CN107039193B - A kind of garlic skin matrix activated carbon electrode material and preparation method for ultracapacitor - Google Patents
A kind of garlic skin matrix activated carbon electrode material and preparation method for ultracapacitor Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 235000004611 garlic Nutrition 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000007772 electrode material Substances 0.000 title claims abstract description 19
- 239000011159 matrix material Substances 0.000 title claims abstract description 14
- 244000245420 ail Species 0.000 title 1
- 240000002234 Allium sativum Species 0.000 claims abstract description 94
- 238000001994 activation Methods 0.000 claims abstract description 52
- 230000004913 activation Effects 0.000 claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 49
- 239000005539 carbonized material Substances 0.000 claims abstract description 27
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 19
- 238000007598 dipping method Methods 0.000 claims abstract description 17
- 238000010792 warming Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims abstract description 5
- 238000001802 infusion Methods 0.000 claims abstract description 4
- 238000004321 preservation Methods 0.000 claims abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 10
- 238000005554 pickling Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 239000012047 saturated solution Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 abstract description 16
- 230000002745 absorbent Effects 0.000 abstract description 5
- 239000002250 absorbent Substances 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 description 17
- 229910052783 alkali metal Inorganic materials 0.000 description 12
- 150000001340 alkali metals Chemical class 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000012190 activator Substances 0.000 description 7
- 239000003990 capacitor Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 239000002956 ash Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000010431 corundum Substances 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000010903 husk Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- 235000017060 Arachis glabrata Nutrition 0.000 description 2
- 244000105624 Arachis hypogaea Species 0.000 description 2
- 235000010777 Arachis hypogaea Nutrition 0.000 description 2
- 235000018262 Arachis monticola Nutrition 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002154 agricultural waste Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 235000020232 peanut Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- 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 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012611 container material Substances 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
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- -1 timber Substances 0.000 description 1
- 235000020234 walnut Nutrition 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
- H01G11/30—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
- H01G11/84—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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
- C01P2006/14—Pore volume
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of garlic skin matrix activated carbon electrode materials and preparation method for ultracapacitor.Garlic skin is heated to 550~700 DEG C under an inert atmosphere, heat preservation a period of time carries out charing and obtains garlic skin carbonized material, garlic skin carbonized material is added to alkali hydroxide soln high temperature time of infusion again and obtains dipping material, then dipping material is warming up to 400~450 DEG C of progress low-temperature activations, low-temperature activation continues to be heated to 700~850 DEG C of progress high-temperature activations for a period of time afterwards, high-temperature activation obtains activated material afterwards for a period of time, finally by activated material post-process up to activated carbon.Activated carbon can be made to activate completely, increase the specific surface area of absorbent charcoal material, improve the energy density of ultracapacitor.
Description
Technical field
The present invention relates to super active carbon material technical fields, and in particular to a kind of garlic skin base for ultracapacitor is lived
Property carbon electrode material and preparation method.
Background technology
Ultracapacitor (also referred to as electrochemical capacitor, double layer capacitor) is one kind between traditional capacitor and battery
Between new type of energy storage device, it has high-energy density, and high power density has extended cycle life, and fast charging and discharging is economic and environment-friendly
The advantages that.There is of crucial importance and wide answer in multiple fields such as information technology, electric vehicle, aerospace and science and techniques of defence
Use foreground.Wherein, electrode material is the critical material for determining performance of the supercapacitor index.
Activated carbon, as a kind of porous carbon material, because of its large specific surface area, pore structure is abundant, stable chemical performance, easily anti-
It is multiple use, the advantages that preparation process flow is easy, cheap, environmental protection, science and techniques of defence, chemical industry, food processing,
There is important application in the fields such as medical and health.China natural resources are abundant, are production and the big export country of activated carbon.With the fast of production
Speed development, the application of activated carbon itself and the various composite materials based on activated carbon will be further expanded, activity
The dosage of charcoal also will constantly increase.Especially capacitance is huge with the super-activated carbon market demand, but domestic production amount very little, exhausted big portion
Divide and relies on import.
