CN108439402B - A kind of supercapacitor ginger stalk matrix activated carbon and preparation method thereof - Google Patents
A kind of supercapacitor ginger stalk matrix activated carbon and preparation method thereof Download PDFInfo
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- 241000234314 Zingiber Species 0.000 title claims abstract description 93
- 235000006886 Zingiber officinale Nutrition 0.000 title claims abstract description 93
- 235000008397 ginger Nutrition 0.000 title claims abstract description 93
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000011159 matrix material Substances 0.000 title abstract description 8
- 239000003610 charcoal Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000005554 pickling Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 230000018044 dehydration Effects 0.000 claims abstract description 4
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 31
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- 239000007772 electrode material Substances 0.000 claims description 19
- 230000004913 activation Effects 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 5
- 238000010828 elution Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 239000010902 straw Substances 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 20
- 239000002585 base Substances 0.000 abstract description 18
- 239000002250 absorbent Substances 0.000 abstract description 10
- 230000002745 absorbent Effects 0.000 abstract description 10
- 238000012545 processing Methods 0.000 abstract description 5
- 238000003306 harvesting Methods 0.000 abstract description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 abstract 1
- 238000001994 activation Methods 0.000 description 24
- 239000003990 capacitor Substances 0.000 description 14
- 229910052796 boron Inorganic materials 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 239000002956 ash Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 244000000231 Sesamum indicum Species 0.000 description 1
- 235000003434 Sesamum indicum Nutrition 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000015505 Sorghum bicolor subsp. bicolor Nutrition 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000010907 stover Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
-
- 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
-
- 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
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Environmental & Geological Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a kind of supercapacitor ginger stalk matrix activated carbons and preparation method thereof, and the ginger stalk after choosing harvest carries out dehydration and drying processing;Ginger stalk after drying is crushed to powder with pulverizer, is placed in drier stand-by;Smashed ginger straw powder is carbonized under inert gas atmosphere;To the end of charring process, gained carbide is subjected to pickling, impurity and ash content therein is removed, then impregnates gained carbide with alkali metal hydroxide, be subsequently placed under inert gas atmosphere and activated;After technique to be activated, resulting ginger straw base porous activated carbon is washed, therein organic and inorganic impurity and drying is removed, supercapacitor ginger straw base absorbent charcoal material can be obtained.Preparation process cleaning of the present invention, product structure multiplicity is controllable, and capacitive property high rate capability is excellent, and with the increase of quality electric current, specific capacitance numerical reduction is slow.
Description
Technical field
The invention belongs to absorbent charcoal material and carbonization-activation preparation process fields, specifically design a kind of forthright with excellent times
The super-activated carbon ginger straw base absorbent charcoal material and its carbonization-activation preparation method and application of energy.
Background technique
Supercapacitor is also known as large value capacitor, electrochemical capacitor or double layer capacitor, is one kind between battery
Have both the new type of energy storage device of the two feature between common power.With ultra-high capacity amount, high-specific-power, charging rate it is fast,
Long service life, cryogenic property are superior, leakage current is minimum, standing time is long, use temperature range is wide, non-maintaining, safety collar
The features such as guarantor.It is applied to electronics industry, electric car and hybrid vehicle, solar energy and wind-power electricity generation, military neck at present more
Domain and industrial circle etc..The U.S., Europe, Japan etc. are also in the research for carrying out supercapacitor.
Electrode material is the core component of supercapacitor, plays key effect to the performance of supercapacitor, therefore
It is content most crucial in supercapacitor research that researching and developing, which has the electrode material of excellent electrochemical performance,.Electrode material mainly has
3 major class of porous carbon material, metal oxide and conducting polymer, wherein porous carbon material is due to its good stable charge/discharge
Extensive concern and currently the only industrialized electrode material by academia and industry.It can be used as super capacitor
The porous charcoal of device electrode material mainly active charcoal, charcoal-aero gel, carbon nanotube etc., wherein active carbon is because having specific surface area
Greatly, pore structure is abundant, chemical stability height, good conductivity, easy Reusability, cheap and preparation process are simply etc. excellent
Point is always the preferred material for preparing electrode of super capacitor.
