187242 A CN200910187242 A CN 200910187242A CN 102013335 B CN102013335 B CN 102013335B
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Abstract
The invention relates to synthesis method for nonmetal-doped functional mesoporous carbon, which is characterized in that inorganic acid containing hetero atoms is added during phenolic resin reaction to obtain functional primary modified phenolic resin. Under the acidic condition, a composite material with a mesoscope structure is obtained through carrying out liquid phase self assembly on a precursor and a non-ionic surface active agent, and the degree of order of the composite material is regulated by the proportion of the precursor and the amount of the non-ionic surface active agent. The composite material is finally converted into a series of nonmetal-doped mesoporous polymers and mesoporous carbon after being roasted and carbonized at high temperature in the inert atmosphere. The liquid phase self assembly method has the characteristics of simplicity, rapidness and the like and can realize large-scale production.
Description
Technical field
The present invention relates to a kind of functional mesoporous charcoal synthetic method of nonmetal doping, specifically a kind of preparation method with high-performance electrode material for super capacitor.This electrode material is specially nonmetal doping ordered mesoporous carbon materials such as phosphorus, boron.
Background technology
The aperture has a wide range of applications in fields such as absorption, separation, catalysis and energy storage between the meso-porous carbon material of 2-50nm, becomes nearly hot subject during the last ten years.Especially in electrochemical capacitor, electrolyte ion is difficult for getting into the too small ultra-fine micropore in aperture, thereby the meso-porous carbon material with bigger serface is a kind of electrode material for super capacitor that has development potentiality.In view of the chemical inertness of carbon material surface, the introducing of nonmetallic heteroatoms, not only help to improve the hydrophily of carbon surface, simultaneously Faraday pseudo-capacitance also there is certain contribution, make it in the research of meso-porous carbon material, obtain increasing concern.
At present, the synthesizing blender ordered mesoporous carbon mainly contains carbon surface is carried out that redox is handled and with oppositely the duplicating of hard template such as SBA-15 (people such as Liang Yanyu, CN101347741; People such as Gao Qiuming, CN101306807) etc.Wherein carbon being carried out the surface-treated method needs strong reductant-oxidant, and condition is harsh, is difficult for keeping ordered structure; And be that " hard template method " of cost takes time and effort to sacrifice a large amount of mould materials, both all are difficult to promote.And then increasing seminar begins concern and obtains doped meso-porous charcoal through simple soft template self-assembling method.Before this; Only there is method that an example is evaporated self assembly (EISA) through solution successfully to obtain the report (people such as Wan Ying of nonmetal doping mesoporous carbon; CN100999316A), and this method is strict to temperature humidity, and the EISA process receives effects limit such as space and still is difficult to realize industrialization.
Summary of the invention
The method that the purpose of this invention is to provide a kind of ordered mesoporous carbon of synthetic non-metallic doping.This material has bigger specific area, bigger pore volume, the aperture structure of homogeneous and the functionalization nonmetalloid that is evenly distributed, and is a kind of capacitor electrode material of excellence.This method is based on soft template one-step method synthetic route, and simple and fast is expected to realize industrialization.
For realizing above-mentioned purpose, the present invention adopts following technical scheme to implement:
A kind of preparation method of ordered mesoporous carbon of nonmetal doping; Under the acid condition of PH＜3; Through STUDY ON THE MODIFICATION OF PENOLIC RESIN being realized the functionalization of its nonmetal doping; Resin modified phenol resin and non-ionic surface active agent F127 prepare the ordered mesoporous carbon material of nonmetal doping through hydrogen bond generation self assembly effect.Meso-porous carbon material according to the invention, institute's doped with non-metals elemental constituent is phosphorus, boron; Wherein the nonmetal quality percentage composition of the doped meso-porous material with carbon element of gained is adjustable 0.01%～5%.
Specific operation process is following,
(1) non-ionic surface active agent F127 is dissolved in the mixed solvent of ethanol and deionized water, adds resorcinol R successively, phosphoric acid or boric acid, 28～37wt%HCl, 15～100wt% formaldehyde F under stirring; The mol ratio of each reactant is:
Deionized water: ethanol: HCl: non-ionic surface active agent: phosphorus source or boron source: R: F=41.5～166: 13.5～54: 0.4～1.6: 0.01～0.04: 0.15～6: 3: 2.3～9;
(2) continue to stir 1 hour or more than, still aging under the room temperature, to the polymer sol and the complete layering of solvent that produce; Remove supernatant liquor, curing is after 24～96 hours down at 70～120 ℃ for lower floor's colloid, and high temperature cabonization obtains the ordered mesoporous carbon of nonmetal doping under inert atmosphere.The nonmetalloid that mixes is evenly distributed in the skeleton of mesoporous charcoal, has higher high-temperature stability.