Biomass is that a kind of important activated carbon prepares raw material, commonly mainly traditional agriculture and forestry biomass, packet
Include various crop stalks, timber, shell, fruit stone, rice husk etc..Such biological material is mostly agriculture and forestry product waste, cost
Cheap and content of ashes is low, and internal there are many holes again, are easy that activator is made to enter, reactivity worth is good, is conducive to hole knot
The formation of structure, high mechanical strength are the excellent materials for preparing activated carbon, have a vast market foreground.
At present in the various electrode materials of ultracapacitor, prepared by chemical activation method as raw material using biomass
Carbon material has higher specific surface area, is a kind of ideal electrode material for super capacitor.Chi-Chang Hu et al.
Its specific surface area is improved by chemical activation as raw material using Fructus Pistaciae Verae shell, but the specific capacitance in the case where the height of 300mv/s sweeps speed
Although only 47F/g (Electrhimica Acta52 (2007) 2498-2505), activated carbon prepared by this kind of method have higher
Specific surface area, but its specific capacitance value decays relatively serious at higher current densities, is not suitable for the operating condition under high current
Lower use.
Chinese patent (publication number CN102417179A), which discloses, uses peanut shell for raw material, and activation process is carried out with KOH,
The specific surface area of gained absorbent charcoal material reaches 1227m2/ g shows preferable stability as capacitor electrode material.
However above-mentioned be used as in the prior art using biomass such as straw, timber, shell, fruit stone, rice husks prepares capacitor
The raw material of electrode activity charcoal, the specific surface area that there is the absorbent charcoal material that the activation effect using activator is poor, prepares is smaller,
The problems such as being difficult to be adjusted the pore structure and specific surface area of activated carbon.
Invention content
In order to overcome the deficiencies of existing technologies, there is provided garlic skins in the work for preparing ultracapacitor for one of mesh of the invention
Application in property carbon electrode material.
China is agricultural production big country in the world, generates a large amount of agricultural wastes every year.It is very big in these wastes
A part is simply discarded, and is affected the beauty of environment, is possibly even caused the pollution of environment, while being also the very big wave of resource
Take.Source area of the China as garlic, with a long history to the plantation of garlic, cultivated area is big.However, due to traditional habit,
The edible only selection garlic meats most in the process of garlic are used, and Cortex Bulbus Allii is often abandoned as processing byproduct.Cause resource wave
Take.The present inventor has found that garlic skin has natural pore structure by research, while containing abundant mineral in garlic skin
Matter, these minerals can play certain activation instead of activator, so that activated carbon activates completely.Garlic skin prepares super
Grade activated carbon, agricultural wastes high-qualityization can be utilized, not only expanded industrial chain added value, but also can obtain a kind of super capacitor
Use high performance electrode material.
In order to realize application of the garlic skin in the active carbon electrode material for preparing ultracapacitor, increase absorbent charcoal material
The purpose of specific surface area, the second object of the present invention is to provide a kind of garlic skin matrix activated carbon electrode material for ultracapacitor
Preparation method, activated carbon can be made to activate completely, increase the specific surface area of absorbent charcoal material, improve the energy of ultracapacitor
Density.
To achieve the goals above, the technical solution of preparation method of the invention is：
A kind of preparation method of garlic skin matrix activated carbon electrode material for ultracapacitor, under an inert atmosphere by garlic skin
550~700 DEG C are heated to, heat preservation a period of time carries out charing and obtains garlic skin carbonized material, then garlic skin carbonized material is added to alkali gold
Belong to hydroxide solution high temperature time of infusion obtain dipping material, then will dipping material be warming up to 400~450 DEG C into
Row low-temperature activation, low-temperature activation continue to be heated to for a period of time 700~850 DEG C of progress high-temperature activations afterwards, when one section of high-temperature activation
Between after obtain activated material, finally activated material post-process up to activated carbon.
The present invention prepares activated carbon using garlic skin first, by being heated to 550~700 DEG C of charings to organic in garlic skin
Object is pyrolyzed, and is changed the structure feature and garlic skin pore character of organic matter, is obtained having certain hole and the garlic of mechanical strength
Skin carbonized material is as intermediate material.Secondly, garlic skin carbonized material is etched using alkali metal hydroxide as activator, on the one hand,
Low-temperature activation is carried out at 400~450 DEG C, generating the carbonate of alkali metal makes Pore development, on the other hand, 700~850 DEG C of progress
High-temperature activation, this temperature are higher than the boiling point of alkali metal, and alkali metal is made to form vapour of an alkali metal, and vapour of an alkali metal can diffuse into difference
Carbon-coating, form new pore structure；Gaseous alkali metal is walked between the synusia of crystallite, struts its change that is distorted such as direction synusia
Shape develops new micropore.Third decomposes in alkali metal hydroxide activation process and generates CO2Equal gases, these gases can rise
To the further progress for promoting activation, the specific surface area of activated carbon is greatly increased, the quality and adsorptivity of activated carbon are improved
Energy.
