CN107285315A - A kind of adjustable aperture obtains soluble alginate base super capacitor active carbon material and one step charing preparation method - Google Patents
A kind of adjustable aperture obtains soluble alginate base super capacitor active carbon material and one step charing preparation method Download PDFInfo
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- CN107285315A CN107285315A CN201710672074.3A CN201710672074A CN107285315A CN 107285315 A CN107285315 A CN 107285315A CN 201710672074 A CN201710672074 A CN 201710672074A CN 107285315 A CN107285315 A CN 107285315A
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- soluble alginate
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- 235000010443 alginic acid Nutrition 0.000 title claims abstract description 56
- 229920000615 alginic acid Polymers 0.000 title claims abstract description 56
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229940072056 alginate Drugs 0.000 title claims abstract description 39
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000003990 capacitor Substances 0.000 title claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 90
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000011148 porous material Substances 0.000 claims abstract description 21
- 238000009826 distribution Methods 0.000 claims abstract description 18
- 239000002585 base Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000003763 carbonization Methods 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 18
- 229960001126 alginic acid Drugs 0.000 claims description 17
- 239000000783 alginic acid Substances 0.000 claims description 17
- 150000004781 alginic acids Chemical class 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 11
- 150000001340 alkali metals Chemical class 0.000 claims description 11
- 239000003610 charcoal Substances 0.000 claims description 11
- 239000010453 quartz Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 6
- 241000512259 Ascophyllum nodosum Species 0.000 claims description 4
- 238000000643 oven drying Methods 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 5
- 230000004913 activation Effects 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000011800 void material Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 22
- 235000010413 sodium alginate Nutrition 0.000 description 22
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 18
- 239000011159 matrix material Substances 0.000 description 18
- 239000000661 sodium alginate Substances 0.000 description 18
- 229940005550 sodium alginate Drugs 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000001816 cooling Methods 0.000 description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
- 238000003801 milling Methods 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 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 description 5
- 239000002250 absorbent Substances 0.000 description 5
- 230000002745 absorbent Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000000737 potassium alginate Substances 0.000 description 5
- 235000010408 potassium alginate Nutrition 0.000 description 5
- MZYRDLHIWXQJCQ-YZOKENDUSA-L potassium alginate Chemical compound [K+].[K+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O MZYRDLHIWXQJCQ-YZOKENDUSA-L 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 241000894007 species Species 0.000 description 5
- 229910000765 intermetallic Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920001222 biopolymer Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000002322 conducting polymer Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241001474374 Blennius Species 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000002341 toxic gas Substances 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
- H01G11/22—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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses the soluble alginate base super capacitor active carbon material and one of a kind of adjustable aperture step charing preparation method, soluble alginate presoma is prepared from the reaction of different alkali metal ions, takes simple step charring to prepare the three-dimensional network shape porous active Carbon Materials with specific pore size distribution.By the species of metal ion and concentration that change soluble alginate, it can obtain different types of presoma, in heating carbonization process, alkali metal ion obtains abundant≤2nm micropore and 2 5nm central hole structure because of activation, duct is got through simultaneously and obtains the three-dimensional network shape carbon frame structure that internal void is interconnected, and produces very high specific capacitance.Meanwhile, such a three-dimensional porous Carbon Materials have substantial amounts of Surface oxygen-containing groups, with high fake capacitance.Therefore class activated carbon has very big bulk density, so as to obtain high volumetric capacitance, can reduce the volume of ultracapacitor device in practical application.
Description
Technical field
Charcoal is walked the present invention relates to the soluble alginate base super capacitor active carbon material and one of a kind of adjustable aperture
Change preparation method, and in particular to the preparation of soluble alginate raw material and presoma, a step condition of carbonization.
Background technology
Ultracapacitor has that charging rate is fast, power density is high, long lifespan the features such as, be to solve power used for electric vehicle
The most effective approach of power supply.The sole power power supply that it can both run as electric vehicle, can also run as electric vehicle
Auxiliary power power supply.Ultracapacitor can be additionally used in photovoltaic cell electric power storage, the stabilization of power grids, radio transmitting constant power device,
And the startup energy of tank, rocket extract；The U.S., Europe, Japan etc. also carry out the research of ultracapacitor.
