CN108584945B - A kind of method of shallot and waste preparation porous charcoal - Google Patents
A kind of method of shallot and waste preparation porous charcoal Download PDFInfo
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- C01B32/00—Carbon; Compounds thereof
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- 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
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- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention relates to a kind of shallot and its methods of waste preparation porous charcoal, are related to the preparation technical field of porous charcoal.The described method includes: (1) is by shallot raw material stoving and crushes, it is subsequently placed in heating furnace, is passed through protective gas, heating charing；(2) after to step (1) products therefrom pickling, then it is washed till neutrality, dried；(3) step (2) products therefrom mixed with activator, impregnated, be subsequently placed in heating furnace the heat-activated under protective atmosphere；(4) to step (3) products therefrom pickling, drying to get green onion base porous charcoal.The present invention is using shallot and its waste as raw material, the porous charcoal ash content of preparation is low, wellability is good, be assembled into two electrode system double electric layers supercapacitors have high specific capacitance, small equivalent series resistance, high charge-discharge efficiencies and low time constant, especially under high magnification charge and discharge have excellent high current charge-discharge ability and energy density.
Description
Technical field
The present invention relates to the preparation technical fields of porous charcoal, and in particular to a kind of supercapacitor porous carbon electrode material and
Preparation method.
Background technique
Supercapacitor work is a kind of novel energy storage apparatus between traditional capacitor and rechargeable battery, has both high energy
Metric density high power density, has extended cycle life, the advantage that charge/discharge speed is fast, temperature window is big and high rate performance is excellent, is believing
The multiple fields such as breath technology, electric car, aerospace and science and techniques of defence have application prospect of crucial importance and wide.
Currently, electrode material for super capacitor mainly includes the following categories: transition metal oxide, conducting polymer and charcoal
Based material.In electrode material for super capacitor, earliest application, using most extensive, current industrialization technology it is most mature be each
The Carbon Materials of kind various kinds, such as active carbon, carbon nanotube, graphene, charcoal-aero gel.Commercialization supercapacitor uses at present
Electrode active material is absorbent charcoal material.Absorbent charcoal material has excellent physicochemical properties, comprising: high conductivity, height
Specific surface area, excellent chemistry and electrochemical stability, relatively low cost etc..Absorbent charcoal material can be utilized by electrolyte
Effective ratio area (electro-chemical activity surface) size be influence its chemical property key factor.Furthermore pore size,
The type in hole and the functional group of pore structure charcoal material surface or heteroatom also have a significant impact its electrochemical capacitor performance.
As long as in general, theoretically the substance containing charcoal may serve to prepare active carbon, therefore can be used for preparing activity
The raw material types very abundant of charcoal.It is several big that raw material according to source can be divided mainly into plant, mineral substance, other wastes etc.
Class.Raw material workable for plant include: timber, coconut husk, peanut shell, moso bamboo, various stalks etc., and plant raw material majority is
Agriculture and forestry organic waste material, content of ashes is low, cheap, is particularly easy to form flourishing microcellular structure, machine with higher after activation
Tool intensity and good absorption property.Plant is the preferred material for preparing active carbon at present.
Farma et al. is in " Preparation of highly porous binderless activated carbon
electrodes from fibres of oil palm empty fruit bunches for application in
Supercapacitors " in (DOI:10.1016/j.biortech.2013.01. 044) text in oil palm fruit empty fruit cluster
The self-adhesion carbon granules that fiber is processed to is presoma, obtains specific surface area 1704m using KOH activation method2·g-1Porous charcoal,
Its specific capacitance reaches 150Fg-1。
104803383 A of patent application CN discloses a kind of side that activated carbon for super capacitors is prepared using camphortree leaf
Method, it is to obtain using camphortree leaf as raw material through washing, drying, acidleach, charing, pickling, drying and processing.Active carbon ratio obtained
Surface area reaches 963.70-1424.19m2/ g, under the discharge current of 300mA/g, specific capacity reaches 95-120F/g.
102417179 A of patent application CN, which is disclosed, uses peanut shell for raw material, is activated with KOH, and gained is living
The specific surface area of property Carbon Materials reaches 1227m2/ g shows preferable stability as capacitor electrode material.