At present in the various electrode materials of supercapacitor, prepared as raw material by chemical activation method using biomass
Carbon material specific surface area with higher is a kind of ideal electrode material for super capacitor.Biomass is a kind of important
Active carbon prepare raw material, commonly mainly traditional agriculture and forestry biomass, including various agricultural crop straws, timber, fruit
Shell, fruit stone, rice husk etc..
Li Xueliang et al. discloses a kind of method with stalk production organic system activated carbon for super capacitors material, wherein
Stalk include rape stalk, wheat stalk, cotton stalk, rice straw, corn stover, broomcorn straw, sesame stalk, bamboo shoots
Clothing, although having biggish specific capacitance value by organic system activated carbon for super capacitors prepared by the above stalk, it is than electricity
Capacitance decays relatively seriously at higher current densities, is not suitable for using under operating condition under larger current.
Therefore, it is necessary to develop the biomass super-activated carbon of the novel supercapacitor of one kind and its preparation side at present
Method, with solve existing product structure is single, capacitive property is low, it is at high cost and with quality electric current increase specific capacitance decaying it is larger
The problem of.
Summary of the invention
For the above prior art, present invention aim to address existing product structure is single, capacitive property is low, at high cost
And decay larger problem as quality electric current increases specific capacitance, therefore, the present invention proposes a kind of with excellent high rate performance
Supercapacitor ginger straw base absorbent charcoal material and its carbonization-activation preparation method, preparation process cleaning, step is simple, product
Various structures are controllable, and capacitive property high rate capability is excellent, and manufacturing cost is low.It is specific:
An object of the present invention is to provide a kind of application of ginger stalk in the electrode material of preparation supercapacitor.
The second object of the present invention is to provide a kind of preparation method of ginger stalk super active carbon.
The third object of the present invention is to provide a kind of ginger stalk super active carbon.
The fourth object of the present invention is to provide a kind of application of ginger stalk super active carbon in supercapacitor.
The fifth object of the present invention is to provide a kind of electrode material for supercapacitor.
To achieve the above object, the present invention specifically uses following technical scheme:
In the first aspect of the invention, a kind of ginger stalk answering in the electrode material of preparation supercapacitor is provided
With.
In the second aspect of the invention, a kind of preparation method of ginger stalk super active carbon is provided, this method includes
Following steps:
(1) raw material preparation: choosing ginger stalk, dry after cleaning removal impurity dehydration;
(2) preparation of presoma: the ginger stalk after drying is crushed to powdered;
(3) it carbonizes: powdered ginger stalk is carbonized under inert gas atmosphere;
(4) pickling: the carbide that charing is obtained carries out pickling;
(5) it activates: the carbide after pickling being impregnated in potassium hydroxide solution, is activated after dipping;
(6) it washs drying: the product after activation being subjected to washing and is dried to obtain ginger stalk super active carbon.
In the third aspect of the invention, a kind of ginger straw base super-active being prepared using the above method is provided
Charcoal.
In the fourth aspect of the invention, a kind of above-mentioned ginger stalk super active carbon answering in supercapacitor is provided
With.
In a fifth aspect of the invention, a kind of electrode material for supercapacitor is provided, which is to adopt
It is prepared with above-mentioned ginger stalk super active carbon.
Compared with prior art, technical solution of the present invention has the advantages that
(1) corresponding ginger straw base porous active Carbon Materials being prepared using potassium hydroxide carbonization-activation method, operation is simple, and
Only by changing the temperature of charing, the pore-size distribution of the time of charing and charcoal alkali than resulting activated carbon sample can be regulated and controled
Its electrode material as supercapacitor of range can be respectively provided with excellent high rate performance, and increase when ratio in quality electric current
The attenuation of capacitor is relatively lower, has potential using value.
(2) rich in potassium and compared to the relatively more boron elements of other biological matter, potassium in the ginger stalk selected by the present invention
Play the role of in activation process promote reaming activation, and boron element prepare benefit played in active carbon process be can
With allow activated carbon surface wetability to be improved between electrolyte and sector electrode impedance reduce, can produce Faraday pseudo-capacitance to
The specific capacitance of active carbon is effectively improved, and silicon content is low in ginger stalk, the salt content insoluble in hydrochloric acid is lower, is easier to
Pickling.Provide a kind of higher value application method for effectively solving ginger place of production ginger stalk.
