CN106744950B - Pine nut based active carbon and its preparation method and application - Google Patents
Pine nut based active carbon and its preparation method and application Download PDFInfo
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Abstract
The present invention provides pine nut based active carbons and its preparation method and application, belong to the technical field of electrode material.Pine nut based active carbon of the present invention be using pine nut shell as raw material, it is hot cracked to obtain made of carbonized material post activation, the activation be will potassium hydroxide and carbonized material mix after deionized water is added, then successively impregnated, filtered, being dried and high temperature under be activated.Method: one, crushing pine nut shell, and dry to constant weight, thermal cracking is taken out after cooling, obtains carbonized material；Two, the carbonized material that step 1 obtains is cleaned, drying to constant weight, sieving, then the carbonized material after potassium hydroxide and sieving is mixed, deionized water is added, impregnates, filtering, drying to constant weight, it places into crucible to be built in Muffle furnace, activates, be cooled to room temperature under high temperature, washing is to neutrality, and drying to constant weight.The present invention is used as electrode material.
Description
Technical field
The invention belongs to the technical fields of electrode material；More particularly to pine nut based active carbon and preparation method thereof and answer
With.
Background technique
Based on the supercapacitor of Cathode/Solution Interface electrochemical process energy storage, there is power density height, cycle life
The characteristics such as long, energy instantaneous large-current fast charging and discharging, pollution-free, it has also become one of the hot spot of mechanism of new electrochemical power sources research.As
The core of supercapacitor, for porous capacitor Carbon Materials due to large specific surface area, specific capacitance is high, has extended cycle life, is widely used in
The electrode material of business supercapacitor.The porous capacitor Carbon Materials developed include active carbon, carbon nanotubes, carbon aerogels,
Vitrescence charcoal, Nanoporous glassy carbon etc. are activated, wherein lower-cost activated carbon application is the most extensive.Comprehensively consider energy environment and
Cost problem, using the biomass such as tea seed episperm, peanut shell, tobacco rod, the leaf of spinach prepare porous capacitor Carbon Materials cause it is more and more
Concern.
Currently, the research for preparing active carbon using pine nut shell as raw material is less, to the Electrochemical Properties of obtained active carbon
Even more it is rarely reported.Pine nut shell structure is fine and close, hard, it is not easy to obtain active carbon with high specific surface area.
Summary of the invention
It is an object of the present invention to provide pine nut based active carbons and its preparation method and application.The present invention is original with pine nut shell
Expect, being activated after thermal cracking with lye (such as KOH) and active carbon being made, the hole of product is flourishing, with high-specific surface area, shows
Preferable capacitance characteristic and cyclical stability can be used as electrode material and have good development prospect.
Pine nut based active carbon is using pine nut shell as raw material in the present invention, and the hot cracked carbonized material post activation that obtains is made
, the activation is deionized water to be added after mixing potassium hydroxide and carbonized material, then successively impregnated, filtered, dried
Be activated under high temperature；Specific preparation method is realized by following step:
Step 1: pine nut shell is crushed, dry to constant weight, thermal cracking is taken out after cooling, obtains carbonized material；
Step 2: the carbonized material that step 1 obtains is cleaned, drying to constant weight, sieving, then by potassium hydroxide and sieving
Carbonized material mixing afterwards, is added deionized water, impregnates, and filtering, drying to constant weight, places into crucible and is built in Muffle furnace, high
The lower activation of temperature, is cooled to room temperature, washing to neutrality, and drying to constant weight to get pine nut based active carbon is arrived.
The present invention is adjusted using dipping, filtering, the dry separate operations being re-activated convenient for the control of activation process；Filtering,
Carrying out high-temperature activation after drying again reduces corrosivity to equipment；Filtrate can reuse by collection, and it is dirty to reduce environment
Dye, it is more environmentally friendly.
Thermal cracking is handled using continuous biomass pyrolysis device in step 1, wherein and thermal cracking temperature is 400~600 DEG C,
The revolving speed of pressure feeding spiral is 10~20r/min, and the heat scission reaction time is 15~30min.
The sieve of 4~6 mesh (i.e. 3.35-4.75mm) is crossed in step 2.
Potassium hydroxide is pressed in step 2 and carbonized material mass ratio is (1~5): charcoal of 1 proportion by potassium hydroxide and after being sieved
Material mixing.