The alginate that this experiment is used, wide material sources, it is easy to extract and prepare.But alginate monovalent metallic ion it
Between can neatly change the species and content of metal ion in presoma, so as to change the structure of presoma, finally obtain not
With the carbon material of pore-size distribution.Simultaneously because itself containing substantial amounts of metallic atom, therefore it need not additionally add anyization
Activating reagent is learned, has broken the yoke that conventional chemical methods activation prepares activated carbon, conventional chemical methods is overcome and prepares active raw material of wood-charcoal
The shortcoming of material.Preparation technology is easy, and corrosion will not be caused to production equipment, and last metal can be easy to reclaim, free from environmental pollution.
, can be by simply changing in presoma and resulting alginate Quito mesoporous activated carbon has controllable pore size distribution range
Metallic element species and different metal content ratio, so that it may regulate and control the aperture of the activated carbon sample of final product.Obtain
Activated carbon sample there is larger specific surface area and total hole volume, while also having the bulk density of super large, reach 0.9
cm3/g.Therefore such a absorbent charcoal material also has the volumetric capacitance of super large as the electrode material of ultracapacitor, can be significantly
Reduce the volume shared by the electrode material of ultracapacitor, with great application prospect.
Zhongrong Geng et al. (Geng Z, Wang H, Wang R, et al.Facile synthesis of
hierarchical porous carbon for supercapacitor with enhanced electrochemical
performance[J].Materials Letters,2016,182:1-5.) research is found, sodium alginate now is carried out into low temperature
Charing, the active carbon electrode material then obtained using NaOH activation methods, with high specific capacitance, can reach 451F/g, together
When with very long and stable cycle life.
Raymundo et al. (E.Leroux F,Béguin F.A High‐Performance
Carbon for Supercapacitors Obtained by Carbonization of a Seaweed Biopolymer
[J].Advanced Materials,2006,18(14):1877-1882.) by simply carrying out low temperature 600 to sodium alginate
DEG C charing, obtain three-dimensional porous carbon material.And its chemical property is analyzed, find the carbon that this presoma is prepared
Material has at a relatively high oxygen content, and on the premise of bulk density is very high, it is used as aqueous super capacitor electrode material
There is high volumetric capacitance.But researcher has only carried out weight analysis to surface nature, a kind of sodium alginate base is only prepared for
Porous carbon materials.
Ma et al. (Ma G F, Mu J J, Zhang Z G, et al.Preparation of Polypyrrole/
Sodium Alginate Nanospheres and Their Application for High-Performance
Supercapacitors[J].Acta Physico-Chimica Sinica,2013,29(11):2385-2391 (7)) prepare
Sodium alginate/Pt/Polypyrrole composite material is obtained, the specific capacity with 347F/g, and 500 cycle performances are good, but for a long time
Cyclical stability is poor, and the composite used is expensive, without actual application value.
(Ma L, Xu L M, Zhou X P, the et al.Biopolymer-assisted hydrothermal such as Ma L
synthesis of flower-like MoS2,microspheres and their supercapacitive
properties[J]. Materials Letters,2014,132:Sodium alginate 291-294.) is used as carrier, is combined
MoS2Metal sulfide is as electrode material for super capacitor, but performance is general, and using expensive metal material, does not have
The prospect of application.
In summary, although someone is carbonized using sodium alginate, activated at present, it is or multiple with conducting polymer
Close, or it is compound etc. with metallic compound, but process is complicated, with certain limitation.And activated using chemical reagent,
Corrosivity is too strong, and equipment investment is excessive, it is impossible to continuous production, and finally produces substantial amounts of toxic gas and liquid and can not return
Receive.In addition, being combined using expensive conducting polymer and metallic compound, step is more, and pollution is big, and performance one
As, cause actual application value not high.
