CN106057496B - A kind of preparation method and its usage of hierarchical porous structure carbon material - Google Patents
A kind of preparation method and its usage of hierarchical porous structure carbon material Download PDFInfo
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Abstract
The present invention provides a kind of preparation method and its usages of hierarchical porous structure carbon material, carry out as steps described below：Ethylenediamine tetra-acetic acid metal sodium salt is dissolved in deionized water, is configured to ethylenediamine tetra-acetic acid metal sodium salt solution；Then mesopore molecular sieve SBA 15 is impregnated into ethylenediamine tetra-acetic acid metal sodium salt solution, ethylenediamine tetra-acetic acid metal sodium salt solution is made to be impregnated into molecular sieve pore passage, and carry out ultrasound, vacuumize process, then pass through centrifugation, precipitation mixture is taken out, is dried in vacuo, for use；Product is put in nickel crucible, is placed in high quartz tube furnace, under inert gas protection; high temperature pyrolysis is carried out, complex carbon material is obtained after pyrolysis, complex carbon material is placed in acid solution and is stirred; then it washs again to neutrality, drying to hierarchical porous structure carbon material.The present invention contains abundant meso-hole structure by hierarchical porous structure carbon material prepared by mesopore molecular sieve regulation and control, has fabulous chemical property, and stability is strong.
Description
Technical field
The invention belongs to electrode material for super capacitor preparation fields, and in particular to a kind of electrode of super capacitor it is more
The preparation method of grade pore structure carbon material.
Background technology
With petroleum resources exhaustion and environment worsening, people to efficiently, cleaning, sustainable green energy resource and
The development and utilization of energy storage technology is increasingly paid close attention to.In some special dimensions, such as aerospace, defence and military, electric vehicle,
The energy storage device of the performances such as especially needed high-energy density, high power density and long-life.Presently, solar energy, wind energy etc.
It is considered as the green energy resource of most potentiality to be exploited, but the transmission of these energy and energy storage technology are extremely weak.In energy storage side
Face, common batteries have preferable energy density, but power density is relatively low, and conventional capacitor is then exactly the opposite.
Ultracapacitor is also referred to as electrochemical capacitor, is the novel energy-storing member to grow up on the basis of traditional capacitor
Part, a kind of energy storage device between common batteries and conventional capacitor.Different electrode material and electrolyte can be used
System, energy storage principle are not quite similar.As a result of novel electrode material and electrolyte system, energy density and functional density
It is obviously improved on the basis of traditional capacitor, as a kind of powerful energy storage device, has filled up common batteries and often
Advise the blank between capacitor.It can be divided by the mechanism difference of storage charge：Double layer capacitor (Electric Double
Layer Capacitor, EDLC), charge is stored by interfacial electric double layer；Redox capacitors (Redox Capacitor),
Charge is stored by the mechanism of Faraday pseudo-capacitance；Hybrid capacitors, two electrodes pass through Faraday pseudo-capacitance and double electricity respectively
Layer capacitance stores charge.The active charcoal of electrode material, metal oxide, conducting polymer and combination electrode material, and activated carbon
Because of its large specific surface area, the advantages that electrochemical stability is good, becomes the most popular electrode material of ultracapacitor.
Typically, the electrode carbon material of ultracapacitor is needed there are hierarchical porous structure carbon material, and micropore enhances charge
Storage capacity, mesoporous presence can accelerate the diffusion of electrode intermediate ion to enhance electric conductivity, and macropore can be used as ion
Buffer pool.Carbon material prepared by Conventional activation methods is difficult to have orderly pore property, and it is physically activated time-consuming,
Efficiency is low, and chemical activation usually there are high energy consumption, pollution it is big the deficiencies of.Therefore, the shortcomings that having at present is overcome to prepare efficient
Orderly carbon material have important practical significance for electrode material for super capacitor.