Impregnated at room temperature in step 2 for 24 hours, the pyrolytic carbon itself that the quick continuous pyrolysis process of the present invention obtains have with
Pore structure based on middle macropore, dipping is so that activator KOH has time enough to enter the hole filled inside pyrolytic carbon
In structure, the tar and part volatile matter organic matter etc. in dissolution pyrolysis carbon surface and internal blocking duct get through original duct simultaneously
Preliminary pore-creating keeps subsequent activation process more abundant.
Activation temperature is 500~900 DEG C in step 2, and activation time is 30~90min,
Above-mentioned pine nut based active carbon is used as electrode material.
The method of the present invention prepares carbonized material with continuous biomass pyrolysis device, can be realized long range high-temperature biomass company
Continuous charing, carbonization time is short, most short to economize on resources for 15min to reduce energy consumption, and reduces CO2 emission.
The carbonized material after potassium hydroxide and sieving is mixed using the present invention, deionized water is added, impregnates, filters, drying
It is re-activated to constant weight, reduces the corrosivity to equipment；Lye is reusable by collecting, and reduces pollution；Separate operations, just
In the control adjustment to process.
The obtained active carbon of the method for the present invention has high specific surface area yield with higher simultaneously.It is 4 in alkali charcoal ratio,
Activation temperature is 900 DEG C, and activation time is that acquisition active carbon (K-AC) specific surface area is 1470.89m under 60min activation condition2/
G, yield 26.8%, mesoporous 31.56%.
The active carbon hole of the method for the present invention preparation is flourishing, and aperture multiplicity, arrangement is random, generates a large amount of micropore or divides
Cloth is in activated carbon surface, or is nested in mesoporous and macropore, forms the hierarchical pore structure for having both macropore, mesoporous and micropore.
The active carbon excellent electrochemical performance of the method for the present invention preparation, under the current density of 1A/g, specific capacitance reaches
232.1F/g；It is recycled 1000 times under the high current density of 2A/g, capacity retention has preferable capacitance characteristic up to 94% or more
And cyclical stability.
Pine nut shell has feasibility and good hair in electrode material through KOH activation method preparation activated carbon application in the present invention
Exhibition prospect.
Detailed description of the invention
Fig. 1 is the SEM figure of the carbonized material prepared under 300 DEG C of thermal cracking temperatures；
Fig. 2 is the SEM figure of the carbonized material prepared under 400 DEG C of thermal cracking temperatures；
Fig. 3 is the SEM figure of the carbonized material prepared under 500 DEG C of thermal cracking temperatures；
Fig. 4 is the SEM figure of the carbonized material prepared under 600 DEG C of thermal cracking temperatures；
Fig. 5 is the SEM figure of the carbonized material prepared under 700 DEG C of thermal cracking temperatures；
Fig. 6 is the SEM figure of PNSC；
Fig. 7 is the SEM figure of K-AC；
Fig. 8 is influence of the alkali carbon ratio to active carbon yield and specific surface area；
Fig. 9 is influence of the activation time to active carbon yield and specific surface area；
Figure 10 is influence of the activation temperature to active carbon yield and specific surface area；
The XRD diagram of Figure 11 PNSC and K-AC；
The FT-IR of Figure 12 PNSC and K-AC scheme；
Figure 13 is PNSC and K-AC (a) N2Adsorption and desorption isotherms；
Figure 14 is BJH method mesoporous pore size distribution map；
Figure 15 is HK method micropore size distribution map；
Figure 16 be sweep speed be 10mV/s when, the cyclic voltammetry curve of PNSC and K-AC electrode；
Figure 17 is constant current charge-discharge curve of the PNSC and K-AC electrode under 1A/g current density；
Figure 18 is the AC impedance figure of PNSC and K-AC electrode (insertion figure is high frequency region enlarged drawing)；
Figure 19 is PNSC and K-AC electrode under 2A/g current density, the relationship of capacity retention and recurring number；
Figure 20 is the apparatus structure schematic diagram that the preparation of specific embodiment one uses；1 in Figure 20 --- driving motor,
2 --- connecting shaft, 3 --- feed box, 4 --- pressure feeding spiral, 5 --- reaction tube, 6 --- resistance furnace, 7 --- gas outlet,
8 --- temperature sensor, 9 --- controller, 10 --- carbon case.