The preferable mol ratio of resorcinol and formaldehyde is 1: 1～2, and optimum mole ratio is 1: 1.3～1.5, and the best PH scope of solution system is 0.7～1.1.Said method best curing temperature is 80～100 ℃, the time be 48 hours or more than; In the said carbonisation, optimum temperature rise speed is 1～5 ℃/minute, keeps removing surfactant in 2～5 hours at 350～500 ℃, obtains phosphorus, boron doped ordered mesoporous carbon in 2～5 hours at 700 ℃～1200 ℃ high temperature cabonizations.When adding phosphoric acid and the resorcinol mol ratio less than 0.7 the time or boric acid and resorcinol mol ratio less than 1 the time, mesoporous charcoal high-sequential; Along with the content increase of doped with non-metals element, the degree of order reduces gradually.
The nonmetal doping ordered mesoporous carbon functional material that this method synthesized has more excellent capacitive property as electrode material for super capacitor than plain mesoporous carbon and microporous carbon.
The present invention utilizes the self assembly effect of hydrogen bond between phenol-formaldehyde resin modified colloidal sol and the non-ionic surface active agent F127, makes the ordered mesoporous carbon material that the doped with non-metals atom is evenly distributed at carbon skeleton.The adding of phosphorus, boron has increased the hydrophily of carbon material surface; Electronic effect changes; And in carbonisation, kept more oxygen-containing functional group, changed the electronic property of charcoal, on the basis of electric double layer capacitance, contributed more Faraday pseudo-capacitance; Be good electrode material for super capacitor, important wide application prospect can be arranged for improving the ultracapacitor capacitive character.
The present invention adds in the reaction of phenolic resins class and contains heteroatomic inorganic acid; Obtain the elementary remodeling phenolic resins of functionalization; Under acid condition; This predecessor and non-ionic surface active agent obtain having the composite material of mesoscopic structure through the method for liquid phase self assembly, and its degree of order is come modulation by the ratio of predecessor and the amount of surfactant.Finally be converted into the mesoporous polymer and the mesoporous charcoal of a series of nonmetal dopings behind roasting under this composite material process inert atmosphere, the high temperature cabonization, have bigger specific area, bigger pore volume, the aperture structure of homogeneous and the functionalization nonmetalloid that is evenly distributed.The method of this liquid phase self assembly has characteristics such as simple, quick, is expected to realize large-scale production.
Description of drawings
Fig. 1 is the TEM picture of embodiment 2,3,4,5 prepared samples.Explanation has the two-dimentional hexagonal structure of high-sequential through the nonmetal doping meso-porous carbon material that the present invention makes.
Fig. 2 is the EDS mapping picture of embodiment 3.The phosphorus doping meso-porous carbon material that explanation makes through the present invention has uniform element and distributes.
Fig. 3 is physical absorption-desorption picture of embodiment 1,2,3,4,5,6,7.Explanation has typical central hole structure through the nonmetal doping meso-porous carbon material that the present invention makes, and pore-size distribution is narrow.
Fig. 4 is the cyclic voltammetry curve under 5mV/ sweep speed second of embodiment 8 and the constant current charge-discharge Test Drawing under the 0.5A/g.
Embodiment
Embodiment 1:
In the mixed solution of 30g ethanol that is dissolved with 2.5g F127 and deionized water (mass ratio is 1: 1), add the 3.3g resorcinol, mix.Add the catalyst of 0.8g HCl (37wt%), stir after 1 hour, add 3g formalin (37wt%) and continue to stir 2 hours as polycondensation reaction.Gained solution room temperature ageing 96 hours, two-layer until being divided into; Remove the upper strata stillness of night, stirred lower floor's polymer phase 0.5 hour.This product 80 ℃ down solidify 48 hours after, under nitrogen atmosphere, be warmed up to 350 ℃ from room temperature and kept 2 hours with 1 ℃/minute heating rate, continuing ℃ kept 2 hours with 1 ℃/minute heating rate temperature to 800.Products therefrom called after OMC.
The pore structure character of product is: specific area 702m
2/ g, pore volume 0.63cm
3/ g, aperture 4.7nm.
Embodiment 2:
In the mixed solution of 30g ethanol that is dissolved with 2.5g F127 and deionized water (mass ratio is 1: 1), add 3.3g resorcinol and 1.04g phosphoric acid (85wt%), mix.Add the catalyst of 0.8g HCl (37wt%), stir after 1 hour, add 3g formalin (37wt%) and continue to stir 2 hours as polycondensation reaction.Gained solution room temperature ageing 96 hours, two-layer until being divided into; Remove the upper strata stillness of night, stirred lower floor's polymer phase 0.5 hour.This product 80 ℃ down solidify 48 hours after, under nitrogen atmosphere, be warmed up to 350 ℃ from room temperature and kept 2 hours with 1 ℃/minute heating rate, continuing ℃ kept 2 hours with 1 ℃/minute heating rate temperature to 800.Products therefrom called after P0.3-OMC.