Invention content
The present invention relates to a kind of orderly more are prepared by the regulation and control of silicon substrate template by the use of organic molecule salt as precursor
The preparation of grade pore structure carbon-based electrode material and modulation process.With ethylenediamine tetra-acetic acid metal sodium salt (EDTA-xNa) for raw material,
Regulated and controled by template, the orderly pore structure carbon material with high specific surface area is prepared in step pyrolysis, also, it have it is excellent
Chemical property.
The technical solution adopted by the present invention is：
A kind of preparation method of the hierarchical porous structure carbon material of electrode of super capacitor, carries out as steps described below：
Ethylenediamine tetra-acetic acid metal sodium salt is dissolved in deionized water by step 1, is configured to ethylenediamine tetra-acetic acid metallic sodium
Salting liquid；Then mesoporous molecular sieve SBA-15 is impregnated into ethylenediamine tetra-acetic acid metal sodium salt solution, makes ethylenediamine tetra-acetic acid
Metal sodium salt solution is impregnated into molecular sieve pore passage, and carries out ultrasound, vacuumize process, and then by centrifugation, it is mixed to take out precipitation
Object is closed, is dried in vacuo, for use；
Product in step 1 is put in nickel crucible by step 2, is placed in high quartz tube furnace, is protected in inert gas
Under, high temperature pyrolysis is carried out, complex carbon material is obtained after pyrolysis, complex carbon material is placed in acid solution and is stirred, Ran Houzai
It washs to neutrality, drying to hierarchical porous structure carbon material.
In step 1, the ethylenediamine tetra-acetic acid metal sodium salt (EDTA-xNa) is disodium EDTA
(EDTA-2Na) or tetrasodium salt of EDTA (EDTA-4Na).
In step 1, when ethylenediamine tetra-acetic acid metal sodium salt solution is configured, ethylenediamine tetra-acetic acid metal sodium salt and deionized water
Mass ratio is 1~2：1.
In step 1, the mass ratio of the mesoporous molecular sieve SBA-15 and ethylenediamine tetra-acetic acid metal sodium salt for 0.05~
0.2：1.
In step 1,6~12h of dip time of the mesoporous molecular sieve SBA-15, ultrasonic time is 1~2h, is vacuumized
Time is 3~6h.
In step 2, the inert gas is N2, one kind of Ar, inert gas flow velocity is 20~90mL/min.
In step 2, the mode of the high temperature pyrolysis is：Heating rate is 3~10 DEG C/min, is warming up to 700~900
DEG C, and 0.5~3h is kept at 700~900 DEG C.
In step 2, the acid is hydrofluoric acid, and volume fraction is 5~20%, and the stir speed (S.S.) is 200~1000r/
Min, the time for 12~for 24 hours.
In step 1, centrifugal rotational speed is 2000~5000r/min in the centrifugal process, and the time is 2~6h；Step 1
In, the vacuum drying temperature is 60~100 DEG C, the time for 8~for 24 hours；In step 2, the drying temperature is 60~80
℃。
Prepared hierarchical porous structure carbon material is used for electrode material for super capacitor.
The beneficial effects of the invention are as follows：
(1) precursor is used as by ethylenediamine tetra-acetic acid metal sodium salt, by this kind of salt special construction of itself (containing rich
Rich carboxyl) self-activation prepares multi-stage porous carbon, cumbersome, dangerous activation step is eliminated, this has great importance.And material
Expect that the nitrogen itself contained can adulterate the basis of nitrogen in situ, this also has beneficial effect for promoting chemical property.
(2) material preparation preparation method is simple, strong operability, saves and extraly material is loaded, is compound and etc.,
And material property can be regulated and controled using the factors such as the amount of alkali metal ion, pyrolysis temperature and heating rate in molecule.
(3) regulated and controled by mesopore molecular sieve, the excellent carbon material of Pore Characteristics can be prepared, containing abundant mesoporous
Structure has fabulous chemical property, and stability is strong, potential to become commercial electrode material.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of carbon material made from embodiment 1；
Fig. 2 is carbon material made from embodiment 1 according to N2The graph of pore diameter distribution and accumulative hole body that adsorption-desorption curve obtains
Butut is integrated, wherein curve (a) is graph of pore diameter distribution, and curve (b) is accumulative pore volume distribution figure.