However, biomass used by the above-mentioned prior art exists as electrode material for super capacitor presoma is prepared
The specific surface area of poor using the activation effect of activator, preparation absorbent charcoal material is smaller, is difficult to hole knot to active carbon
The problems such as structure and specific surface area are adjusted, therefore, it is necessary to develop a kind of new supercapacitor porous carbon electrode material and
Preparation method.
Summary of the invention
For above-mentioned problems of the prior art, the present invention is intended to provide a kind of shallot and its waste prepare it is porous
The method of charcoal.Compared to traditional biological material, the present invention uses shallot and its waste as raw material, since shallot contains
Mineral matter element abundant while can effectively reducing the use of activator, increases the specific surface area of porous charcoal to obtain more
Big charge storage space.Porous charcoal ash content prepared by the present invention is low, and wellability is good, be assembled into two electrode system electric double layers are super
Grade capacitor specific capacitance with higher, lesser equivalent series resistance, higher efficiency for charge-discharge and low time are normal
Number, charge and discharge have excellent high current charge-discharge ability and energy density especially under high magnification.
A kind of method that an object of the present disclosure is to provide shallot and its waste preparation porous charcoal.
Second purpose of the invention is to provide the porous charcoal of a kind of shallot and its waste preparation.
Third purpose of the present invention is to provide the porous charcoal pole of a kind of shallot for supercapacitor and its waste preparation
Material.
4th purpose of the invention is to provide a kind of supercapacitor comprising porous charcoal prepared by the present invention.
5th purpose of the invention is to provide method, shallot and its waste system of even shallot and its waste preparation porous charcoal
The application of porous charcoal pole material, supercapacitor prepared by standby porous charcoal, shallot and its waste.
For achieving the above object, specifically, the invention discloses following technical proposals:
Firstly, a kind of method that the present invention provides shallot and its waste preparation porous charcoal, includes the following steps:
(1) it by shallot raw material stoving and crushes, is subsequently placed in heating furnace, be passed through protective gas, heating charing；
(2) after to step (1) products therefrom pickling, then it is washed till neutrality, dried；
(3) step (2) products therefrom mixed with activator, impregnated, is subsequently placed in heating furnace under protective atmosphere
Heat-activated；
(4) to step (3) products therefrom pickling, drying to get green onion base porous charcoal.
In the present invention, the shallot raw material includes allium and its waste, preferably shallot and its waste.
It further, further include the pretreatment to shallot raw material in step (1), specifically: after taking shallot raw material to clean,
Shallot raw material is extracted with organic solvent water-bath heating, is dried again after extraction, pulverization process.
The pretreated reason of shallot raw material is: shallot raw material (especially Bulbus Allii Fistulosi) can be extracted by pretreatment
In extract, to further increase hemicellulose and C content accounting in shallot raw material, C content, hemicellulose level accounting
It is higher, higher specific surface area more is obtained useful as the shallot raw material charcoal of preparation porous charcoal, more preferably pore structure, has
Better chemical property；Moreover, the products such as general flavone extracted from shallot principle have high medicine after pretreatment
With value, the industrial chain added value of shallot raw material can be significantly widened, realizes that high-qualityization of shallot raw material utilizes.
Preferably, in the pretreatment, the solid-liquid ratio of shallot raw material and organic solvent is 1g:8-15ml, further preferably
For 1g:10mL.
Preferably, in the pretreatment, organic solvent includes but is not limited to the one or more of of the solution such as ethyl alcohol, acetone
Combination.
Preferably, in the pretreatment, the concentration of organic solvent is 80-100% (quality).
Preferably, in the pretreatment, bath temperature is 80-100 DEG C, and the heating water bath time is 8h.
In step (1), the protective gas includes one or more of the inert gases such as nitrogen, helium, argon gas group
It closes, preferably nitrogen.
In step (1), the protective gas flow is 0.1-2L/min, preferably 1.5L/min.
In step (1), the heating rate of the heating carbonization is 5-100 DEG C/min, preferably 5 DEG C/min.
In step (1), the carbonization temperature is 400-800 DEG C, time 2h, preferably 600 DEG C.
In step (2), the acid that the pickling uses include but is not limited to one of sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid or
Several combinations, preferably hydrochloric acid.