The pore structure character of product is: specific area 614m
2/ g, pore volume 0.59cm
3/ g, aperture 5.8nm, phosphorus content are 0.90wt%.
Embodiment 3:
The preparation process is with instance 2, and difference is to add phosphoric acid (85wt%) amount and is 1.75g.Products therefrom called after P0.5-OMC.
The pore structure character of product is: specific area 610m
2/ g, pore volume 0.57cm
3/ g, aperture 5.9nm, phosphorus content are 1.42wt%.
Embodiment 4:
The preparation process is with instance 2, and difference is to add phosphoric acid (85wt%) amount and is 3.15g.Products therefrom called after P0.7-MC.
The pore structure character of product is: specific area 592m
2/ g, pore volume 0.44cm
3/ g, aperture 6.4nm, phosphorus content are 2.12wt%.
Embodiment 5:
In the mixed solution of 30g ethanol that is dissolved with 2.5g F127 and deionized water (mass ratio is 1: 1), add 3.3g resorcinol and 0.56g boric acid, mix.Add the catalyst of 0.8g HCl (37wt%), stir after 1 hour, add 3g formalin (37wt%) and continue to stir 2 hours as polycondensation reaction.Gained solution room temperature ageing 96 hours, two-layer until being divided into; Remove the upper strata stillness of night, stirred lower floor's polymer phase 0.5 hour.This product 80 ℃ down solidify 48 hours after, under nitrogen atmosphere, be warmed up to 350 ℃ from room temperature and kept 2 hours with 1 ℃/minute heating rate, continuing ℃ kept 2 hours with 1 ℃/minute heating rate temperature to 800.Products therefrom called after B0.3-OMC.
The pore structure character of product is: specific area 723m
2/ g, pore volume 0.43cm
3/ g, aperture 5.0nm, boron content are 0.09wt%.
Embodiment 6:
The preparation process is with instance 5, and it is 0.93g that difference is to add the boric acid amount.Products therefrom called after B0.5-OMC.
The pore structure character of product is: specific area 707m
2/ g, pore volume 0.44cm
3/ g, aperture 5.0nm, boron content are 0.31wt%.
Embodiment 7:
The preparation process is with instance 5, and it is 1.3g that difference is to add the boric acid amount.Products therefrom called after B0.7-OMC.
The pore structure character of product is: specific area 640.9m
2/ g, pore volume 0.44cm
3/ g, aperture 5.0nm, boron content are 0.42wt%.
Embodiment 8:
Respectively gained phosphorus, boron doping ordered mesopore carbon, blank mesoporous carbon and the commercial Norit active carbon of buying are evenly mixed in 90: 5: 5 ratio of mass ratio with conductive carbon black, polytetrafluoroethylene (60wt%) as active material; Half oven dry of gained slurry; Compressing tablet, punching.Get wherein that a slice places in the middle of two nickel foam of cutting out, the pressure compressing tablet that adds 5～10MPa makes electrode.As to electrode, in the KOH of 6M solution, carry out the cyclic voltammetry curve test as reference electrode, nickel sheet as work electrode, saturated calomel electrode with above-mentioned electrode.Other gets two above-mentioned electrodes that the active material quality is suitable, separates, compresses with nonwoven fabrics, is assembled into a sandwich type ultracapacitor; And with saturated calomel electrode as reference electrode, in the KOH of 6M solution, carry out constant current charge-discharge test.Wherein the sweeping under the speed of 5mV/s, the per surface area of Norit activated carbon, blank mesoporous charcoal, P0.3-OMC, P0.5-OMC, P0.7-MC, P0.9-MC is respectively 0.18,0.17,0.23,0.28,0.31 and 0.35F/cm than electric capacity
2, and when improve sweep speed to 50mV/s sweep speed the time, it is original 69% that the Norit active carbon is reduced to than electric capacity, blank mesoporous charcoal is original 73%, and mix P0.3-OMC afterwards and P0.5-OMC etc. all remain on more than 80% of former capacitance.Experimental result shows that phosphorus, the boron doping ordered mesopore carbon that utilizes this preparation method to obtain has excellent capacitive property.