The content of the invention
In order to which the preparation process for solving existing super capacitor active carbon production technology presence is seriously polluted, step is more, and production
Product structure is single, and capacitive property is low, the problem of cost is high, and the present invention proposes that a kind of soluble alginate base of adjustable aperture surpasses
Level electric capacity absorbent charcoal material and one step charing preparation method, preparation process cleaning, step are simple, and product structure is various adjustable
Control, capacitive property is high, and manufacturing cost is low.
The technical scheme is that：A kind of soluble alginate base super capacitor active carbon material of adjustable aperture
One step carbonizes preparation method, comprises the following steps：
The first step, the preparation of presoma：Alginic acid and alkali metal soln reaction are obtained into soluble alginate, fully washed
Wash, be placed in oven drying.
Second step, charing：Presoma is placed in quartz boat, is put into tube furnace, nitrogen is passed through, from room temperature to most
Whole carbonization temperature, held for some time；
3rd step, washing and drying：Treat that a step charring process terminates, temperature is down to room temperature, by gained soluble alginate
Quito mesoporous activated carbon carries out pickling, and washing removes alkali metal ion, and drying is fully ground, and obtains the solvable of different pore size distribution
Property alginic acid alkali super capacitor active carbon material.
The source of described alginic acid include bulk kelp, sea-tangle, green alga any one.
The mass percent concentration of alkali metal soln is 1-10%.
The flow velocity of nitrogen when being carbonized in the 3rd step：1L/min, during charing, is heated up with 10 DEG C/min heating rate.
The final carbonization temperature of charing is 700-1000 DEG C, soaking time 30-120min.
Described alkali metal soln is potassium hydroxide or sodium hydrate aqueous solution.
A kind of preparation method of the soluble alginate base super capacitor active carbon material of described adjustable aperture is obtained
Activated carbon, specific surface area 400-1400m2/ g, quality specific capacitance 100-300F/g, volumetric capacitance 100-300F/cm3, can
Presoma is prepared by adjusting raw material and alkali metal proportioning, the super capacitor activity with specific pore size distribution is obtained by charing
Charcoal.
Beneficial effect：
1. soluble alginate Quito mesoporous activated carbon material of characteristic aperture distribution, step are prepared using one-step method charing
Simply, operate it is simple, and only by changing the species and content of metal ion in presoma, it becomes possible to the work obtained by conveniently regulating and controlling
The pore size distribution range of property charcoal product, it can have high specific capacitance, good multiplying power respectively as the electrode material of ultracapacitor
Performance, excellent cycling performance etc., so as to be applied in different demands.
2. whole technique need not use the chemical reagent that pollution reaches, it is only necessary to simple step heating charing, you can
To last activated carbon sample.
3. the present invention takes simple step charring to prepare the three-dimensional network shape porous active with specific pore size distribution
Carbon Materials.By changing the species of metal ion and concentration of soluble alginate, different types of presoma is can obtain, is being risen
In warm carbonization process, alkali metal ion obtains abundant≤2nm micropore and 2-5nm central hole structure because of activation, simultaneously
Get through duct and obtain the three-dimensional network shape carbon frame structure that internal void is interconnected, and produce very high specific capacitance.Meanwhile, this
Planting three-dimensional porous Carbon Materials has substantial amounts of Surface oxygen-containing groups, with high fake capacitance.Therefore class activated carbon has very big
Bulk density, so as to obtain high volumetric capacitance, the volume of ultracapacitor device in practical application can be reduced.Prepare
Process is simple, efficient, environmental protection.The present invention prepares different pore size distribution suitable for any step charing of soluble alginate one
Super capacitor active carbon.
Brief description of the drawings
Fig. 1 is sodium alginate matrix activated carbon N prepared by embodiment2Adsorption-desorption isothermal.
Fig. 2 is sodium alginate matrix activated carbon pore size distribution range prepared by embodiment.
Fig. 3 is potassium alginate matrix activated carbon N prepared by embodiment2Adsorption-desorption isothermal.
Fig. 4 is potassium alginate matrix activated carbon pore size distribution range prepared by embodiment.