In step (2), the concentration for the acid that the pickling uses is 0.1-6M, preferably 3M.
In step (2), the pickling and the temperature for being washed till neutrality are 80 DEG C.
In step (3), the chemical activating agent includes but is not limited to KOH, NaOH, K2CO3、H3PO4, ZnCl one kind or
It is a variety of, preferably KOH.
In step (3), the impregnating ratio (i.e. the mass ratio of product and chemical activating agent) of the product and chemical activating agent is
1:(1-5), preferably 1:4.
In step (3), the dipping temperature is 80-100 DEG C, dip time 1-4h, preferably 80 DEG C, 2h.
In step (3), the protective gas includes one or more of the inert gases such as nitrogen, helium, argon gas group
It closes, preferably nitrogen.
In step (3), the protective gas flow is 0.1-2L/min, preferably 1.5L/min.
In step (3), the activation process is divided into low-temperature activation and high-temperature activation, wherein low-temperature activation temperature is 300-
400 DEG C, time 30-50min, preferably 350 DEG C, 45min；High-temperature activation temperature is 700-900 DEG C, time 60-140min,
Preferably 800 DEG C, 120min.Low temperature pre-activate carbonization stage provides necessary K for the high-temperature activation stage2CO3And K2O is simple substance
The generation of K plays important premise effect.During high-temperature activation, on the one hand by generating K2CO3And the carbon consumed makes hole
Development；On the other hand, K simple substance is generated in the high-temperature activation stage, when temperature is more than metallic potassium boiling point (762 DEG C), potassium steam meeting
Different carbon-coatings is diffused into, new pore structure is formed, gaseous metallic potassium is walked between the synusia of crystallite, and strutting fragrant synusia makes
It is distorted or deforms, and creates new hole.
In step (4), the acid that the pickling uses include but is not limited to one of sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid or
Several combinations, preferably hydrochloric acid.
In step (4), the concentration for the acid that the pickling uses is 0.1-6M, preferably 0.1M.
In step (4), the pickling and the temperature for being washed till neutrality are 80 DEG C.
Secondly, the present invention provides the porous charcoal of a kind of shallot and its waste preparation, the porous charcoal specific surface area exists
2179m2/ g or more, Kong Rong are in 1.3cm3/ g or more, aperture is within 2.4nm.The specific surface area of superelevation can provide more work
Property site can increase substantially the energy density of supercapacitor to adsorption charge.
Again, the present invention provides the porous charcoal pole material of a kind of shallot for supercapacitor and its waste preparation,
Porous charcoal pole material is made of porous charcoal prepared by the present invention.
Thirdly, the present invention provides a kind of supercapacitor, and the charcoal pole material of the supercapacitor is prepared by the present invention
Porous charcoal be made.
Finally, the invention discloses the method for shallot and its waste preparation porous charcoal, shallot and its waste preparations
Porous charcoal, the porous charcoal pole material of shallot and its waste preparation, supercapacitor are in traffic and transport field, energy storage material
Using.
Green onion is Liliaceae allium, and perennial herb is the important seasoning food materials in China, more than China extensive kind
It plants, yield is very big, and the four seasons can harvest.Meanwhile shallot has a high medical value, the dregs of a decoction often quilt is extracted after medicinal ingredient in production
It is discarded, cause a large amount of green onion waste to be not used.The present invention passes through research discovery: green onion and allium not only have naturally
Pore structure, it is often more important that minerals rich in can effectively replace activator, play good activation, subtract
The use of few chemical activating agent；Simultaneously as undertaking absorption, assimilation, storage, ventilation, transfer function containing a large amount of in Bulbus Allii Fistulosi
Parenchymal tissue (nutritive issue), the pore structure in Bulbus Allii Fistulosi is relatively more flourishing, and extract and half fiber in parenchymal tissue
It is higher to tie up cellulose content, therefore C content is also relatively higher；For this purpose, the present invention is extracted in Bulbus Allii Fistulosi by pre-processing to green onion material
Extract, further increase hemicellulose and C content accounting in Bulbus Allii Fistulosi, and flourishing pore structure, minerals abundant are high
The C element of content accounting can make green onion have higher specific surface area as the Supercapacitor carbon of precursor preparation, more preferably hole
Gap structure, better chemical property can both obtain high-performance super capacitor with shallot and its waste preparation porous charcoal
Electrode material, but high-qualityization that waste may be implemented utilizes, and expands industrial chain added value.
