CN106057496A - Preparation method and use of hierarchical pore structure carbon material - Google Patents
Preparation method and use of hierarchical pore structure carbon material Download PDFInfo
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- CN106057496A CN106057496A CN201610356633.5A CN201610356633A CN106057496A CN 106057496 A CN106057496 A CN 106057496A CN 201610356633 A CN201610356633 A CN 201610356633A CN 106057496 A CN106057496 A CN 106057496A
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- ethylenediaminetetraacetic acid
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 15
- 239000002149 hierarchical pore Substances 0.000 title abstract 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002808 molecular sieve Substances 0.000 claims abstract description 18
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011148 porous material Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000197 pyrolysis Methods 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001291 vacuum drying Methods 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000010453 quartz Substances 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 229910052799 carbon Inorganic materials 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 33
- 239000003990 capacitor Substances 0.000 claims description 27
- 239000007772 electrode material Substances 0.000 claims description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 2
- 229910052756 noble gas Inorganic materials 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000002242 deionisation method Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract 3
- 230000008021 deposition Effects 0.000 abstract 2
- 238000005119 centrifugation Methods 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- 238000004146 energy storage Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000013066 combination product Substances 0.000 description 3
- 229940127555 combination product Drugs 0.000 description 3
- 230000009514 concussion Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910021426 porous silicon Inorganic materials 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 241000186216 Corynebacterium Species 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical group Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Manufacturing & Machinery (AREA)
Abstract
The invention provides a preparation method and use of a hierarchical pore structure carbon material. The method is performed according to the following steps: an ethylenediaminetetraacetic acid metal sodium salt is dissolved in deionized water, and then an ethylenediaminetetraacetic acid metal sodium salt solution is prepared; a mesoporous molecular sieve SBA-15 is dipped into the ethylenediaminetetraacetic acid metal sodium salt solution, so the ethylenediaminetetraacetic acid metal sodium salt solution are soaked into pore passages of the molecular sieve, ultrasonic processing and vacuum-pumping processing are performed, a deposition mixture is taken out through centrifugation then, and the deposition mixture goes through vacuum drying to be stand-by; the product is placed in a nickel crucible and placed in a high-temperature quartz tube furnace to carry out high-temperature pyrolysis under protection of an inert gas flow, a composite carbon material is obtained through the pyrolysis, the composite carbon material is placed in an acid solution, stirring is performed, the composite carbon material is then washed to be neutral, and then a hierarchical pore structure carbon material is obtained through drying. The hierarchical pore structure carbon material prepared through regulation and control of the mesoporous molecular sieve has abundant-mesoporous structure, excellent electrochemical performance and high stability.
Description
Technical field
The invention belongs to electrode material for super capacitor preparation field, be specifically related to a kind of electrode of super capacitor many
The preparation method of level pore structure material with carbon element.
Background technology
Along with the exhaustion of petroleum resources and going from bad to worse of environment, people to efficiently, cleaning, continuable green energy resource and
The development and utilization of energy storage technology is increasingly paid close attention to.At some special dimensions, such as Aero-Space, defence and military, electric vehicle etc.,
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 is the weakest with energy storage technology.In energy storage side
Face, common batteries has preferable energy density, but power density is on the low side, conventional capacitor then contrast.
Ultracapacitor is also referred to as electrochemical capacitor, is the novel energy-storing unit grown up on the basis of traditional capacitor
Part, a kind of energy storage device between common batteries and conventional capacitor.Different electrode materials and electrolyte can be used
System, its energy storage principle is not quite similar.Owing to have employed 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 with often
Blank between rule capacitor.Can be divided into by the mechanism difference storing electric charge: double layer capacitor (Electric Double
Layer Capacitor, EDLC), store electric charge by interfacial electric double layer；Redox capacitors (Redox Capacitor),
Electric charge is stored by the mechanism of Faraday pseudo-capacitance；Hybrid capacitors, two electrodes are respectively by Faraday pseudo-capacitance and double electricity
Layer capacitance stores electric charge.The active charcoal of electrode material, metal-oxide, conducting polymer and combination electrode material, and activated carbon
Because its specific surface area is big, the advantages such as electrochemical stability is good become the most popular electrode material of ultracapacitor.
Typically, the electrode carbon material of ultracapacitor needs to exist hierarchical porous structure material with carbon element, and micropore strengthens electric charge
Storage capacity, mesoporous existence can accelerate the diffusion of electrode intermediate ion to strengthen electric conductivity, and macropore can be as ion
Buffer Pool.Material with carbon element prepared by Conventional activation methods is difficult to have orderly pore property, and physically activated time-consuming length,
Efficiency is low, and chemical activation is usually present, and energy consumption is high, pollute the deficiencies such as big.Therefore, the preparation of current existing shortcoming is overcome efficiently
Orderly material with carbon element have important practical significance for electrode material for super capacitor.