Specific embodiment
With reference to specific implementation example, the present invention will be further described：
Embodiment 1
It weighs 10g disodium ethylene diamine tetraacetates to be dissolved in 5mL deionized waters, fully shaking, ultrasonic dissolution.Then it adds in
0.5g mesoporous molecular sieve SBA-15s (SBA-15：EDTA-2Na=0.05：1) molecular sieve, is made to be sufficiently impregnated in EDTA-2Na solution
Middle 12h, then ultrasound 2h, vacuumize 3h processing after, mixture under 2000r/min rotating speeds is centrifuged into 6h, extracts deposit, will
It is dried in vacuo 8h at 100 DEG C and dries to obtain dry product.
Then dried above-mentioned combination product is put in nickel crucible, be placed in high quartz tube furnace, in inert gas
N2Under (gas flow rate 20mL/min) protections, 700 DEG C are warming up to the heating rate of 3 DEG C/min, maintains natural cooling after 3h,
The complex carbon material of black is obtained after pyrolysis.Then the hydrofluoric acid solution of excess volume a concentration of 5%, setting stirring are added in
Rate stirs 12h fully to remove remaining porous silicon for 1000r/min, is then washed with a large amount of hot water and deionized water into
Property, drying is to orderly hierarchical porous structure carbon electrode material at a temperature of 60 DEG C.
Using it for the test method of electrode material for super capacitor is：
First by the carbon material through the levigate powder to grain size less than 30 μm of agate mortar, in mass ratio 85: 10: 5 weigh
Above-mentioned porous carbon, acetylene black and Kynoar (Poly (vinylidene fluoride), PVDF), add in appropriate N- methyl
Pyrrolidones (N-Methyl pyrrolidone, NMP) is sufficiently mixed and sizes mixing, and is 1.2 × 2.0cm it was evenly coated on size
Nickel foam on, after its drying after, covered on hand oil-pressure machine with 10MPa pressure and electrode be made, and further vacuum drying
For use.Electrode test uses three-electrode system, wherein being Pt pieces to electrode, reference electrode is saturated calomel electrode (Hg/HgO),
6M KOH aqueous solutions are used as electrolyte.
By scan image (Fig. 1) as can be seen that the material is interconnected to constitute netted in corynebacterium.It is inhaled according to nitrogen
Attached-desorption isotherm, the BET specific surface area of the material is 1294m2/ g, pore volume 1.01cm3/ g, wherein, according to t-plot
The micropore specific area that method calculates is 714m2/ g, micropore volume 0.57cm3/ g has apparent mesoporous and macroporous structure
(Fig. 2), average pore diameter 2.93nm.Electro-chemical test is used it for, specific capacitance is 128.4F/g under 1A/g current densities.
Embodiment 2
It weighs 10g disodium ethylene diamine tetraacetates to be dissolved in 7mL deionized waters, fully shaking, ultrasonic dissolution.Then 1g is added in
Mesoporous molecular sieve SBA-15 (SBA-15：EDTA-2Na=0.1：1) molecular sieve, is made to be sufficiently impregnated the 8h in EDTA-2Na solution,
Then ultrasound 1h, vacuumize 4h processing after, mixture under 3600r/min rotating speeds is centrifuged into 4h, deposit is extracted, by it 80
DEG C vacuum drying 16h dry to obtain dry product.
Then dried above-mentioned combination product is put in nickel crucible, be placed in high quartz tube furnace, in inert gas
N2Under (gas flow rate 50mL/min) protections, 800 DEG C are warming up to the heating rate of 5 DEG C/min, maintains natural cooling after 1h,
The complex carbon material of black is obtained after pyrolysis.Then the hydrofluoric acid solution of excess volume a concentration of 15% is added in, setting is stirred
Mix rate for 200r/min stir 12h fully to remove remaining porous silicon, then with a large amount of hot water and deionized water wash to
Neutrality, drying is to orderly hierarchical porous structure carbon electrode material at a temperature of 70 DEG C.