Fig. 5 sodium alginates/potassium matrix activated carbon constant current charge-discharge curve (0.5A g-1)。
Fig. 6 sodium alginates/potassium matrix activated carbon cyclic voltammetric Tequ line (5mV s-1)。
Fig. 7 sodium alginates/potassium matrix activated carbon high rate performance.
Fig. 8 sodium alginates/potassium matrix activated carbon impedance behavior.
Fig. 9 is flow sheet of the invention.
Embodiment
Test side of the present invention to institute's adjustable aperture ultracapacitor soluble alginate matrix activated carbon material property
Method is as follows：
(1) specific surface area, the measure of pore volume：Using measure of the activated carbon under the conditions of liquid nitrogen to nitrogen adsorption isotherm,
Specific surface area is calculated according to BET formula.
(2) surface topography uses the S-4800 type cold field emission electron microscope observations of FDAC (Hitachi) company.
(3) measure of specific capacitance：Determined using electrochemical workstation under constant current.
A kind of adjustable aperture ultracapacitor soluble alginate matrix activated carbon material and one step charing preparation side
Method, comprises the following steps：
The first step, raw material prepares：Marine alga is soaked, cleaned, is crushed, then through digesting separation of solid and liquid, adds sodium carbonate and water
Converted, extract alginic acid, go the removal of impurity, dried；Commercially available alginic acid can directly be used.
Second step, the preparation of presoma：Obtained alginic acid is reacted with certain density corresponding alkali metal soln
To soluble alginate.Finally obtained sample is fully washed, oven drying is placed in.Alkali metal soln be sodium hydroxide or
Potassium hydroxide.
3rd step, charing：Obtained presoma is placed in quartz boat, is put into tube furnace, nitrogen is passed through.With 10 DEG C/
Min heating rate is from room temperature to final carbonization temperature；
4th step, washing and drying：Treat that a step charring process terminates, temperature is down to room temperature, by gained soluble alginate
Quito mesoporous activated carbon carries out pickling, and repeatedly washing removes metallic compound therein, is finally placed in 110 DEG C of baking ovens and fully dries
Dry 12h, the activated carbon sample of drying is fully ground through row, is placed in dry environment, you can obtain different pore size distribution can
Solubility alga hydrochlorate base super capacitor active carbon material.
It is any number of including bulk kelp, sea-tangle, green alga using marine alga raw material in the method for the present invention.Alkali metal soln mass concentration
The mass ratio of 1-10%, alginic acid and sodium/potassium is 1:(0.1~0.5).Charing is the flow velocity under inert gas shielding：1L/
Min, charing final temperature is 700-1000 DEG C, carbonization time 30-120min, and inert atmosphere is nitrogen or argon gas.Obtained activated carbon
Sample is first by volume ratio 1：9 hydrochloric acid and the aqueous solution is washed through row, is reused deionized water and is washed 2-4 times, is finally placed in
Dry, cool down in baking oven, milling obtains ultracapacitor soluble alginate matrix activated carbon material.
A kind of described adjustable aperture ultracapacitor is obtained with the preparation method of soluble alginate matrix activated carbon material
The absorbent charcoal material arrived, it is characterised in that specific surface area 400-1400m2/ g, quality specific capacitance 100-300 F/g, volume ratio electricity
Appearance can reach 100-300F/cm3, the absorbent charcoal material that different presomas are prepared has different pore size distribution ranges, can
Obtain based on respectively micropore, based on small mesopore, and big mesopore, the absorbent charcoal material based on macropore.