(3) technique, which can be prepared efficiently, collects the chemicals such as terpene, phenol, acid, aldehyde in ginger stalk pyrolytic process, recycles ginger straw
The fertilizer elements such as potassium, boron in stalk.
Detailed description of the invention
The Figure of description for constituting a part of the invention is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.
Fig. 1 is ginger stalk matrix activated carbon (800 DEG C) N prepared by example 12Adsorption-desorption isothermal.
Fig. 2 is ginger stalk matrix activated carbon (800 DEG C) pore size distribution range figure prepared by example 1.
Fig. 3 is ginger stalk matrix activated carbon (800 DEG C) constant current charge-discharge curve prepared by example 1.
Fig. 4 is ginger stalk matrix activated carbon (800 DEG C) Cyclic voltamogram curve prepared by example 1.
Fig. 5 is ginger stalk matrix activated carbon (800 DEG C) high rate performance prepared by example 1.
Specific embodiment
It is noted that described further below be all exemplary, it is intended to provide further instruction to the present invention.Unless another
It indicates, all technical and scientific terms used herein has usual with general technical staff of the technical field of the invention
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to exemplary embodiments of the present invention.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation and/or their combination.
As background technique is introduced, deposited in the prior art as the activated carbon from activated sludge of electrode material for super capacitor
In certain deficiency, in order to solve technical problem as above, the invention proposes a kind of ginger stalks in preparation supercapacitor
Application in electrode material.
In the present invention, ginger stalk has very high Determination of Potassium, is 70~80 (w/w) % in content of ashes,
Low-down silicon content is less than or equal to 2.5 (w/w) % in content of ashes, and different compared to other stalks certain
Boron content, in content of ashes be 5~10 (w/w) %.
It is verified by research of the invention, rich in potassium and compared to the relatively more boron members of other biological matter in ginger stalk
Element, potassium play the role of in activation process promote reaming activation, and boron element prepare it is good played in active carbon process
Place is that the impedance that activated carbon surface wetability can be allowed to be improved between electrolyte and sector electrode reduces, and can produce the counterfeit electricity of faraday
Hold the specific capacitance for effectively improving active carbon, and silicon content is low in ginger stalk, the salt content insoluble in hydrochloric acid is more
It is low, it is easier to pickling.In addition, the present invention chooses electrode material of the ginger stalk as supercapacitor, solves ginger place of production ginger stalk
Difficult multicontaminated problem.
In the preferred embodiment of the present invention, the ginger stalk comes from Shandong Province of China, the new fresh ginger stalk of green in
Harvest season before the Frost's Descent obtains.The ash element of ginger stalk is as shown in table 1.
The ash element content analysis (mass percent %) of 1 ginger stalk of table
In a typical embodiment of the invention, a kind of preparation method of ginger stalk super active carbon is provided, it should
Method the following steps are included:
(1) raw material preparation: choosing ginger stalk, dry after cleaning removal impurity dehydration;
(2) preparation of presoma: the ginger stalk after drying is crushed to powdered;
(3) it carbonizes: powdered ginger stalk is carbonized under inert gas atmosphere;
(4) pickling: the carbide that charing is obtained carries out pickling;
(5) it activates: the carbide after pickling being impregnated in potassium hydroxide solution, is activated after dipping;
(6) it washs drying: the product after activation being subjected to washing and is dried to obtain ginger stalk super active carbon.
In the preferred embodiment of the present invention, in step (1), using press dewatering.
In the preferred embodiment of the present invention, in step (2), crushing mesh number is 60-300 mesh.
Carbonization process influences the formation and development of carbonated material pore structure, to ensure that carbonated material has more gap
Structure, suitable pore-size distribution and specific surface area, the present invention have carried out screening and optimizing to carbonization condition, in currently preferred reality
It applies in mode, in step (3), charing is under nitrogen or argon atmosphere, and charing final temperature is 600-700 DEG C, carbonization time 30-
120min, heating rate are 3-10 DEG C/min.
In the preferred embodiment of the present invention, in step (4), pickling is molten with the hydrochloric acid of 0.1mol/L~6mol/L
Liquid, and a large amount of impurity and ash content therein have been washed away after pickling.