The third object of the present invention is to provide a kind of activated carbon prepared by above-mentioned preparation method.
Activated carbon activation produced by the present invention is complete, and specific surface area is up to 2818.22m2/ g can provide the suction of more multipotency
The active site of attached charge is conducive to the energy density for improving ultracapacitor；Its hole, which holds, is up to 1.32cm3/ g, pore-size distribution
It concentrates within 4nm, it is adjustable in pore-size distribution and porosity a certain range.
The fourth object of the present invention is to provide a kind of garlic skin matrix activated carbon electrode material for ultracapacitor, in use
Activated carbon is stated to be prepared.
The fifth object of the present invention is to provide a kind of application of above-mentioned activated carbon in ultracapacitor.
First, the activated carbon that prepared by the present invention is applicable to various electrolyte systems, and is provided for the ion in electrolyte
Quick channel makes it have more excellent high current charge-discharge ability and its energy density.Secondly, activity prepared by the present invention
Charcoal ash content is low, and wellability is good, be assembled into two electrode system double electric layers supercapacitors have higher specific capacitance, smaller etc.
Series resistance, higher efficiency for charge-discharge and low time constant are imitated, charge and discharge are with higher especially under high magnification
Energy density etc..
Beneficial effects of the present invention are：
1. garlic skin material itself has abundant fiber conduit, with other biological materials such as coconut husk, peanut shell, walnut shell phase
Than being more advantageous to obtain larger specific surface area to provide the storage space of charge, garlic skin matrix activated carbon specific surface area is up to
2800m2/g；Similarly serving to favor rational hole and pore-size distribution, (garlic skin base is lived to balance the requirement between specific capacitance and high rate performance
Property charcoal aperture integrated distribution in 0.6~1nm, what is played a major role to capacitance is the enterable micropore of ion, aperture is 0.5~
2nm)；
2. the present invention provides a kind of ultracapacitor garlic skin matrix activated carbon materials and preparation method thereof, using orthogonal reality
The method of testing has studied carbonization temperature, carbonization time, alkali carbon ratio, activation temperature, soak time to activated carbon specific surface area and aperture
It influences, the purpose is to which the most probable pore size (0.5~2nm of aperture) of most suitable electron channel can be reached by aperture control, carries
High electrochemical performance；
3. electrode material ash content provided by the invention is low, series resistance is small, and conductivity height ensures high rate charge-discharge
It can (such as Fig. 6) and high power density (power density is 3307.64W/kg when energy density is 8.79Wh/kg)；Good infiltration
Property to promote ion to spread, increase ion accessible surface product；
4. activated carbon using the present invention can prepare the ultracapacitor under high current use condition, in water system
Under electrolyte conditions, the specific capacitance under current density 0.5A/g, 1.0A/g, 2.0A/g, 3.0A/g, 5.0A/g respectively reaches
318.67F/g, 284.53F/g, 269.33F/g, 262.51F/g, 253.01F/g.
5. professional application of the present invention is strong, and design technology process is simple, and cost is relatively low, clean environment firendly, is easy to industry
Change and realizes.
Description of the drawings
The accompanying drawings which form a part of this application are used for providing further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation do not constitute the improper restriction to the application for explaining the application.
Fig. 1 is the stereoscan photograph of activated carbon made from embodiment 1；
Fig. 2 is the N of activated carbon made from embodiment 12Adsorption/desorption figure；
Fig. 3 is activated carbon pore size distribution map made from embodiment 1；
Fig. 4 is activated carbon capillary graph of pore diameter distribution made from embodiment 1；
Fig. 5 is the constant current charge-discharge curve under 0.5A/g electric currents of activated carbon electrodes prepared by embodiment 1；
Fig. 6 be embodiment 1 prepare activated carbon electrodes in 5mV/s, 10mV/s, 20mV/s, 50mV/s's, 100mV/s sweeps
Retouch the cyclic voltammetry curve under rate；
Fig. 7 is 5000 cycle performances of activated carbon electrodes prepared by embodiment 1 (assay method is constant current charge-discharge).