Claims (7)
1. the preparation method of an electrode material for super capacitor is characterized in that:
Under the acid condition of PH＜3,, prepare the ordered mesoporous carbon material of nonmetal doping by containing doped chemical resin modified phenol resin gel and non-ionic surface active agent generation liquid phase self assembly effect; Detailed process is following,
1) non-ionic surface active agent is dissolved in alcohol/deionized water mixed solvent, adds resorcinol R, phosphorus source and/or boron source, 28-37wt%HCl, 15-100wt% formaldehyde F successively under stirring;
The mol ratio of reactant is:
Deionized water: alcohol: HCl: deionization surfactant: phosphorus source or boron source: R: F=41.5～166: 13.5～54: 0.4～1.6: 0.01～0.04: 0.15～6: 3: 2.3～9;
2) continue to stir more than 1 hour, room temperature is still aging to layering fully;
Remove supernatant liquor, lower floor's colloid is after solidifying 24～96h under 70～120 ℃; High temperature cabonization obtains the ordered mesopore carbon of nonmetal doping under inert atmosphere.
2. according to the described preparation method of claim 1, it is characterized in that:
Said non-ionic surface active agent is F127 or P123, and solvent alcohol is ethanol or isopropyl alcohol, and said phosphorus source is phosphoric acid or phosphate, and said boron source is boric acid or borate.
3. according to the described preparation method of claim 1, it is characterized in that: used non-ionic surface active agent is F127, and solvent alcohol is an ethanol, and phosphorus source and boron source are phosphoric acid and boric acid.
4. according to the described preparation method of claim 1, it is characterized in that: the mol ratio of said resorcinol and formaldehyde is 1: 1～2, and the pH value of solution system is less than 1.
5. according to the described preparation method of claim 1, it is characterized in that: the optimum mole ratio of resorcinol and formaldehyde is 1: 1.3～1.5, and the best PH scope of solution system is 0.7～1.1.
6. according to the described preparation method of claim 1, it is characterized in that: said digestion time is more than 48 hours or 48 hours; Said inert gas is a nitrogen; The high temperature cabonization process is that colloid is warming up to more than 700 ℃ or 700 ℃ from room temperature with 1～5 ℃/minute heating rate, and high temperature cabonization 2～5 hours kept 2～5 hours at 350～500 ℃ therebetween, to remove surfactant.
7. according to the described preparation method of claim 1, it is characterized in that: said curing temperature is 80～100 ℃, and the time is 48-96 hour; In the said carbonisation, optimum temperature rise speed is 1～5 ℃/minute, keeps removing surfactant in 2～5 hours at 350～500 ℃, obtains phosphorus, boron doped ordered mesoporous carbon in 2～5 hours at 700 ℃～1200 ℃ high temperature cabonizations.
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| CN103172043B (en) * | 2011-12-20 | 2016-03-02 | 中国科学院大连化学物理研究所 | Mesoporous carbon block materials of a kind of sulfur functionalization and preparation method thereof |
| CN102616766A (en) * | 2012-01-19 | 2012-08-01 | 中国科学院山西煤炭化学研究所 | Preparation method for heteratom-containing ordered mesoporous carbon with high specific capacitance |
| CN104192819B (en) * | 2014-07-14 | 2016-06-08 | 上海应用技术学院 | A kind of bar-shaped phosphorus doping mesoporous carbon and its preparation method and application |
| CN105709792A (en) * | 2016-01-19 | 2016-06-29 | 上海师范大学 | Co-doped ordered mesoporous titanium oxide/carbon nano-composite materials and method for preparing same |
| CN112421041B (en) * | 2020-11-17 | 2022-07-19 | 奇瑞商用车（安徽）有限公司 | B-Mo-C carrier and preparation method and application thereof |
| CN115072720B (en) * | 2022-07-22 | 2024-04-02 | 燕山大学 | Oxygen-doped porous carbon electrode material with high pseudocapacitance activity and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100999316A (en) * | 2006-12-29 | 2007-07-18 | 上海师范大学 | Synthesis of high mechanical stability non-metal element doped ordered mosopore carbon material |
| CN101347741A (en) * | 2008-07-29 | 2009-01-21 | 南京航空航天大学 | Method for preparing phosphorus-ordered mesoporous carbon complex and fuel-cell catalyst using the complex as carrier |
| CN101462737A (en) * | 2007-12-19 | 2009-06-24 | 中国科学院大连化学物理研究所 | Preparation of ordered mesoporous carbon material and Ir-containing composite material thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100999316A (en) * | 2006-12-29 | 2007-07-18 | 上海师范大学 | Synthesis of high mechanical stability non-metal element doped ordered mosopore carbon material |
| CN101462737A (en) * | 2007-12-19 | 2009-06-24 | 中国科学院大连化学物理研究所 | Preparation of ordered mesoporous carbon material and Ir-containing composite material thereof |
| CN101347741A (en) * | 2008-07-29 | 2009-01-21 | 南京航空航天大学 | Method for preparing phosphorus-ordered mesoporous carbon complex and fuel-cell catalyst using the complex as carrier |
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