Different activation methods and activation condition can significantly affect active carbon specific surface area and pore structure, for difference
Activated carbon raw material select suitable activation method and activation condition is the key that prepare active carbon.For higher ratio is prepared
The active carbon that surface area and hole appearance etc. are had excellent performance, the present invention has carried out screening and optimizing to activation condition, currently preferred
In embodiment, in step (5), be added potassium hydroxide according to charcoal alkali ratio 1:1.5~1:3, water be completely dissolved according to aqueous slkali and
It is sufficiently impregnated carbide to take the circumstances into consideration to be added, stir the mixture for sticky shape, in 85 DEG C of at a temperature of dipping 2h~6h, and first
For pre-activate to 300-350 DEG C, the pre-activate time is 30-60min, and then activating final temperature is 600-800 DEG C, activation time 90-
240min.Through a large amount of experimental analysis and verifying, 85 DEG C of potassium hydroxide dipping of the invention and low-temperature activation (300-350
DEG C) processing, the carbonate for generating alkali metal keeps hole more flourishing, to prepare the better electrode of super capacitor material of capacitive property
Material provides may.
Charcoal alkali ratio refers to the quality of carbonized product (i.e. charcoal) and the mass ratio of alkali KOH be added in the present invention.
In the preferred embodiment of the present invention, in step (6), using the salt acid elution of 3~6mol/L, reuse from
Sub- water washing is to neutrality.
The equal recoverable of all salinities, such as sylvite in the cleaning solution that the present invention generates during the preparation process.
The ginger stalk that the present invention uses is from a wealth of sources as raw material, cheap, is easy to collect.Ginger stalk itself has
Relatively special eucaryotic cell structure, and have special metallic element and content of heteroatoms.After carbonization-activation of the present invention, it can obtain
To the porous active Carbon Materials with three-dimensional network shape microstructure.This preparation method will be in its biomass by the pickling of hydrochloric acid
Some extra ash contents are taken away, and generate potassium atom in activation process as activator by potassium hydroxide and disappear with carbon-coating
Solution acts on and produces a large amount of micropore and central hole structure.Since ginger stalk itself has relatively high boron content, so that
The ginger straw base porous active carbon surface finally obtained has a large amount of content of heteroatoms (N, P, O, B), can increase such material
Surface wettability, while improving its chemical property.Such absorbent charcoal material raw materials are by this discarded money of ginger stalk
Source is used, and environmental protection is renewable, and such absorbent charcoal material as electrode material for super capacitor with excellent forthright again
Can, and with the increase of quality electric current, the decaying of specific capacitance is slow, can solve commercialization activated carbon for super capacitors material at present
The defect of material has extraordinary application prospect.
In another exemplary embodiment of the invention, the ginger straw base super-active that is prepared using the above method
Charcoal.
In the preferred embodiment of the present invention, the ginger stalk super active carbon is what three-dimensional network shape communicated with one another
Pore structure, specific surface area are 2000~3000 ㎡/g, and quality specific capacitance is 150~380F/g, and with the increase of quality electric current,
Slowly, the specific capacitance attenuation when specific capacitance in 50A/g compares 0.5A/g is lower than 10% for specific capacitance decaying.
The supercapacitor of the present invention specific surface area of ginger stalk super active carbon, pore-size distribution, pore volume can pass through
The temperature and time and impregnating ratio of table charcoal activation are regulated and controled.
In another exemplary embodiment of the invention, the ginger stalk super active carbon is provided in super capacitor
Application in device.
In another exemplary embodiment of the invention, a kind of electrode material for supercapacitor, the electricity are provided
Pole material is prepared using the ginger stalk super active carbon.
To a kind of supercapacitor with excellent high rate performance ginger straw base absorbent charcoal material in the embodiment of the present invention
The test method of performance is as follows:
(1) measurement of specific surface area, pore volume: the measurement using active carbon under the conditions of liquid nitrogen to nitrogen adsorption isotherm,
Specific surface area is calculated according to BET formula.
(2) it the measurement of specific capacitance: is measured under constant current using electrochemical workstation.
In order to enable those skilled in the art can clearly understand technical solution of the present invention, below with reference to tool
The embodiment of the body technical solution that the present invention will be described in detail.