Specific implementation mode
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific implementation mode, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also 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, device, component and/or combination thereof.
Heretofore described low-temperature activation refers to and high-temperature activation the step of being activated for 400~450 DEG C
It refer to 700~850 DEG C of the step of being activated.
Unit " M " expression " mol/L " in the present invention.
The step of heretofore described high temperature dipping refers to the dipping that temperature is 80~100 DEG C.
As background technology is introduced, exist in the prior art that the activation effect using activator is poor, activated carbon is lived
Change incomplete defect, in order to solve technical problem as above, present applicant proposes garlic skins in the activity for preparing ultracapacitor
Application in carbon electrode material.
The present inventor has found that garlic skin has natural pore structure by research, while containing abundant in garlic skin
Minerals, these minerals can play certain activation instead of activator, so that activated carbon activates completely.Utilize garlic
The raw material that skin is prepared as activated carbon had not only solved the utilization of waste high-qualityization, but also solved that prepare a kind of absorption property excellent
Environmental protection, energy and material.
In a kind of typical embodiment of the present invention, a kind of garlic skin matrix activated carbon electricity for ultracapacitor is provided
Garlic skin is heated to 550~700 DEG C by the preparation method of pole material under an inert atmosphere, and heat preservation a period of time carries out charing acquisition
Garlic skin carbonized material, then time of infusion is impregnated after garlic skin carbonized material is added to alkali hydroxide soln high temperature
Material, is then warming up to 400~450 DEG C of progress low-temperature activations by dipping material, and low-temperature activation continues to be heated to for a period of time afterwards
700~850 DEG C of progress high-temperature activations, high-temperature activation obtain activated material, are finally post-processed activated material i.e. afterwards for a period of time
Obtain activated carbon.
First, activated carbon is prepared using garlic skin, the organic matter in garlic skin is carried out by being heated to 550~700 DEG C of charings
Pyrolysis, changes the structure feature and garlic skin pore character of organic matter, obtains having certain hole and the charing of the garlic skin of mechanical strength
Material is used as intermediate material.Secondly, the etching garlic skin carbonized material using alkali metal hydroxide as activator, on the one hand, 400~
450 DEG C of progress low-temperature activations, generating the carbonate of alkali metal makes Pore development, on the other hand, 700~850 DEG C of progress high temperature work
Change, this temperature is higher than the boiling point of alkali metal, and alkali metal is made to form vapour of an alkali metal, and vapour of an alkali metal can diffuse into different carbon
Layer, forms new pore structure；Gaseous alkali metal is walked between the synusia of crystallite, struts its deformation that is distorted such as direction synusia,
Develop new micropore.Third decomposes in alkali metal hydroxide activation process and generates CO2Equal gases, these gases can play
The progress for further promoting activation, greatly increases the specific surface area of activated carbon, improves the quality and absorption property of activated carbon.
Efficiency is carbonized in order to which garlic skin will be improved, it is preferred that charing process is carried out after being pre-processed garlic skin.
It is further preferred that the pretreated step is to dry or dry for the first time after taking garlic skin to clean, crush, mistake
80 mesh sieve.Garlic skin charing efficiency can be further increased.
Still more preferably, the temperature dried is 20~30 DEG C, and the temperature of the drying is 100~110 DEG C.
Preferably, the heating rate for being heated to 550~700 DEG C is 5 DEG C/min, and soaking time is 2~5h.It can ensure garlic
Organic matter in skin is pyrolyzed completely.
Above-mentioned inert atmosphere refers to one or more of nitrogen, argon gas, helium.
Preferably, the alkali hydroxide soln is the saturated solution of alkali metal hydroxide.It can make garlic skin charcoal
Material can impregnate more alkali metal hydroxides.
Preferably, alkali metal hydroxide is one or both of potassium hydroxide, sodium hydroxide.Potassium hydroxide, hydrogen-oxygen
That changes sodium compares otheralkali metal hydroxide, and abundance, cost is relatively low.