Summary of the invention
The present invention relates to a kind of utilize organic molecule salt as precursor by silica-based template regulation and control prepare orderly many
The preparation of level pore structure carbon-based electrode material and modulation process.With ethylenediaminetetraacetic acid metal sodium salt (EDTA-xNa) as raw material,
Being regulated and controled by template, the orderly pore structure material with carbon element with high specific surface area is prepared in a step pyrolysis, and, it possesses excellent
Chemical property.
The technical solution used in the present invention is:
The preparation method of the hierarchical porous structure material with carbon element of a kind of electrode of super capacitor, is carried out as steps described below:
Step 1, ethylenediaminetetraacetic acid metal sodium salt is dissolved in deionized water, is configured to ethylenediaminetetraacetic acid metallic sodium
Saline solution；Then mesoporous molecular sieve SBA-15 is impregnated in ethylenediaminetetraacetic acid metallic sodium saline solution, makes ethylenediaminetetraacetic acid
Metallic sodium saline solution is impregnated into molecular sieve pore passage, and carries out ultrasonic, evacuation process, then by centrifugal, takes out precipitation and mixes
Compound, vacuum drying, stand-by；
Step 2, the product in step 1 is put in nickel crucible, is placed in high quartz tube furnace, protect at inert gas
Under, carry out high temperature pyrolysis, after pyrolysis, obtain complex carbon material, complex carbon material is placed in acid solution stirring, the most again
Washing is to neutral, and drying is to hierarchical porous structure material with carbon element.
In step 1, described ethylenediaminetetraacetic acid metal sodium salt (EDTA-xNa) is disodium EDTA
Or tetrasodium salt of EDTA (EDTA-4Na) (EDTA-2Na).
In step 1, during configuration ethylenediaminetetraacetic acid metallic sodium saline solution, ethylenediaminetetraacetic acid metal sodium salt and deionized water
Mass ratio is 1～2:1.
In step 1, the mass ratio of described mesoporous molecular sieve SBA-15 and ethylenediaminetetraacetic acid metal sodium salt be 0.05～
0.2:1.
In step 1, the dip time 6～12h of described mesoporous molecular sieve SBA-15, ultrasonic time is 1～2h, evacuation
Time is 3～6h.
In step 2, described inert gas is N2, the one of Ar, noble gas flow velocity is 20～90mL/min.
In step 2, the mode of described high temperature pyrolysis is: heating rate is 3～10 DEG C/min, is warming up to 700～900
DEG C, and at 700～900 DEG C, keep 0.5～3h.
In step 2, described acid is Fluohydric acid., and volume fraction is 5～20%, and described stir speed (S.S.) is 200～1000r/
Min, the time is 12～24h.
In step 1, in described centrifugal process, centrifugal rotational speed is 2000～5000r/min, and the time is 2～6h；Step 1
In, described vacuum drying temperature is 60～100 DEG C, and the time is 8～24h；In step 2, described baking temperature is 60～80
℃。
Prepared hierarchical porous structure material with carbon element is for electrode material for super capacitor.
The invention has the beneficial effects as follows:
(1) by ethylenediaminetetraacetic acid metal sodium salt as precursor, by the special construction of this kind of salt self (containing rich
Rich carboxyl) self-activation prepares multi-stage porous carbon, eliminates loaded down with trivial details, dangerous activation step, and this has great importance.And material
Expecting that the nitrogen element self contained can adulterate the basis of nitrogen in situ, this also has beneficial effect for promoting chemical property.
(2) material prepares preparation method simply, and strong operability saves steps such as loading material extraly, be combined,
And can utilize the factor such as the amount of alkali metal ion, pyrolysis temperature and heating rate in molecule that material behavior is regulated and controled.
(3) regulated and controled by mesopore molecular sieve, the material with carbon element that Pore Characteristics is excellent can be prepared, mesoporous containing enrich
Structure, has fabulous chemical property, and stability is strong, potential becomes commercial electrode material.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the material with carbon element that embodiment 1 prepares；
Fig. 2 is that the prepared material with carbon element of embodiment 1 is according to N2Graph of pore diameter distribution that adsorption-desorption curve obtains and accumulative hole body
Integration Butut, wherein curve (a) is graph of pore diameter distribution, and curve (b) is accumulative pore volume distribution figure.
Detailed description of the invention
Below in conjunction with being embodied as example, the present invention will be further described:
Embodiment 1
Weigh 10g disodiumedetate to be dissolved in 5mL deionized water, fully concussion, ultrasonic dissolution.It is subsequently adding
0.5g mesoporous molecular sieve SBA-15 (SBA-15:EDTA-2Na=0.05:1), makes molecular sieve be sufficiently impregnated with in EDTA-2Na solution
After middle 12h, the most ultrasonic 2h, evacuation 3h process, by mixture centrifugal 6h under 2000r/min rotating speed, extract deposit, will
It dries, at 100 DEG C of vacuum drying 8h, the product obtaining being dried.