Compared with prior art, the beneficial effect that the present invention obtains is:
1, the present invention has natural hole compared to traditional biological material using shallot and its waste as raw material
Structure, and mineral matter element rich in can effectively reduce the use of activator, and it is bigger to obtain to increase specific surface area
Charge storage space.
2, the present invention not only improves the percentage composition of wherein C element by the pretreatment to shallot raw material, and can be
More multi-pore structure is obtained before activation, so that the porous charcoal of later period preparation has higher specific surface area, more reasonable hole knot
Structure obtains a kind of more ideal porous carbon material for supercapacitor；Contain in the extracting solution obtained after pre-processing simultaneously
General flavone etc. has high medical value, can significantly widen the industrial chain added value of shallot raw material, realizes shallot raw material
High-qualityization utilizes.
3, the present invention carries out pickling to the product after charing, with the ash content accumulated in material after removing charing, makes activator
It is sufficiently reacted with material surface, improves the utilization efficiency of activator, reduce production cost, step is simple, it is easy to accomplish is big
Large-scale production utilizes.
4, the present invention effectively removes the impurity introduced in activation process simultaneously using reasonable purifying and heat treatment process
Content of ashes is reduced, porosity is improved, optimizes pore-creating effect, further promotes the cycle performance of active carbon.
5, of the invention preparation method is simple, at low cost, clean and environmental protection, is more easily achieved industrialization.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.
Fig. 1 is the SEM figure that sample powder is made in 1 step 1 of embodiment.
Fig. 2 is the SEM figure of porous charcoal made from embodiment 1.
Fig. 3 is the N of porous charcoal made from embodiment 12Adsorption/desorption figure.
Fig. 4 is porous charcoal mesoporous pore size distribution map made from embodiment 1.
Fig. 5 is constant current charge-discharge curve of the porous carbon electrode material made from embodiment 1 under 1A/g current density.
Fig. 6 is porous carbon electrode material made from embodiment 1 in 10mV/s, 20mV/s, 50mV/s, 100mV/s, 200mV/
Cyclic voltammetry curve under the sweep speed of s.
Specific embodiment
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 embodiment, 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 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, device, component and/or their combination.
As background technique is introduced, biomass used by the prior art is as preparing electrode material for super capacitor
Presoma, the specific surface area that there is poor, preparation the absorbent charcoal material of the activation effect using activator is smaller, is difficult to activity
The problems such as pore structure and specific surface area of charcoal are adjusted, therefore, the invention proposes a kind of shallots and its waste to prepare
The method of porous charcoal, the present invention is described further with reference to the accompanying drawings and detailed description.
It should be understood that unless otherwise specified, heretofore described unit " M " expression " mol/L ".
Embodiment 1
A kind of method of shallot and its waste preparation porous charcoal, includes the following steps:
Step 1 is placed in the ethanol solution that mass concentration is 80% after cleaning shallot chopping by solid-liquid ratio 1g:10ml,
It dries and crushes after heating water bath 8h at 80 DEG C；
Sample powder obtained by step 1 is placed in tube type resistance furnace, in nitrogen atmosphere (flow 1.5L/ by step 2
Min 600 DEG C are heated under), heating rate is 5 DEG C/min, keeps the temperature 2h, is cooled to room temperature, and green onion carbonized material is made；
Step 3, first by green onion carbonized material 3M hydrochloric acid solution pickling at 80 DEG C obtained by step 2, then with 80 DEG C of deionizations
It is washed to neutrality, is dried for standby；
Step 4 weighs step 3 products therefrom 4g, weighs KOH solid 16g according to charcoal alkali ratio 1:4 and is configured to be saturated molten
Saturation KOH solution and step 3 products therefrom are put it into air dry oven after mixing and impregnate 2h with 80 DEG C of high temperature by liquid,
Material after must impregnating.