Specific surface area, pore-size distribution, the pore volume of soluble alginate base super capacitor active carbon material of the present invention can
By changing the species and content of metal ion in presoma, to carry out quantitative regulation and control.The work that identical presoma is obtained simultaneously
The temperature and time that property charcoal sample structure is carbonized by a step is come through row control.The present invention has simply selected soluble alginate
Two kinds therein as an example, and such a method is used in any step charing of soluble alginate one and prepares different pore size distribution model
The porous carbon materials enclosed.Marine alga is soaked, cleaned, is crushed, separation of solid and liquid is digested, adds sodium carbonate and water is converted, extract
Alginic acid, goes the removal of impurity, dries；Obtained alginic acid is obtained into soluble alginate with the reaction of corresponding alkali：Sodium alginate,
Potassium alginate presoma.Finally obtained sample is fully washed, oven drying is placed in.Obtained presoma is placed in quartz boat
In, it is put into tube furnace, is passed through nitrogen.With 10 DEG C/min heating rate from room temperature to final carbonization temperature；Treat a step
Charring process terminates, and temperature is down to room temperature, and gained soluble alginate Quito mesoporous activated carbon is carried out into pickling, and repeatedly washing is removed
Metallic compound therein is removed, fully drying 12h is finally placed in 110 DEG C of baking ovens, the activated carbon sample of drying is abundant through row
Grinding, is placed in dry environment, you can obtain the ultracapacitor soluble alginate matrix activated carbon of different pore size distribution
Material.
Embodiment 1
(1) prepared by presoma：By kelp soaking, clean, crush, digest separation of solid and liquid, add sodium carbonate and water is turned
Change, extract alginic acid, soaked with 1%wt.NaOH solution, the means processing such as washing obtains pure drying sodium alginate forerunner
Body.
(2) carbonize：Sodium alginate is placed in quartz boat and is put into tube furnace, nitrogen is passed through with 1L/min flows, with 10 DEG C/
Min heating rate keeps 60min, is naturally cooling to room temperature from room temperature to 700 DEG C.
After the completion of the charing of (3) one steps, the activated carbon sample of cooling is used into volume ratio 1：9 water is with hydrochloric acid mixed solution through row
Washing, reuses deionized water and washs 2-4 times, be finally placed in baking oven and dry, cool down, and milling obtains ultracapacitor marine alga
Sour sodium matrix activated carbon material.Its specific surface area is 482m2/ g, total pore volume is 0.26cm3/ g, compares under 0.5A/g current density
Electric capacity 144F/g.
Embodiment 2
(1) prepared by presoma：The NaOH of alginic acid in being extracted from sea-tangle and 5%wt. is soaked, at the means such as washing
Reason, obtains pure drying sodium alginate presoma.
(2) carbonize：Sodium alginate is placed in quartz boat and is put into tube furnace, nitrogen is passed through with 1L/min flows, with 10
DEG C/min heating rate from room temperature to 800 DEG C, keep 60min, be naturally cooling to room temperature.
After the completion of the charing of (3) one steps, the activated carbon sample of cooling is used into volume ratio 1：9 water is with hydrochloric acid mixed solution through row
Washing, reuses deionized water and washs 2-4 times, be finally placed in baking oven and dry, cool down, and milling obtains ultracapacitor marine alga
Sour sodium matrix activated carbon material.Its specific surface area is 1030m2/ g, total pore volume is 0.60 cm3/ g, under 0.5A/g current density
Specific capacitance 152F/g.
Embodiment 3
(1) prepared by presoma：The NaOH of alginic acid in being extracted from marine alga and 5%wt. is soaked, at the means such as washing
Reason, obtains pure drying sodium alginate white powder.
(2) carbonize：Sodium alginate is placed in quartz boat and is put into tube furnace, nitrogen is passed through with 1L/min flows, with 10
DEG C/min heating rate from room temperature to 900 DEG C, keep 60min, be naturally cooling to room temperature.
After the completion of the charing of (3) one steps, the activated carbon sample of cooling is used into volume ratio 1：9 water is with hydrochloric acid mixed solution through row
Washing, reuses deionized water and washs 2-4 times, be finally placed in baking oven and dry, cool down, and milling obtains ultracapacitor marine alga
Sour sodium matrix activated carbon material.Its specific surface area is 1221m2/ g, total pore volume is 0.81 cm3/ g, under 0.5A/g current density
Specific capacitance 212F/g.
Embodiment 4
(1) prepared by presoma：The NaOH of alginic acid in being extracted from marine alga and 10%wt. is soaked, the means such as washing
Processing, obtains pure drying sodium alginate white powder.
(2) carbonize：Sodium alginate is placed in quartz boat and is put into tube furnace, nitrogen is passed through with 1L/min flows, with 10
DEG C/min heating rate from room temperature to 1000 DEG C, keep 60min, be naturally cooling to room temperature.