Then dried above-mentioned combination product is put in nickel crucible, is placed in high quartz tube furnace, at inert gas
N2Under (gas flow rate is 20mL/min) protection, it is warming up to 700 DEG C with the heating rate of 3 DEG C/min, maintains natural cooling after 3h,
The complex carbon material of black is obtained after pyrolysis.It is subsequently adding the hydrofluoric acid solution that excess volume concentration is 5%, sets stirring
Speed be 1000r/min stirring 12h with the abundant porous silicon removing residual, then with a large amount of hot water and deionized water wash extremely in
Property, at a temperature of 60 DEG C, drying is to orderly hierarchical porous structure carbon electrode material.
The method of testing using it for electrode material for super capacitor is:
First by described material with carbon element through the levigate powder being less than 30 μm to particle diameter of agate mortar, in mass ratio 85: 10: 5 weigh
Above-mentioned porous carbon, acetylene black and Kynoar (Poly (vinylidene fluoride), PVDF), add appropriate N-methyl
Ketopyrrolidine (N-Methyl pyrrolidone, NMP) is sufficiently mixed and sizes mixing, and is uniformly coated on a size of 1.2 × 2.0cm
Nickel foam on, treat that it is dried, hand oil-pressure machine cover with 10MPa pressure and makes electrode, and vacuum drying further
Stand-by.Electrode test uses three-electrode system, is wherein Pt sheet to electrode, and reference electrode is saturated calomel electrode (Hg/HgO),
Using 6M KOH aqueous solution is electrolyte.
By scanogram (Fig. 1) it can be seen that this material is corynebacterium, it is interconnected to constitute netted.Inhale according to nitrogen
Attached-desorption isotherm, the BET specific surface area of this material is 1294m2/ g, pore volume is 1.01cm3/ g, wherein, according to t-plot
The micropore specific area that method calculates is 714m2/ g, micropore volume is 0.57cm3/ g, has the most mesoporous and macroporous structure
(Fig. 2), average pore diameter is 2.93nm.Use it for electro-chemical test, be 128.4F/g than electric capacity under 1A/g electric current density.
Embodiment 2
Weigh 10g disodiumedetate to be dissolved in 7mL deionized water, fully concussion, ultrasonic dissolution.It is subsequently adding 1g
Mesoporous molecular sieve SBA-15 (SBA-15:EDTA-2Na=0.1:1), makes molecular sieve be sufficiently impregnated with 8h in EDTA-2Na solution,
After the most ultrasonic 1h, evacuation 4h process, by mixture centrifugal 4h under 3600r/min rotating speed, extract deposit, by it 80
DEG C vacuum drying 16h is dried and is obtained the product that is dried.
Then dried above-mentioned combination product is put in nickel crucible, is placed in high quartz tube furnace, at inert gas
N2Under (gas flow rate is 50mL/min) protection, it is warming up to 800 DEG C with the heating rate of 5 DEG C/min, maintains natural cooling after 1h,
The complex carbon material of black is obtained after pyrolysis.Being subsequently adding the hydrofluoric acid solution that excess volume concentration is 15%, setting is stirred
Mix speed be 200r/min stirring 12h with the abundant porous silicon removing residual, then with a large amount of hot water and deionized water wash extremely
Neutrality, at a temperature of 70 DEG C, drying is to orderly hierarchical porous structure carbon electrode material.
According to nitrogen adsorption-desorption isotherm, the BET specific surface area of this material is 1307m2/ g, pore volume is 1.12cm3/
G, wherein, is 698m according to the micropore specific area that t-plot method calculates2/ g, micropore volume is 0.61cm3/ g, has substantially
Mesoporous and macroporous structure, average pore diameter is 2.88nm.Use it for electro-chemical test, under 1A/g electric current density, compare electric capacity
For 123.4F/g.
Embodiment 3
Weigh 10g tetrasodium ethylenediamine tetraacetate to be dissolved in 10mL deionized water, fully concussion, ultrasonic dissolution.It is subsequently adding
2g mesoporous molecular sieve SBA-15 (SBA-15:EDTA-4Na=0.2:1), makes molecular sieve be sufficiently impregnated with in EDTA-4Na solution
After 6h, the most ultrasonic 2h, evacuation 6h process, by mixture centrifugal 2h under 5000r/min rotating speed, extract deposit, by it
The product obtaining being dried is dried at 60 DEG C of vacuum drying 24h.