Step 5, by material after the dipping in step 4 be put into Muffle furnace in a nitrogen atmosphere (flow 1.5L/min) into
Row activation is warming up to 350 DEG C of progress low-temperature activations from room temperature with 5 DEG C/min of heating rate, 45min is kept the temperature, then with identical
Heating rate is warming up to 800 DEG C of progress high-temperature activations, keeps the temperature 2h, is cooled to room temperature taking-up to temperature to get activated material；
Step 6 first washs the activated material in step 5 at 80 DEG C to neutrality with 0.1M hydrochloric acid solution, then with 80 DEG C
Deionized water repeated flushing is all removed to chloride ion, and products therefrom is dried to get green onion base porous charcoal.
Embodiment 2
A kind of method of shallot and its waste preparation porous charcoal, with embodiment 1, difference is: charcoal alkali ratio is 1:3.
Embodiment 3
A kind of method of shallot and its waste preparation porous charcoal, with embodiment 1, difference is: in step 1, only need by
Shallot dries and crushes after cleaning, and pre-processes without heating water bath.
Embodiment 4
A kind of method of shallot and its waste preparation porous charcoal, with embodiment 1, difference is: in step 1, raw material is adopted
With shallot waste, the waste is extracts the remaining dregs of a decoction of general flavone using Bulbus Allii Fistulosi.
Embodiment 5
A kind of method of shallot and its waste preparation porous charcoal, includes the following steps:
Step 1 is placed in the acetone soln that mass concentration is 100% after cleaning shallot chopping by solid-liquid ratio 1g:8ml,
It dries and crushes after heating water bath 8h at 100 DEG C；
Sample powder obtained by step 1 is placed in tube type resistance furnace, in argon atmosphere (flow 0.1L/ by step 2
Min 800 DEG C are heated under), heating rate is 100 DEG C/min, keeps the temperature 2h, is cooled to room temperature, and green onion carbonized material is made；
Step 3, first by green onion carbonized material 0.1M sulfuric acid solution pickling at 80 DEG C obtained by step 2, then with 80 DEG C go from
Son is washed to neutrality, is dried for standby；
Step 4 weighs step 3 products therefrom 4g, weighs K according to charcoal alkali ratio 1:52CO3Solid 20g simultaneously is configured to be saturated
Solution will be saturated K2CO3Solution and step 3 products therefrom are put it into air dry oven after mixing and are soaked with 100 DEG C of high temperature
Stain 1h, material after must impregnating.
Step 5, by material after the dipping in step 4 be put into Muffle furnace under an argon atmosphere (flow 0.1L/min) into
Row activation is warming up to 400 DEG C of progress low-temperature activations from room temperature with 5 DEG C/min of heating rate, 30min is kept the temperature, then with identical
Heating rate is warming up to 700 DEG C of progress high-temperature activations, keeps the temperature 140min, is cooled to room temperature taking-up to temperature to get activated material；
Activated material in step 5 is first washed at 80 DEG C to neutrality with 6M sulfuric acid solution, then is gone with 80 DEG C by step 6
Ionized water repeated flushing is all removed to chloride ion, and products therefrom is dried to get green onion base porous charcoal.
Embodiment 6
A kind of method of shallot and its waste preparation porous charcoal, includes the following steps:
Step 1 is placed in the ethanol solution that mass concentration is 90% after cleaning shallot chopping by solid-liquid ratio 1g:15ml,
It dries and crushes after heating water bath 8h at 90 DEG C；
Sample powder obtained by step 1 is placed in tube type resistance furnace, at nitrogen atmosphere (flow 2L/min) by step 2
Under be heated to 400 DEG C, heating rate is 10 DEG C/min, keeps the temperature 2h, is cooled to room temperature, and green onion carbonized material is made；
Step 3, first by green onion carbonized material 6M hydrofluoric acid solution pickling at 80 DEG C obtained by step 2, then with 80 DEG C go from
Son is washed to neutrality, is dried for standby；
Step 4 weighs step 3 products therefrom 4g, weighs H according to charcoal alkali ratio 1:13PO4Solid 4g simultaneously is configured to be saturated molten
Liquid will be saturated H3PO4Solution and step 3 products therefrom are put it into air dry oven after mixing and are impregnated with 90 DEG C of high temperature
4h, material after must impregnating.