According to nitrogen adsorption-desorption isotherm, the BET specific surface area of the material is 1307m2/ g, pore volume 1.12cm3/
G, wherein, it is 698m according to the micropore specific area that t-plot methods calculate2/ g, micropore volume 0.61cm3/ g has apparent
Mesoporous and macroporous structure, average pore diameter 2.88nm.Electro-chemical test is used it for, the specific capacitance under 1A/g current densities
For 123.4F/g.
Embodiment 3
It weighs 10g tetrasodium ethylenediamine tetraacetates to be dissolved in 10mL deionized waters, fully shaking, ultrasonic dissolution.Then it adds in
2g mesoporous molecular sieve SBA-15s (SBA-15：EDTA-4Na=0.2：1) molecular sieve, is made to be sufficiently impregnated in EDTA-4Na solution
6h, then ultrasound 2h, vacuumize 6h processing after, mixture under 5000r/min rotating speeds is centrifuged into 2h, deposit is extracted, by it
In 60 DEG C of vacuum drying, drying obtains dry product for 24 hours.
Then dried above-mentioned combination product is put in nickel crucible, be placed in high quartz tube furnace, in inert gas
Under Ar (gas flow rate 90mL/min) protections, 900 DEG C are warming up to the heating rate of 10 DEG C/min, remains naturally cold after 0.5h
But, the complex carbon material of black is obtained after pyrolysis.Then the hydrofluoric acid solution of excess volume a concentration of 20%, setting are added in
Stir speed (S.S.) is stirred for 200r/min for 24 hours fully to remove remaining porous silicon, is then washed with a large amount of hot water and deionized water
To neutrality, drying is to orderly hierarchical porous structure carbon electrode material at a temperature of 80 DEG C.
According to nitrogen adsorption-desorption isotherm, the BET specific surface area of the material is 1195m2/ g, pore volume 1.07cm3/
G, wherein, it is 551m according to the micropore specific area that t-plot methods calculate2/ g, micropore volume 0.44cm3/ g has apparent
Mesoporous and macroporous structure, average pore diameter 3.11nm.Electro-chemical test is used it for, the specific capacitance under 1A/g current densities
For 101.9F/g.
Claims (9)
1. the preparation method of the hierarchical porous structure carbon material of a kind of electrode of super capacitor, which is characterized in that according to following steps
It is rapid to carry out：
Ethylenediamine tetra-acetic acid metal sodium salt is dissolved in deionized water by step 1, and it is molten to be configured to ethylenediamine tetra-acetic acid metal sodium salt
Liquid；Then mesoporous molecular sieve SBA-15 is impregnated into ethylenediamine tetra-acetic acid metal sodium salt solution, makes ethylenediamine tetra-acetic acid metal
Sodium salt solution is impregnated into molecular sieve pore passage, and carries out ultrasound, vacuumize process, then by centrifugation, takes out precipitation mixture,
Vacuum drying, for use；
Product in step 1 is put in nickel crucible by step 2, is placed in high quartz tube furnace, under inert gas protection, into
Row high temperature pyrolysis, obtains complex carbon material after pyrolysis, and complex carbon material is placed in acid solution and is stirred, then wash again to
Neutrality, drying to hierarchical porous structure carbon material；
In step 1, when ethylenediamine tetra-acetic acid metal sodium salt solution is configured, ethylenediamine tetra-acetic acid metal sodium salt and deionized water quality
Than being 1 ~ 2：1.
2. a kind of preparation method of the hierarchical porous structure carbon material of electrode of super capacitor according to claim 1,
It is characterized in that, in step 1, the ethylenediamine tetra-acetic acid metal sodium salt is disodium EDTA or ethylenediamine tetra-acetic acid
Tetrasodium salt.