Preferably, the mass ratio of alkali metal hydroxide and garlic skin carbonized material is 3.0~4.5:1.
Preferably, the temperature of the dipping is 80 DEG C, and the time of the dipping is 2h.Alkali metal hydroxide at this temperature
Molecular motion performance it is higher, alkali metal hydroxide can be made to rapidly enter in garlic skin carbonized material.2h can ensure enough
Alkali metal hydroxide enters in garlic skin carbonized material.
Preferably, it is 5 DEG C/min to be warming up to 400~450 DEG C and be warming up to 700~850 DEG C of heating rate.
Preferably, the time of the low-temperature activation is 45min.
Preferably, the time of the high-temperature activation is 1~2.5h.
Preferably, the post-processing includes first wash, pickling, second wash, second of drying, grinding successively.
First wash described in present embodiment, second wash be in order to indicate water-washing steps different twice, and
Be not configured to limit the precedence of water-washing step.
Drying for the first time described in present embodiment, second drying be in order to indicate baking steps different twice, and
Be not configured to limit the precedence of baking step.
It is further preferred that the temperature of the first wash and second wash is 80 DEG C.
Into preferred once, the pickling the specific steps are be washed till pH 6~7 using acid solution at 80 DEG C.
It is further preferred that a concentration of 0.1M for the acid solution that the pickling uses.It prevents acid solutions excessively high, destroys
The hole of activated carbon, to reduce the specific surface area of activated carbon.
It is further preferred that the acid solution is one or more of hydrochloric acid, sulfuric acid, nitric acid.
Present embodiment additionally provides a kind of activated carbon prepared by above-mentioned preparation method.
Activated carbon activation obtained is complete, and specific surface area is up to 2818.22m2The super-activated carbon of/g can provide more
The active sites of energy adsorption charge are conducive to the energy density for improving ultracapacitor；Hole, which holds, is up to 1.32cm3/ g, pore-size distribution
It concentrates within 4nm, it is adjustable in pore-size distribution and porosity a certain range.
Present embodiment additionally provides a kind of garlic skin matrix activated carbon electrode material for ultracapacitor, using above-mentioned work
Property charcoal is prepared.
Present embodiment additionally provides a kind of application of above-mentioned activated carbon in ultracapacitor.
First, the activated carbon that prepared by the present invention is applicable to various electrolyte systems, and is provided for the ion in electrolyte
Quick channel makes it have more excellent high current charge-discharge ability and its energy density.Secondly, activity prepared by the present invention
Charcoal ash content is low, and wellability is good, be assembled into two electrode system double electric layers supercapacitors have higher specific capacitance, smaller etc.
Series resistance, higher efficiency for charge-discharge and low time constant are imitated, charge and discharge are with higher especially under high magnification
Energy density etc..
In order to enable those skilled in the art can clearly understand the technical solution of the application, below with reference to tool
The technical solution of the application is described in detail with comparative example for the embodiment of body.
Raw material explanation：The raw material garlic skin used in following embodiment, is derived from Shandong Jinxiang, wherein moisture account for 3.2~
3.6wt%, 4.5~4.9wt% of ash content, 91.5~92.3wt% of organic matter, organic matter are mainly cellulose and lignin.