Then dried above-mentioned combination product is put in nickel crucible, is placed in high quartz tube furnace, at inert gas
Under Ar (gas flow rate is 90mL/min) protection, it is warming up to 900 DEG C with the heating rate of 10 DEG C/min, the coldest after maintaining 0.5h
But, after pyrolysis, obtain the complex carbon material of black.It is subsequently adding the hydrofluoric acid solution that excess volume concentration is 20%, sets
Stir speed (S.S.) is the 200r/min stirring 24h porous silicon with abundant removal residual, then with a large amount of hot water and deionized water wash
To neutral, at a temperature of 80 DEG C, drying is to orderly hierarchical porous structure carbon electrode material.
According to nitrogen adsorption-desorption isotherm, the BET specific surface area of this material is 1195m2/ g, pore volume is 1.07cm3/
G, wherein, is 551m according to the micropore specific area that t-plot method calculates2/ g, micropore volume is 0.44cm3/ g, has substantially
Mesoporous and macroporous structure, average pore diameter is 3.11nm.Use it for electro-chemical test, under 1A/g electric current density, compare electric capacity
For 101.9F/g.
Claims (10)
1. the preparation method of the hierarchical porous structure material with carbon element of an electrode of super capacitor, it is characterised in that according to following step
Suddenly carry out:
Step 1, ethylenediaminetetraacetic acid metal sodium salt is dissolved in deionized water, is configured to ethylenediaminetetraacetic acid metal sodium salt molten
Liquid；Then mesoporous molecular sieve SBA-15 is impregnated in ethylenediaminetetraacetic acid metallic sodium saline solution, makes ethylenediaminetetraacetic acid metal
Sodium salt solution is impregnated into molecular sieve pore passage, and carries out ultrasonic, evacuation process, then by centrifugal, takes out precipitation mixture,
Vacuum drying, stand-by；
Step 2, the product in step 1 is put in nickel crucible, is placed in high quartz tube furnace, under inert gas is protected, enter
Row high temperature pyrolysis, through pyrolysis after obtain complex carbon material, complex carbon material is placed in acid solution stirring, wash the most again to
Neutrality, drying is to hierarchical porous structure material with carbon element.
The preparation method of the hierarchical porous structure material with carbon element of a kind of electrode of super capacitor the most according to claim 1, its
Being characterised by, in step 1, described ethylenediaminetetraacetic acid metal sodium salt is disodium EDTA or ethylenediaminetetraacetic acid
In tetrasodium salt.
The preparation method of the hierarchical porous structure material with carbon element of a kind of electrode of super capacitor the most according to claim 1, its
It is characterised by, in step 1, during configuration ethylenediaminetetraacetic acid metallic sodium saline solution, ethylenediaminetetraacetic acid metal sodium salt and deionization
Water quality ratio is 1～2:1.
The preparation method of the hierarchical porous structure material with carbon element of a kind of electrode of super capacitor the most according to claim 1, its
Be characterised by, in step 1, the mass ratio of described mesoporous molecular sieve SBA-15 and ethylenediaminetetraacetic acid metal sodium salt be 0.05～
0.2:1.
The preparation method of the hierarchical porous structure material with carbon element of a kind of electrode of super capacitor the most according to claim 1, its
Being characterised by, in step 1, the dip time 6～12h of described mesoporous molecular sieve SBA-15, ultrasonic time is 1～2h, takes out true
The empty time is 3～6h.
The preparation method of the hierarchical porous structure material with carbon element of a kind of electrode of super capacitor the most according to claim 1, its
Being characterised by, in step 2, described inert gas is N2, the one of Ar, noble gas flow velocity is 20～90mL/min.
The preparation method of the hierarchical porous structure material with carbon element of a kind of electrode of super capacitor the most according to claim 1, its
Being characterised by, in step 2, the mode of described high temperature pyrolysis is: heating rate is 3～10 DEG C/min, is warming up to 700～900
DEG C, and at 700～900 DEG C, keep 0.5～3h.
The preparation method of the hierarchical porous structure material with carbon element of a kind of electrode of super capacitor the most according to claim 1, its
Being characterised by, in step 2, described acid is Fluohydric acid., and volume fraction is 5～20%, and described stir speed (S.S.) is 200～1000r/
Min, the time is 12～24h.
The preparation method of the hierarchical porous structure material with carbon element of a kind of electrode of super capacitor the most according to claim 1, its
Being characterised by, in step 1, in described centrifugal process, centrifugal rotational speed is 2000～5000r/min, and the time is 2～6h；Step 1
In, described vacuum drying temperature is 60～100 DEG C, and the time is 8～24h；In step 2, described baking temperature is 60～80
℃。
10. the purposes of hierarchical porous structure material with carbon element prepared by the method described in claim 1～9 any one, it is characterised in that
Described hierarchical porous structure material with carbon element is used for electrode material for super capacitor.
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