3. a kind of preparation method of the hierarchical porous structure carbon material of electrode of super capacitor according to claim 1,
Be characterized in that, in step 1, the mass ratio of the mesoporous molecular sieve SBA-15 and ethylenediamine tetra-acetic acid metal sodium salt for 0.05 ~
0.2：1.
4. a kind of preparation method of the hierarchical porous structure carbon material of electrode of super capacitor according to claim 1,
It is characterized in that, in step 1,6 ~ 12 h of dip time of the mesoporous molecular sieve SBA-15, ultrasonic time is 1 ~ 2 h, is taken out true
The empty time is 3 ~ 6 h.
5. a kind of preparation method of the hierarchical porous structure carbon material of electrode of super capacitor according to claim 1,
It is characterized in that, in step 2, the inert gas is N2, one kind of Ar, inert gas flow velocity is 20 ~ 90 mL/min.
6. a kind of preparation method of the hierarchical porous structure carbon material of electrode of super capacitor according to claim 1,
It is characterized in that, in step 2, the mode of the high temperature pyrolysis is：Heating rate is 3 ~ 10 oC/min, is warming up to 700 ~ 900 o
C, and 0.5 ~ 3 h is kept under 700 ~ 900 oC.
7. a kind of preparation method of the hierarchical porous structure carbon material of electrode of super capacitor according to claim 1,
It is characterized in that, in step 2, the acid is hydrofluoric acid, and volume fraction is 5 ~ 20%, and the stir speed (S.S.) is 200 ~ 1000 r/
Min, time are 12 ~ 24 h.
8. a kind of preparation method of the hierarchical porous structure carbon material of electrode of super capacitor according to claim 1,
It is characterized in that, in step 1, centrifugal rotational speed is 2000 ~ 5000 r/min in the centrifugal process, and the time is 2 ~ 6 h；Step 1
In, the vacuum drying temperature is 60 ~ 100 oC, and the time is 8 ~ 24 h；In step 2, the drying temperature is 60 ~ 80 o
C。
9. the purposes of hierarchical porous structure carbon material prepared by the method described in claim 1 ~ 8 any one, which is characterized in that institute
Hierarchical porous structure carbon material is stated for electrode material for super capacitor.
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| CN108584912B (en) * | 2018-07-03 | 2020-03-10 | 南京大学 | Synthetic method of novel nitrogen-doped ordered mesoporous carbon material |
| CN109133051A (en) * | 2018-09-26 | 2019-01-04 | 桂林电子科技大学 | A kind of HEDTA base porous carbon materials and its preparation method and application |
| CN110028069A (en) * | 2019-04-18 | 2019-07-19 | 河南师范大学 | A kind of preparation method of the advanced carbon electrode material of multi-stage porous for supercapacitor |
| CN110155982A (en) * | 2019-05-23 | 2019-08-23 | 福建工程学院 | A kind of carbon burns SBA-15 mesopore molecular sieve and preparation method thereof and its application in water system battery |
| CN110773222A (en) * | 2019-11-13 | 2020-02-11 | 河南师范大学 | Universal preparation method and application of hierarchical pore nitrogen-doped carbon catalyst based on double-pore-foaming agent synthesis |
| CN112973625B (en) * | 2021-02-05 | 2022-05-10 | 中南林业科技大学 | Lignin-based carbon nanotube and preparation method and application thereof |
| CN114334475A (en) * | 2021-10-01 | 2022-04-12 | 中国科学院宁波材料技术与工程研究所 | One-step synthesized high-specific-surface-area hierarchical pore carbon electrode material and preparation method and application thereof |
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| CN103964412B (en) * | 2013-01-30 | 2016-12-28 | 北京化工大学 | A kind of preparation method of N doping loose structure material with carbon element |
| CN104211040B (en) * | 2013-11-14 | 2016-05-11 | 中国石油大学(北京) | The preparation method of high specific surface area porous carbon nano rod |
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