Specific embodiment
Specific embodiment 1: the preparation method of pine nut based active carbon is realized by following step in present embodiment
:
Step 1: the sub- shell of Korean pine is crushed, dries under the conditions of 75 DEG C to constant weight, be placed in continuous biomass pyrolysis device
In, thermal cracking 15min under the conditions of temperature is 500 DEG C, the revolving speed of pressure feeding spiral is 15r/min takes out after cooling, obtains charcoal
Material；
Step 2: step 1 carbonized material is cleaned with distilled water, drying to constant weight under the conditions of 105 DEG C, crosses the sieve of 8mm,
Then it is that the carbonized material that 4:1 is matched by potassium hydroxide and after being sieved mixes by potassium hydroxide and carbonized material mass ratio, 100ml is added
Deionized water impregnates for 24 hours at room temperature, and filtering, drying to constant weight, places into crucible and is built in Muffle furnace, is warming up to 900 DEG C
60min is activated, is cooled to room temperature, washing to neutrality, drying to constant weight under the conditions of 105 DEG C to get pine nut based active carbon is arrived
(being labeled as K-AC).
Continuous biomass pyrolysis device described in present embodiment step 1 uses China Patent Publication No. 105542812A,
A kind of device disclosed in entitled " continuous biomass pyrolysis device and its temperature measure monitoring and control method ", structure
Figure is as shown in 16, wherein the device continuous biomass pyrolysis device includes resistance furnace 6, the reaction being located inside resistance furnace 6
One end of pipe 5, the pressure feeding spiral 4 being located inside reaction tube 5, pressure feeding spiral 4 is connected by connecting shaft 2 with driving motor 1；Instead
Should 5 one end of pipe be connected with feed box 3, the other end connects gas outlet 7 and charcoal case 10；8 one end of temperature sensor passes through reaction tube 5
End be inserted into inside pressure feeding spiral 4, the other end is connected with controller 9 controls heating temperature；Controller 9 controls resistance furnace
6 pairs of reaction tubes 5 heat.
Active carbon yield calculation formula are as follows: Y=m/m0× 100% (1)
Wherein, Y is active carbon yield；M is pine nut shell quality of activated carbon, unit: g；m0For the pyrolysis carbonaceous for activation
Amount, unit: g.The yield of active carbon is 26.8% in present embodiment.
It is 1470.89m that present implementation method, which obtains active carbon specific surface area,2/ g, mesoporous is 31.56%, total pore volume
Up to 0.919ml/g.Under the current density of 1A/g, the specific capacitance of the active carbon of present implementation preparation reaches 232.1F/g；In 2A/
It recycles 1000 times under the high current density of g, is reached using the capacity retention that active carbon prepared by present implementation method makees electrode
94% or more.
The XRD spectrum of PNSC made from present embodiment and K-AC is as shown in figure 11, it can be seen from fig. 11 that original heat
All there are 2 obvious broad peaks in the X diffracting spectrum of solution charcoal and active carbon, be typical charcoal undefined structure.PNSC is in 2 θ
=23 ° or so there is C (002) diffraction maximum, more gentle C (100) diffraction maximum occur between -45 ° of 2 θ=40 °.By KOH
After activation, C (002) diffraction maximum and C (100) diffraction maximum acuity all be increased, it may be possible to because in activation process, it is some
Hetero atom is overflowed from carbon structure, so that microcrystalline internal carbon atom rearranges, structure ordering degree becomes larger, and is formed increasingly
Apparent carbonization structure.
The FT-IR spectrogram of PNSC made from present embodiment and K-AC is as shown in figure 12.As shown in Figure 12, PNSC exists
3686cm-1There is a more sharp absorption peak at place, may caused by being the stretching vibration of free hydroxyl or intermolecular hydrogen bonding O-H
It is the presence because of hydrone；3151cm-1Locate corresponding to be unsaturated C-H stretching vibration；1699cm-1The peak at place is attributed to carboxylic
The C=O of base or carbonyl is flexible；1573cm-1The peak nearby occurred is C=C skeletal vibration, may be alkene and aromatic compound；
1348cm-1The peak that place occurs is C-H bending vibration；1164cm-1And 1082cm-1The peak that place occurs is C-O stretching vibration；
880cm-1Neighbouring peak is as caused by C-H out-of-plane bending vibration.So there is also alcohol, ether, phenol, alkene, aromatizations in PNSC
Close the organic matter that object, ester etc. are not pyrolyzed completely.After overactivation, most curve trend does not change, but K-AC exists
1500--500cm-1The absorption peak at place significantly reduces, and shows that the organic matter in pyrolytic carbon further decomposes, surface functional group portion
Divide removal.KOH activation process is conducive to the graphitization of pyrolytic carbon, this is consistent with X-ray diffraction analysis result.