Embodiment 1
It dries or dries after taking garlic skin to clean, crush, cross 80 mesh sieve, garlic skin powder is made；Garlic skin powder is positioned over tubular type
In resistance furnace, 600 DEG C are heated under inert atmosphere (flow 2L/min), heating rate is 5 DEG C/min, keeps the temperature 2h, cooling
To room temperature, garlic skin carbonized material is made；At room temperature, it is 4 according to the mass ratio of KOH solids and garlic skin carbonized material:1, take garlic skin to carbonize
Expect 6g, corresponding KOH solids be 24g, will saturation KOH solution be thoroughly mixed with garlic skin carbonized material, after put it into air blast
Drying box impregnates 2h, material after must impregnating with 80 DEG C of high temperature；Material after dipping is put into Muffle furnace to activate, from room temperature to rise
5 DEG C/min of warm rate is warming up to 400 DEG C of progress low-temperature activations, keeps the temperature 45min, after with identical heating rate be warming up to 800 DEG C
High-temperature activation is carried out, 2.5h is kept the temperature, takes out corundum crucible after activation, cooled to room temperature is to get activated material；It takes out
Activated material is washed with 80 DEG C of distilled water, the rear HCl solution with 0.1M under 80 DEG C of high temperature pickling to neutral pH 6~7, then according to
It is so washed with 80 DEG C of distilled water, is dried under the conditions of last 105 DEG C, ground, activated carbon 3.03g is made.To the activated carbon of preparation into
Row structural characterization, structural characterization result as shown in figures 1-4, can show that prepared activated carbon activation is complete from Fig. 1~4,
Micropore is flourishing, specific surface area 2818.22m2/ g, Kong Rongwei 1.32cm3/ g, average pore size 2.62nm.By above-mentioned garlic skin matrix activated carbon
By activating substance：Conductive agent：Binder=80：10：10 ratio is mixed, and electrode slice is made.It is adopted in 6M KOH solutions
The test of specific capacitance is carried out under different scanning rates with cyclic voltammetry.Its test result is as shown in Fig. 5~7, for example, in 6M
Current density is 0.5A/g, 1.0A/g, 2.0A/g in KOH electrolyte, and the specific capacitance under 3.0A/g, 5.0A/g respectively reaches
318.67F/g, 284.53F/g, 269.33F/g, 262.51F/g, 253.01F/g, 5000 times under the current density of 3.0A/g
Constant current charge-discharge capacitance conservation rate reaches 94%, is the ideal hyper electricity of a kind of high power of practicability, high-energy density
Container material.
Embodiment 2
It dries or dries after taking garlic skin to clean, crush, cross 80 mesh sieve, garlic skin powder is made；Garlic skin powder is positioned over tubular type
In resistance furnace, 600 DEG C are heated under inert atmosphere (flow 2L/min), heating rate is 5 DEG C/min, keeps the temperature 2h, cooling
To room temperature, garlic skin carbonized material is made；At room temperature, it is 3.5 according to the mass ratio of KOH solids and garlic skin carbonized material:1, take garlic skin charcoal
Material 6g, corresponding KOH solids be 24g, will saturation KOH solution be thoroughly mixed with garlic skin carbonized material, after put it into drum
Wind drying box impregnates 2h, material after must impregnating with 80 DEG C of high temperature；Material after dipping is put into Muffle furnace to activate, from room temperature with
5 DEG C/min of heating rate is warming up to 400 DEG C of progress low-temperature activations, keeps the temperature 45min, after with identical heating rate be warming up to 850
DEG C carry out high-temperature activation, keep the temperature 2h, corundum crucible is taken out after activation, cooled to room temperature is to get activated material；It takes out
Activated material is washed with 80 DEG C of distilled water, the rear HCl solution with 0.1M under 80 DEG C of high temperature pickling to neutral pH 6~7, then according to
It is so washed with 80 DEG C of distilled water, is dried under the conditions of last 105 DEG C, ground, activated carbon 3.91g is made.To the activated carbon of preparation into
Row structural characterization, specific surface area 2542.77m2/ g, Kong Rongwei 0.93cm3/ g, average pore size 2.17nm.By above-mentioned garlic skin base activity
Charcoal presses activating substance：Conductive agent：Binder=80：10：10 ratio is mixed, and electrode slice is made.In 6M KOH solutions
Constant current charge-discharge is used to measure under the current density of 0.5A/g capacitance as 253.70F/g.And the methylene of activated carbon
Blue adsorptive value is 39mL/0.1g.