Embodiment 1
A kind of preparation method of the ginger straw base absorbent charcoal material of the supercapacitor with excellent high rate performance, including with
Lower step:
(1) precursor preparation: select ginger stalk as raw material.The new fresh ginger stalk of green is chosen, is cleaned and is cleaned with pure water
It after matter, is placed in squeezer and carries out squeezing processing and slag-liquid separation, it is small that residue is then placed in baking oven at 105 DEG C dry 15
When.Obtained clean ginger stalk pulverizer is crushed into the powder for 200 mesh, is placed in drier stand-by.
(2) it carbonizes: obtained ginger stalk powder being placed in ceramic crucible, nitrogen atmosphere stove is put into, in a nitrogen atmosphere,
With the heating rate of 5 DEG C/min from room temperature to 600 DEG C of final carbonization temperature, and keep 120min.
(3) pickling: obtained carbide is carried out room temperature pickling 3 times with the hydrochloric acid of 6mol/L, is then filtered, obtains
Filter residue.
(4) it activates: obtained acid-leached product being placed in nickel crucible and is impregnated at 85 DEG C with the potassium hydroxide of charcoal alkali ratio 1:3
2h is subsequently placed in nitrogen atmosphere stove, in a nitrogen atmosphere, is first warming up to 350 DEG C of progress pre-activate with 5 DEG C/min, is kept
Then 30min is warming up to 800 DEG C of final activation temperature again with 5 DEG C/min, keep 120min.
(5) washing and drying: after to be activated, temperature is down to room temperature, and gained ginger straw base porous activated carbon is first used salt
Acid elution, is then washed to neutrality with deionized water again, is finally placed in 105 DEG C of baking ovens and sufficiently dries 12h, is placed in dry environment
In.Obtained its specific surface area of ginger straw base super active carbon material is 2600 ㎡/g, total pore volume 1.591cm3/ g, N2Absorption-
Desorption isotherm as shown in Figure 1, pore size distribution range as shown in Fig. 2, the performance test results as seen in figures 3-5, in the electricity of 1A/g
Specific capacitance 225A/g under current density, and with the increase of quality electric current, specific capacitance decaying is slow, the specific capacitance phase in 50A/g
Specific capacitance attenuation when than 0.5A/g is 8.6%.
Embodiment 2
A kind of preparation method of the ginger straw base absorbent charcoal material of the supercapacitor with excellent high rate performance, including with
Lower step:
(1) precursor preparation: select ginger stalk as raw material.The new fresh ginger stalk of green is chosen, is cleaned and is cleaned with pure water
It after matter, is placed in squeezer and carries out squeezing processing and slag-liquid separation, it is small that residue is then placed in baking oven at 105 DEG C dry 15
When.Obtained clean ginger stalk pulverizer is crushed into the powder for 120 mesh, is placed in drier stand-by.
(2) it carbonizes: obtained ginger stalk powder being placed in ceramic crucible, nitrogen atmosphere stove is put into, in a nitrogen atmosphere,
With the heating rate of 10 DEG C/min from room temperature to 700 DEG C of final carbonization temperature, and keep 120min.
(3) pickling: obtained carbide is carried out room temperature pickling 3 times with the hydrochloric acid of 3mol/L, is then filtered, obtains
Filter residue.
(4) it activates: obtained acid-leached product being placed in nickel crucible and is soaked at 85 DEG C with the potassium hydroxide of charcoal alkali ratio 1:1.5
Stain 3h, is subsequently placed in nitrogen atmosphere stove, in a nitrogen atmosphere, is first warming up to 350 DEG C of progress pre-activate with 10 DEG C/min, keeps
Then 30min is warming up to 600 DEG C of final activation temperature again with 5 DEG C/min, keep 120min.
(5) washing and drying: after to be activated, temperature is down to room temperature, and gained ginger straw base porous activated carbon is first used salt
Acid elution, is then washed to neutrality with deionized water again, is finally placed in 105 DEG C of baking ovens and sufficiently dries 12h, is placed in dry environment
In.Obtained its specific surface area of ginger straw base super active carbon material is 2213 ㎡/g, total pore volume 1.435cm3/ g, in 1A/g
Current density under specific capacitance 207F/g and with the increase of quality electric current, specific capacitance decaying slowly, the specific capacitance in 50A/g
Specific capacitance attenuation when compared to 0.5A/g is 9.2%%
Embodiment 3
A kind of preparation method of the ginger straw base absorbent charcoal material of the supercapacitor with excellent high rate performance, including with
Lower step:
(1) precursor preparation: select ginger stalk as raw material.The new fresh ginger stalk of green is chosen, is cleaned and is cleaned with pure water
It after matter, is placed in squeezer and carries out squeezing processing and slag-liquid separation, it is small that residue is then placed in baking oven at 105 DEG C dry 15
When.Obtained clean ginger stalk pulverizer is crushed into the powder for 80 mesh, is placed in drier stand-by.