In order to more intuitively observe grain structure and the pattern variation of pyrolytic carbon activation front and back, to made from present embodiment
PNSC and K-AC does scanning electron microscope, and as shown in Figure 6,7, as seen from Figure 6, PNSC inner surface level is straggly, and there are some sizes
Different " shallow hole ", the presence of these pore structures have conducive to activator dipping when KOH entrance, promote subsequent activation process into
It is more sufficiently capable.The K-AC short texture obtained after KOH is activated, relatively in a jumble, the trace being etched is more apparent,
Extension extends to form random pore structure flourishing and abundant on the inner wall of macropore；The hierarchical pore structure that K-AC is mutually communicated,
The pore interior that active carbon can be can smoothly enter into for electrolyte ion provides condition.
Pore structure is analyzed, as a result as shown in Figure 13,14 and 15 and table 1.
The specific surface area and aperture structure of 1 pine nut shell base Carbon Materials of table
The N of PNSC made from present embodiment and K-AC2Suction-desorption isotherm is as shown in figure 13, and comparing two curves can
To find out, activation greatly improves the absorption property of sample.PNSC adsorbance is minimum and adsorption desorption line essentially coincides, and thus can push away
Survey the pore-size distribution relative narrower of PNSC.Classified according to IUPAC, the N of K-AC2Suction-desorption isotherm belongs to typical I type isothermal
Line, in relative pressure < 0.1, adsorbance increases sharply, and adsorbance increases slowly after relative pressure > 0.1, this shows sample
In hole be based on micropore.Suction-desorption curve of K-AC is in slow ascendant trend in entire pressure limit, and in phase
To there is H4 type hysteresis loop after pressure > 0.4, this is because N2Occur what capillary condensation generated in mesoporous, illustrates that K-AC is deposited
In a certain number of mesoporous.So K-AC be with for based on micropore, and with the level hole carbon structure of part mesoporous and macropore, this
One conclusion is confirmed again in table 2.
The mesoporous pore size distribution map and micropore size distribution map of PNSC made from present embodiment and K-AC is respectively such as Figure 14
Shown in 15, by Figure 14 and 15 it is found that K-AC mesoporous is mainly distributed in 2-4nm.Micropore is mainly distributed on 0.5-0.9nm.KOH electricity
Solve the K in liquid system+And OH-Diameter be both less than 0.4nm, such pore-size distribution is conducive to biography of the electrolyte ion in hole
It passs.
The cyclic voltammetry curve of PNSC and K-AC electrode made from present embodiment is as shown in figure 17, as shown in Figure 17,
Under biggish sweep speed, the cyclic voltammetry curve of PNSC electrode is close to triangle, and the cyclic voltammetry curve of K-AC electrode
Comparatively ideal rectangle is kept, and K-AC area under the curve is significantly greater than PNSC.After KOH is activated, K-AC has preferable this explanation
Capacitance characteristic, and specific capacitance is greatly improved.This is attributed to a certain number of mesoporous and biggish ratio in K-AC structure
Surface area, so that electrolyte ion more easily transmits inside it, a large amount of micropore surface is fully utilized, and generates densification
Electric double layer.
Constant current charge-discharge curve graph 18 of the PNSC and K-AC electrode made from present embodiment under the current density of 1A/g
It is shown.As can be seen from Figure 18, K-AC curve is linear and is in symmetrical triangle shape, illustrate electrode charge and discharge invertibity compared with
It is good, there is comparatively ideal charge and discharge coulombic efficiency.And the K-AC charge and discharge time is much larger than PNSC, according to constant current charge-discharge curve meter
It calculates specific capacitance formula (2), show that the specific capacitance of PNSC is 26.2F/g, the specific capacitance of K-AC is 232.1F/g, and activation process makes
Specific capacitance increases.
PNSC and K-AC electrode made from present embodiment is 10 in test frequency-2~105Resulting exchange within the scope of Hz
Impedance spectra is as shown in figure 19, and small figure therein is the enlarged drawing of high frequency region.As can be seen that curve is all by one of high frequency region
The straight line of semicircle and low frequency range composition.The intersection point of high frequency region curve and real axis is the equivalent series resistance (ESR) of sample；It is low
The frequency area straight line vertical with abscissa is saturated by charge and is controlled, related with substance diffusion impedance, represents pure capacitance behavior, tiltedly
Rate is bigger, and capacitance behavior is better.It appears from figure 19 that the ESR of PNSC and K-AC electrode is respectively 1.0 Ω and 0.6 Ω, K-AC's
Slope is greater than PNSC, illustrates after overactivation, and the intrinsic solution resistance of system electrolyte becomes smaller, times of capacitance characteristic and charge and discharge
Rate performance improves.