Material after dipping in step 4 is put into Muffle furnace (flow 2L/min) under helium atmosphere and carried out by step 5
Activation is warming up to 300 DEG C of progress low-temperature activations from room temperature with 5 DEG C/min of heating rate, 50min is kept the temperature, then with identical liter
Warm rate is warming up to 900 DEG C of progress high-temperature activations, keeps the temperature 60min, is cooled to room temperature taking-up to temperature to get activated material；
Activated material in step 5 is first washed at 80 DEG C to neutrality with 3M nitric acid solution, then is gone with 80 DEG C by step 6
Ionized water repeated flushing is all removed to chloride ion, and products therefrom is dried to get green onion base porous charcoal.
Performance test:
Specific surface area, Kong Rong, the average pore size to the embodiment 1-4 porous charcoal prepared are calculated using BET method, as a result such as table
Shown in 1.
It is mixed with the porous charcoal and electrically conductive graphite, polytetrafluoroethylene (PTFE) of embodiment 1-4 preparation by the mass ratio of 8:1:1
Electrode for super capacitor material, constant current charge-discharge test is carried out using the KOH of 6M as electrolyte, and test current density is 1
The specific capacitance value of A/g, 10A/g, the results are shown in Table 2.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Specific surface area/m2/g | 2855 | 2776 | 2691 | 2179 |
| Kong Rong/cm3/g | 1.7 | 1.6 | 1.6 | 1.3 |
| Average pore size/nm | 2.4 | 2.2 | 2.3 | 2.1 |
Table 2
As can be seen from Table 1: prepared porous carbon material specific surface area is in 2179m in the embodiment of the present invention2/ g with
On, reach as high as 2855m2/g；Kong Rong is in 1.3cm3/ g or more；Average pore size concentrates on 2.4nm or less.Its specific surface area is far high
Porous carbon material in existing literature and patent.
From Table 2, it can be seen that porous carbon material prepared in the embodiment of the present invention is under 1A/g current density than electricity
Appearance reaches 278.10F/g or more, reaches as high as 381.51F/g, under the high current density of 10A/g, can still reach
The specific capacitance of 278.98F/g has good high rate performance.Compared to existing porous carbon electrode material, the present invention provides one
Kind chemical property is more excellent, specific capacitance and the more good porous carbon electrode material of high rate performance.
It will be seen from figure 1 that there is irregular hole and split in sample surfaces after the pre-treatment step in step 1
Seam, facilitates the diffusion and infiltration of KOH in activation process.
Figure it is seen that porous carbon surface made from embodiment 1 is carved wherein having by KOH there are a large amount of pore structure
The hole for having the elongated crack formula formed due to by high temperature action close to circular hole is lost into, also melt and penetrates through and is formed random
Hole then, hole is flourishing, well-formed.
From figure 3, it can be seen that the adsorption isothermal curve that porous charcoal is made in embodiment 1 has apparent hysteresis loop, belong to typical case
IV type thermoisopleth, show the sign that porous charcoal contains mesoporous pore structure, illustrate during preparation, in addition to micropore is raw
At mesoporous is also developed, and the appearance of mesoporous makes isothermal shape that corresponding change have occurred.And thermoisopleth is with opposite
The raising of pressure, N2 adsorbance is in the trend of increase always, when relative pressure is higher, still not up to saturation absorption, and adsorbance
Continuation slowly increases, and the phenomenon that platform does not occur, illustrates to contain a certain number of mesoporous in sample.
From fig. 4, it can be seen that pore-size distribution almost concentrates within 4nm, and high in the voids content of 2nm or so, hole
After diameter is more than 2nm, with the increase in aperture, voids content is reduced rapidly.The pore-size distribution that porous charcoal is made is relatively narrow, aperture point
Cloth is relatively uniform.
From fig. 5, it can be seen that constant current charge-discharge curve of the porous charcoal made from embodiment 1 under the current density of 1A/g
For well-symmetric isosceles triangle, illustrate that it has good electrochemical stability and invertibity.