(2) it carbonizes: obtained ginger stalk powder being placed in ceramic crucible, nitrogen atmosphere stove is put into, in a nitrogen atmosphere,
With the heating rate of 10 DEG C/min from room temperature to 450 DEG C of final carbonization temperature, and keep 120min.
(3) pickling: obtained carbide is carried out room temperature pickling 3 times with the hydrochloric acid of 3mol/L, is then filtered, obtains
Filter residue.
(4) it activates: obtained acid-leached product being placed in nickel crucible and is impregnated at 85 DEG C with the potassium hydroxide of charcoal alkali ratio 1:2
1h is subsequently placed in nitrogen atmosphere stove, in a nitrogen atmosphere, is first warming up to 350 DEG C of progress pre-activate with 3 DEG C/min, is kept
Then 30min is warming up to 700 DEG C of final activation temperature again with 5 DEG C/min, keep 120min.
(5) washing and drying: after to be activated, temperature is down to room temperature, and gained ginger straw base porous activated carbon is first used salt
Acid elution, is then washed to neutrality with deionized water again, is finally placed in 105 DEG C of baking ovens and sufficiently dries 12h, is placed in dry environment
In.Obtained its specific surface area of ginger straw base super active carbon material is 2126 ㎡/g, total pore volume 1.514cm3/ g, in 1A/g
Current density under specific capacitance 196F/g and with the increase of quality electric current, specific capacitance decaying slowly, the specific capacitance in 50A/g
Specific capacitance attenuation when compared to 0.5A/g is 9.1%
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (7)
1. a kind of preparation method of ginger stalk super active carbon, characterized in that method includes the following steps:
(1) raw material preparation: choosing ginger stalk, dry after cleaning removal impurity dehydration;
(2) preparation of presoma: the ginger stalk after drying is crushed to powdered;
(3) it carbonizes: powdered ginger stalk is carbonized under inert gas atmosphere;
(4) pickling: the carbide that charing is obtained carries out pickling;
(5) it activates: the carbide after pickling being impregnated in potassium hydroxide solution, is activated after dipping;
(6) it washs drying: the product after activation being subjected to washing and is dried to obtain ginger stalk super active carbon;
Wherein, in step (3), charing is under nitrogen or argon atmosphere, and charing final temperature is 600-700 DEG C, carbonization time 30-
120min, heating rate are 3-10 DEG C/min;
In step (4), pickling is the hydrochloric acid solution of 0.1mol/L~6mol/L;
In step (5), with the potassium hydroxide of charcoal alkali ratio 1:1.5~1:3,85 DEG C at a temperature of impregnate 2h~6h, and first pre- work
Change to 300-350 DEG C, the pre-activate time is 30-60min, and then activating final temperature is 600-800 DEG C, activation time 90-
240min。
2. preparation method as described in claim 1, it is characterized in that: in step (1), using press dewatering;In step (2), powder
Broken mesh number is 60-300 mesh.
3. preparation method as described in claim 1, it is characterized in that:
In step (6), using the salt acid elution of 3~6mol/L, reuses deionized water and wash to neutrality.
4. the ginger stalk super active carbon being prepared using method of any of claims 1-3.
5. ginger stalk super active carbon as claimed in claim 4, it is characterized in that: the ginger stalk super active carbon is three
The network-like pore structure to communicate with one another is tieed up, specific surface area is 2000~3000m2/ g, quality specific capacitance are 150~380F/g, and
With the increase of quality electric current, slowly, the specific capacitance in 50A/g compares specific capacitance attenuation when 0.5A/g for specific capacitance decaying
Lower than 10%.
6. application of the ginger stalk super active carbon described in claim 4 or 5 in supercapacitor.
7. a kind of electrode material for supercapacitor, it is characterized in that: the electrode material is using described in claim 4 or 5
Ginger stalk super active carbon be prepared.
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