PNSC and K-AC electrode recycles 1000 times under the high current density of 2A/g, the pass of capacity retention and cycle-index
System is as shown in figure 19.The capacitor of PNSC electrode is in large range of irregular variation, and after KOH is activated, the capacitor of K-AC is protected
Holdup reaches 94% or more, shows good cyclical stability.
Specific embodiment 2: present embodiment is not both with specific embodiment one: the temperature of cracking described in step 1
It is 400 DEG C that degree, which is thermal cracking temperature,；Other steps and parameter are same as the specific embodiment one.
Specific embodiment 3: present embodiment is not both with specific embodiment one: the temperature of cracking described in step 1
It is 600 DEG C that degree, which is thermal cracking temperature,；Other steps and parameter are same as the specific embodiment one.
Specific embodiment 4: present embodiment is not both with specific embodiment one: in step 2 by potassium hydroxide and
Carbonized material mass ratio is that 5:1 is matched the carbonized material mixing after potassium hydroxide and sieving；Other steps and parameter and specific implementation
Mode one is identical.
Specific embodiment 5: present embodiment is not both with specific embodiment one: in step 2 by potassium hydroxide and
Carbonized material mass ratio is that 3:1 is matched the carbonized material mixing after potassium hydroxide and sieving；Other steps and parameter and specific implementation
Mode one is identical.
Specific embodiment 6: present embodiment is not both with specific embodiment one: activation temperature is 800 in step 2
℃；Other steps and parameter are same as the specific embodiment one.
Specific embodiment 7: present embodiment is not both with specific embodiment one: activation temperature is 700 in step 2
℃；Other steps and parameter are same as the specific embodiment one.
Specific embodiment 8: present embodiment is not both with specific embodiment one: activation time is in step 2
90min；Other steps and parameter are same as the specific embodiment one.
Specific embodiment 8: present embodiment is not both with specific embodiment one: activation time is in step 2
30min；Other steps and parameter are same as the specific embodiment one.
Using following verification experimental verification invention effects:
1. reagent and material
Potassium hydroxide, potassium iodide, sodium thiosulfate, are that analysis is pure, and by Tianjin, recovery development in science and technology Co., Ltd is raw
It produces, iodine (AR) is provided by Tianjin recovery fine chemistry industry research institute, and natrium carbonicum calcinatum (AR) is had by Tianjin day power chemical reagent
The production of limit company, from the source battery sales department of Taiyuan City's power, test water is for nickel foam, polytetrafluoroethylene (PTFE), acetylene carbon black
Homemade deionized water.
Test pine nut shell used is selected from of the Korean pine in Heilongjiang Province, is dried at 75 DEG C for 24 hours to constant weight using preceding
It is spare.The Industrial Analysis (GB/T 28731-2012) and elemental analysis of raw material are listed in table 2.
The Industrial Analysis and elemental analysis of 2 pine nut shell of table
Table2.Proximate analysis and elemental analysis ofpine nut shell
2. the preparation of active carbon
The preparation method of pine nut shell pyrolytic carbon: pine nut shell charcoal is anti-by the quick continuous pyrolysis of varying pitch biomass of independent research
It answers system to be made, 500 DEG C of preset temperature, revolving speed 15r/min is adjusted, by the pine nut shell material after drying by funnel through variable-pitch propeller
It send into device and carries out fast pyrolysis, reaction time about 15min.It takes out after cooling, obtains pine nut shell carbonized material.
The preparation method of pine nut shell active carbon: carbonized material is cleaned, 75 DEG C drying to constant weight, and screening granularity 8mm is as activation
Material.KOH solid is mixed with carbonized material by certain mass ratio, and deionized water is added, and is impregnated at room temperature for 24 hours, filtering, 105 DEG C of drying
To constant weight.It weighs about 10g sample and is put into crucible and be built in Muffle furnace, no N2Protection, is warming up to activation temperature, when keeping the temperature one section
Between.Finally, being cooled to room temperature, sample is washed to neutrality, 105 DEG C of dryings for 24 hours, obtain activated material.Alkali charcoal ratio is 1:1~5:1,
500~900 DEG C of activation temperature, activation time is 30~90min.
3. activated carbon structure and performance
Specific surface area and pore-size distribution are measured using specific surface and Porosimetry (3H-2000PS1, Bei Shide),
N is measured at 77K2Adsorption and desorption isotherms, deaerate at 300 DEG C 6h before sample test.Specific surface area is obtained by BET method, mesoporous
Pore-size distribution is fitted by BJH method, and micropore size distribution is fitted by HK method, and t-plot method calculates the Micropore volume of sample.