After the completion of the charing of (3) one steps, the activated carbon sample of cooling is used into volume ratio 1：9 water is with hydrochloric acid mixed solution through row
Washing, reuses deionized water and washs 2-4 times, be finally placed in baking oven and dry, cool down, and milling obtains ultracapacitor marine alga
Sour sodium matrix activated carbon material.Its specific surface area is 1424m2/ g, total pore volume is 0.89 cm3/ g, under 0.5A/g current density
Specific capacitance 190F/g.
Embodiment 5
(1) prepared by presoma：By from marine alga extract in alginic acid respectively with mass percent concentration be 1%, 2%,
5%th, 10% KOH soaks, the means processing such as washing, obtains pure drying potassium alginate presoma.
(2) carbonize：Potassium alginate is placed in quartz boat and is put into tube furnace, nitrogen is passed through with 1L/min flows, with 10
DEG C/min heating rate from room temperature to 800 DEG C, keep 60min, be naturally cooling to room temperature.
After the completion of the charing of (3) one steps, the activated carbon sample of cooling is used into volume ratio 1：9 water is with hydrochloric acid mixed solution through row
Washing, reuses deionized water and washs 2-4 times, be finally placed in baking oven and dry, cool down, and milling obtains ultracapacitor marine alga
Sour potassium matrix activated carbon material.Its specific surface area is respectively 889,1177,1445,1292 m2/ g, total pore volume is 0.30,0.49,
0.66,0.61cm3/ g, specific capacitance is respectively 323,309,263,206F/g under 0.5A/g current density.
Claims (7)
1. a kind of step charing preparation method of the soluble alginate base super capacitor active carbon material of adjustable aperture, it is special
Levy and be, comprise the following steps：
The first step, the preparation of presoma：Alginic acid and alkali metal soln reaction are obtained into soluble alginate, fully washing,
It is placed in oven drying.
Second step, charing：Presoma is placed in quartz boat, is put into tube furnace, nitrogen is passed through, from room temperature to final charcoal
Change temperature, held for some time；
3rd step, washing and drying：Treat that a step charring process terminates, temperature is down to room temperature, by gained soluble alginate Quito
Mesoporous activated carbon carries out pickling, and washing removes alkali metal ion, and drying is fully ground, and obtains the solubility sea of different pore size distribution
Alginic acid alkali super capacitor active carbon material.
2. a kind of preparation of the soluble alginate base super capacitor active carbon material of adjustable aperture as claimed in claim 1
Method, it is characterised in that the source of described alginic acid include bulk kelp, sea-tangle, green alga any one.
3. a kind of preparation of the soluble alginate base super capacitor active carbon material of adjustable aperture as claimed in claim 1
Method, it is characterised in that the mass percent concentration of alkali metal soln is 1-10%.
4. a kind of preparation of the soluble alginate base super capacitor active carbon material of adjustable aperture as claimed in claim 1
Method, it is characterised in that the flow velocity of nitrogen when being carbonized in the 3rd step：1L/min, during charing, with 10 DEG C/min heating rate liter
Temperature.
5. a kind of preparation of the soluble alginate base super capacitor active carbon material of adjustable aperture as claimed in claim 1
Method, it is characterised in that the final carbonization temperature of charing is 700-1000 DEG C, soaking time 30-120min.
6. a kind of preparation of the soluble alginate base super capacitor active carbon material of adjustable aperture as claimed in claim 1
Method, it is characterised in that described alkali metal soln is potassium hydroxide or sodium hydrate aqueous solution.
7. a kind of soluble alginate base super capacitor active carbon material of any described adjustable apertures of claim 1-6
The activated carbon that preparation method is obtained, it is characterised in that specific surface area 400-1400m2/ g, quality specific capacitance 100-300F/g, body
Product specific capacitance 100-300F/cm3, presoma can be prepared by adjusting raw material and alkali metal proportioning, obtain that there is spy by charing
The super capacitor active carbon of set aperture distribution.
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Application publication date: 20171024 |