Embodiment 3
It dries or dries after taking garlic skin to clean, crush, cross 80 mesh sieve, garlic skin powder is made；Garlic skin powder is positioned over tubular type
In resistance furnace, 600 DEG C are heated under inert atmosphere (flow 2L/min), heating rate is 5 DEG C/min, keeps the temperature 5h, cooling
To room temperature, garlic skin carbonized material is made；At room temperature, it is 4 according to the mass ratio of KOH solids and garlic skin carbonized material:1, take garlic skin to carbonize
Expect 6g, corresponding KOH solids be 24g, will saturation KOH solution be thoroughly mixed with garlic skin carbonized material, after put it into air blast
Drying box impregnates 2h, material after must impregnating with 80 DEG C of high temperature；Material after dipping is put into Muffle furnace to activate, from room temperature to rise
5 DEG C/min of warm rate is warming up to 400 DEG C of progress low-temperature activations, keeps the temperature 45min, after with identical heating rate be warming up to 800 DEG C
High-temperature activation is carried out, 1h is kept the temperature, takes out corundum crucible after activation, cooled to room temperature is to get activated material；It takes out and lives
Material is washed with 80 DEG C of distilled water, and rear with the HCl solution of 0.1M, pickling is to neutral pH 6~7 under 80 DEG C of high temperature, then still
It is washed with 80 DEG C of distilled water, is dried under the conditions of last 105 DEG C, ground, activated carbon 3.72g is made.Prepared activated carbon activation
Completely, micropore is flourishing.Specific surface area is 2077.21m2/ g, Kong Rongwei 0.89cm3/ g, average pore size 2.24nm.By above-mentioned garlic
Scytoblastema activated carbon presses activating substance：Conductive agent：Binder=80：10：10 ratio is mixed, and electrode slice is made.In 6M
Constant current charge-discharge is used to measure under the current density of 0.5A/g capacitance as 191.06F/g in KOH solution.And activity
The methylene blue adsorption value of charcoal is 35mL/0.1g.
Embodiment 4
It dries or dries after taking garlic skin to clean, crush, cross 80 mesh sieve, garlic skin powder is made；Garlic skin powder is positioned over tubular type
In resistance furnace, 550 DEG C are heated under inert atmosphere (flow 2L/min), heating rate is 5 DEG C/min, keeps the temperature 5h, cooling
To room temperature, garlic skin carbonized material is made；At room temperature, it is 4.5 according to the mass ratio of KOH solids and garlic skin carbonized material:1, take garlic skin charcoal
Material 6g, corresponding KOH solids be 24g, will saturation KOH solution be thoroughly mixed with garlic skin carbonized material, after put it into drum
Wind drying box impregnates 2h, material after must impregnating with 80 DEG C of high temperature；Material after dipping is put into Muffle furnace to activate, from room temperature with
5 DEG C/min of heating rate is warming up to 400 DEG C of progress low-temperature activations, keeps the temperature 45min, after with identical heating rate be warming up to 750
DEG C carry out high-temperature activation, keep the temperature 2h, corundum crucible is taken out after activation, cooled to room temperature is to get activated material；It takes out
Activated material is washed with 80 DEG C of distilled water, the rear HCl solution with 0.1M under 80 DEG C of high temperature pickling to neutral pH 6~7, then according to
It is so washed with 80 DEG C of distilled water, is dried under the conditions of last 105 DEG C, ground, activated carbon 4.96g is made.Prepared activated carbon is lived
Change complete, micropore prosperity, specific surface area 1507.59m2/ g, aperture 0.66cm3/ g, average pore size 2.30nm.By above-mentioned garlic skin
Matrix activated carbon presses activating substance：Conductive agent：Binder=80：10：10 ratio is mixed, and electrode slice is made.In 6M KOH
Constant current charge-discharge is used to measure under the current density of 0.5A/g capacitance as 159.30F/g in solution.And activated carbon
Methylene blue adsorption value be 22mL/0.1g.
Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not to invention protection domain
Limitation, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art are not required to
It is still within the scope of the present invention to make the creative labor the various modifications or changes that can be made.
Claims (20)
1. a kind of preparation method of garlic skin matrix activated carbon electrode material for ultracapacitor, characterized in that by garlic skin lazy
Property atmosphere under be heated to 550~700 DEG C, heat preservation a period of time carries out charing and obtains garlic skin carbonized material, then garlic skin carbonized material is added
Enter to alkali hydroxide soln high temperature time of infusion and obtain dipping material, dipping material is then warming up to 400
~450 DEG C of progress low-temperature activations, low-temperature activation continue to be heated to 700~850 DEG C of progress high-temperature activations for a period of time afterwards, and high temperature is lived
Activated material is obtained after changing a period of time, finally by activated material post-process up to activated carbon.
2. preparation method as described in claim 1, characterized in that carry out charing process after being pre-processed garlic skin.