As can be seen from Figure 6 it can be seen from the figure that under the sweep speed of 10~200mV/s, all cyclic voltammetrics are bent
Line is well-symbolized, and porous carbon material shows quasi- rectangular characteristic, occurs without redox peaks, this illustrated capacitor is almost
There is no the presence of fake capacitance, electrode reaction is mainly electric double layer charge transfer reaction, and electrode material has typical electrochemistry electricity
Container feature.With being gradually increased for sweep speed, the response current of material is gradually increased, but the shape of curve is almost kept not
Become.Even if cyclic voltammetry curve is still able to maintain good quasi- rectangular characteristic under the rate that exposes thoroughly of 200mV/s, show fabulous
Symmetry.Therefore electrode material has lesser equivalent series resistance and quick Ion response ability, illustrates the hole of material
Road structure is conducive to electrolyte ion in the quick diffusion transport of material internal, so that material be made to show higher capacitive character
Energy.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for those skilled in the art
For member, various changes and changes are possible in this application.Within the spirit and principles of this application, it is made it is any modification,
Equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (38)
1. a kind of method of shallot and its waste preparation porous charcoal, it is characterised in that:
The porous charcoal specific surface area is in 2179m2/ g or more, Kong Rong are in 1.3cm3/ g or more, aperture is within 2.4nm；
Preparation method includes the following steps:
(1) it by shallot raw material stoving and crushes, is subsequently placed in heating furnace, be passed through protective gas, heating charing；
(2) after to step (1) products therefrom pickling, then it is washed till neutrality, dried；
(3) step (2) products therefrom mixed with activator, impregnated, be subsequently placed in heating furnace and heated under protective atmosphere
Activation；
(4) to step (3) products therefrom pickling, drying to get green onion base porous charcoal；
Wherein, in step (1) further include pretreatment to shallot raw material, specifically: after taking shallot raw material to clean, use organic solvent
Heating water bath extracts shallot raw material, is dried again after extraction, pulverization process.
2. the method for shallot as described in claim 1 and its waste preparation porous charcoal, it is characterised in that: in step (1), institute
Stating protective gas includes the combination of one or more of nitrogen, helium, argon gas.
3. the method for shallot as claimed in claim 2 and its waste preparation porous charcoal, it is characterised in that: in step (1), institute
Stating protective gas is nitrogen.
4. the method for shallot as described in claim 1 and its waste preparation porous charcoal, it is characterised in that: in step (1), institute
Stating protective gas flow is 0.1-2L/min.
5. the method for shallot as claimed in claim 4 and its waste preparation porous charcoal, it is characterised in that: in step (1), institute
Stating protective gas flow is 1.5L/min.
6. the method for shallot as described in claim 1 and its waste preparation porous charcoal, it is characterised in that: in step (1), institute
The heating rate for stating heating carbonization is 5-100 DEG C/min.
7. the method for shallot as claimed in claim 6 and its waste preparation porous charcoal, it is characterised in that: in step (1), institute
The heating rate for stating heating carbonization is 5 DEG C/min.
8. the method for shallot as described in claim 1 and its waste preparation porous charcoal, it is characterised in that: in step (1), institute
Stating carbonization temperature is 400-800 DEG C, time 2h.
9. the method for shallot as claimed in claim 8 and its waste preparation porous charcoal, it is characterised in that: in step (1), institute
Stating carbonization temperature is 600 DEG C.
10. the method for shallot as described in claim 1 and its waste preparation porous charcoal, it is characterised in that: in step (2),
The acid that the pickling uses includes the combination of one or more of sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid.
11. the method for shallot as claimed in claim 10 and its waste preparation porous charcoal, it is characterised in that: in step (2),
The acid that the pickling uses is hydrochloric acid.
12. the method for shallot as described in claim 1 and its waste preparation porous charcoal, it is characterised in that: in step (2),
The concentration for the acid that the pickling uses is 0.1-6M.
13. the method for shallot as claimed in claim 12 and its waste preparation porous charcoal, it is characterised in that: in step (2),
The concentration for the acid that the pickling uses is 3M.
14. the method for shallot as described in claim 1 and its waste preparation porous charcoal, it is characterised in that: in step (2),
The pickling and the temperature for being washed till neutrality are 80 DEG C.
15. the method for shallot as described in claim 1 and its waste preparation porous charcoal, it is characterised in that: in step (3),
The activator includes KOH, NaOH, K2CO3、H3PO4、ZnCl2One of or it is a variety of.
16. the method for shallot as claimed in claim 15 and its waste preparation porous charcoal, it is characterised in that: in step (3),
Activator is KOH.