3. preparation method as claimed in claim 2, characterized in that the pretreated step is to be dried after taking garlic skin to clean
Or dry for the first time, it crushes, crosses 80 mesh sieve.
4. preparation method as claimed in claim 3, characterized in that the temperature dried is 20~30 DEG C, the drying
Temperature is 100~110 DEG C.
5. preparation method as described in claim 1, characterized in that the heating rate for being heated to 550~700 DEG C is 5 DEG C/min,
Soaking time is 2~5h.
6. preparation method as described in claim 1, characterized in that the alkali hydroxide soln is alkali metal hydroxide
The saturated solution of object.
7. preparation method as described in claim 1, characterized in that alkali metal hydroxide is in potassium hydroxide, sodium hydroxide
One or two.
8. preparation method as described in claim 1, characterized in that the mass ratio of alkali metal hydroxide and garlic skin carbonized material is
3.0~4.5：1.
9. preparation method as described in claim 1, characterized in that the temperature of the dipping is 80 DEG C, the time of the dipping
For 2h.
10. preparation method as described in claim 1, characterized in that be warming up to 400~450 DEG C and be warming up to 700~850 DEG C
Heating rate be 5 DEG C/min.
11. preparation method as described in claim 1, characterized in that the time of the low-temperature activation is 45min.
12. preparation method as described in claim 1, characterized in that the time of the high-temperature activation is 1~2.5h.
13. preparation method as described in claim 1, characterized in that it is described post-processing successively include first wash, pickling,
Second wash, second of drying, grinding.
14. preparation method as claimed in claim 13, characterized in that the temperature of the first wash and second wash is equal
It is 80 DEG C.
15. preparation method as claimed in claim 13, characterized in that the pickling the specific steps are existed using acid solution
PH 6~7 is washed till at 80 DEG C.
16. preparation method as claimed in claim 13, characterized in that a concentration of 0.1M for the acid solution that the pickling uses.
17. the preparation method as described in claim 15 or 16, characterized in that the acid solution is in hydrochloric acid, sulfuric acid, nitric acid
It is one or more of.
18. activated carbon prepared by a kind of any preparation method of claim 1~17.
19. a kind of garlic skin matrix activated carbon electrode material for ultracapacitor, characterized in that using described in claim 18
Activated carbon is prepared.
20. a kind of application of the activated carbon described in claim 18 in ultracapacitor.
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| CN108365184A (en) * | 2018-01-02 | 2018-08-03 | 江苏大学 | A kind of lithium ion battery porous SiOC negative materials of rich carbon and preparation method thereof |
| CN108516548A (en) * | 2018-03-06 | 2018-09-11 | 合肥工业大学 | A kind of preparation method of high mesoporous rate activated carbon and its activated carbon of acquisition |
| CN108493007A (en) * | 2018-03-13 | 2018-09-04 | 河南工程学院 | The preparation method of electrode slice with high electrochemical performance |
| CN108557819B (en) * | 2018-05-30 | 2020-05-15 | 山东大学 | Method for preparing porous carbon material from garlic-based waste and application |
| CN110734061B (en) * | 2018-07-19 | 2021-12-31 | 深圳市环球绿地新材料有限公司 | Super-capacity carbon, preparation method and application thereof |
| CN110697709B (en) * | 2019-11-13 | 2021-08-06 | 山东大学 | Porous carbon prepared from biomass unburned carbon and application of porous carbon in super capacitor |
| CN110817867A (en) * | 2019-12-12 | 2020-02-21 | 山东大学 | Preparation method and application of garlic skin based super activated carbon |
| CN111268677A (en) * | 2020-01-20 | 2020-06-12 | 辽宁大学 | Preparation method and application of novel lithium ion battery negative electrode material carbonized grape seed |
| CN111634908B (en) * | 2020-04-22 | 2022-03-01 | 山东大学 | Method for preparing porous carbon by nitrogen and oxygen co-doping porous carbon and L-lysine and application |
| CN111573671B (en) * | 2020-05-08 | 2022-09-02 | 福建农林大学 | Method for preparing supercapacitor electrode material by using perilla-based activated carbon and application of supercapacitor electrode material |
| CN113830766B (en) * | 2021-08-20 | 2023-05-02 | 华中农业大学 | Preparation method of porous activated biochar through fermentation, activation and oxidation |
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