17. the method for shallot as described in claim 1 and its waste preparation porous charcoal, it is characterised in that: in step (3),
The impregnating ratio of the product and activator is 1:1-5.
18. the method for shallot as claimed in claim 17 and its waste preparation porous charcoal, it is characterised in that: in step (3),
The impregnating ratio of the product and activator is 1:4.
19. the method for shallot as described in claim 1 and its waste preparation porous charcoal, it is characterised in that: in step (3),
The dipping temperature is 80-100 DEG C, dip time 1-4h.
20. the method for shallot as claimed in claim 19 and its waste preparation porous charcoal, it is characterised in that: in step (3),
The dipping temperature is 80 DEG C, dip time 2h.
21. the method for shallot as described in claim 1 and its waste preparation porous charcoal, it is characterised in that: in step (3),
The protective gas includes the combination of one or more of nitrogen, helium, argon gas.
22. the method for shallot as claimed in claim 21 and its waste preparation porous charcoal, it is characterised in that: in step (3),
The protective gas is nitrogen.
23. the method for shallot as described in claim 1 and its waste preparation porous charcoal, it is characterised in that: in step (3),
The protective gas flow is 0.1-2L/min.
24. the method for shallot as claimed in claim 23 and its waste preparation porous charcoal, it is characterised in that: in step (3),
The protective gas flow is 1.5L/min.
25. the method for shallot as described in claim 1 and its waste preparation porous charcoal, it is characterised in that: in step (3),
The activation process is divided into low-temperature activation and high-temperature activation, wherein low-temperature activation temperature is 300-400 DEG C, time 30-50min；
High-temperature activation temperature is 700-900 DEG C, time 60-140min.
26. the method for shallot as claimed in claim 25 and its waste preparation porous charcoal, it is characterised in that: in step (3),
Low-temperature activation temperature is 350 DEG C, time 45min；High-temperature activation temperature is 800 DEG C, time 120min.
27. the method for shallot as described in claim 1 and its waste preparation porous charcoal, it is characterised in that: in step (4),
The acid that the pickling uses includes but is not limited to the combination of one or more of sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid.
28. the method for shallot as claimed in claim 27 and its waste preparation porous charcoal, it is characterised in that: in step (4),
The acid that the pickling uses is hydrochloric acid.
29. the method for shallot as described in claim 1 and its waste preparation porous charcoal, it is characterised in that: in step (4),
The concentration for the acid that the pickling uses is 0.1-6M.
30. the method for shallot as claimed in claim 29 and its waste preparation porous charcoal, it is characterised in that: in step (4),
The concentration for the acid that the pickling uses is 0.1M.
31. the method for shallot as described in claim 1 and its waste preparation porous charcoal, it is characterised in that: in step (4),
The pickling and the temperature for being washed till neutrality are 80 DEG C.
32. the method for shallot as described in claim 1 and its waste preparation porous charcoal, it is characterised in that: in pretreatment, greatly
The solid-liquid ratio of green onion raw material and organic solvent is 1g:8-15ml.
33. the method for shallot as claimed in claim 32 and its waste preparation porous charcoal, it is characterised in that: in pretreatment,
The solid-liquid ratio of shallot raw material and organic solvent is 1g:10mL.
34. the method for shallot as described in claim 1 and its waste preparation porous charcoal, it is characterised in that: in pretreatment, have
Solvent includes one of ethyl alcohol, acetone or combinations thereof；The concentration of organic solvent is mass fraction 80-100%.
35. the method for shallot as described in claim 1 and its waste preparation porous charcoal, it is characterised in that: in pretreatment, water
Bath temperature is 80-100 DEG C, and the heating water bath time is 8h.
36. a kind of porous charcoal pole material prepared for the shallot of supercapacitor and its waste, it is characterised in that: described more
Hole charcoal pole material is the porous charcoal of the described in any item method preparations of claim 1-35.
37. a kind of supercapacitor, it is characterised in that: the charcoal pole material of the supercapacitor is more described in claim 36
Hole charcoal pole material.
38. such as the porous charcoal of claim 1-35 described in any item methods preparation and/or as claimed in claim 36 porous
The application of charcoal pole material and/or supercapacitor as claimed in claim 37 in traffic and transport field, energy storage material.
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| 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 |
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