Sample topography is characterized using scanning electron microscope (SEM, S-3400, Japan).The crystal phase structure of sample is by X
Ray powder diffractometer (XRD, MiniFlex-600, Japan) analysis, Cu-K α as radiation source, 2 θ of the angle of diffraction from 10 °~80 °,
20 °/min of scanning speed.Fourier infrared spectrograph (FT-IR, Tensor 27, the Germany) measurement of the surface functional group of sample,
500~4000cm of detection range-1。
4. activated carbon electrodes preparation and performance
The chemical property of Carbon Materials sample is measured by three-electrode system.Activated carbon sample obtained is ground to granularity
Less than 0.075mm, acetylene carbon black does conductive agent, and polytetrafluoroethylene (PTFE) (PTFE) is binder, adds after mixing in mass ratio for 8:1:1
Enter appropriate dehydrated alcohol to mix well to thick, using nickel foam as carrier, paints the nickel foam strip electrode of 1cm × 1cm, done at 70 DEG C
Dry 10 hours, working electrode is pressed under 10MPa, the active material on electrode slice is about 10mg.Platinum plate electrode is used as to electrode,
Silver-silver chloride electrode is as reference electrode, using 6mol/L KOH solution as electrolyte, carries out electrochemistry after electrode is impregnated 2h
Test, testing electrochemical workstation used is EC-Lab, SP-150.Carry out cyclic voltammetry, constant current charge-discharge test and
Ac impedance measurement.
The voltage scan range of cyclic voltammetry is -1.1~0.1V；Ac impedance measurement frequency range is 10-2~
105Hz；Charging/discharging voltage range is -1.1V~0.1V, the calculation formula of specific capacitance C are as follows:
C=I × △ t/ (m × △ V) (2)
Wherein, C is specific capacitance, unit: F/g；I is current density, unit: A/cm2；△ t is discharge time, unit: s；m
For the quality of active material, unit: g；△ V is voltage window range, unit: V.
5. the influence of alkali charcoal ratio
Test is by activation temperature control at 900 DEG C, and activation time is controlled in 60min, and alkali charcoal ratio is at 1~5 to active carbon
The influence of specific surface area and yield, as a result as shown in Figure 8.Fig. 8 shows the increase with alkali charcoal ratio, active carbon yield by
55.1% is persistently down to 20.4%.This is because the main component of pine nut shell pyrolytic carbon is C, by activator KOH impregnation drying
Afterwards, under the high temperature conditions, KOH+C → K+H occurs2+K2CO3；K2CO3→K2O+CO2；K2CO3+C→K2O+CO；K2O+C→K+CO；
K+CO2→K2The series reactions such as O+CO, with the increase of alkali charcoal ratio, KOH proportion is increase accordingly, promote reaction forward into
Row, so that a large amount of C is detached from the form of CO, on the other hand, some organic matters not being pyrolyzed completely existing for pyrolytic carbon itself,
Can further volatilize spilling in activation process, so that active carbon yield reduces.Specific surface area is presented with the increase of alkali charcoal ratio
First increase the trend reduced afterwards, when alkali charcoal ratio is 4, reaches maximum value 1470.89m2/g.This is because alkali charcoal makes than increasing
C and KOH reaction aggravation is obtained, a large amount of H is generated2And CO, it navigates in pyrolytic carbon, forms microcellular structure abundant, and activate
(900 DEG C) of temperature when being higher than boiling point (762 DEG C) of simple substance potassium, the K simple substance of generation is in gaseous state, also promotes the development of pore structure.But
It is the excess air continuation reaming for reacting generation after alkali charcoal ratio is greater than 4, causes the collapsing of microcellular structure, form part and be situated between
Hole and macropore, so that specific surface area be made to reduce.
6. the influence of activation time
Test uses alkali charcoal ratio 4:1, and 900 DEG C of activation temperature, activation time is to active carbon specific surface area in 30~90min
With the influence of yield, as a result as shown in Figure 9.As shown in Figure 9, with the increase of activation time, the yield of active carbon is constantly reduced.
This is because activation time is longer, the organic matter volatilization not being pyrolyzed completely overflow it is more, and activator and pyrolytic carbon react into
Capable is more abundant, and C is detached from more in the form of CO, so that the yield of active carbon is lower.Specific surface area first increases to be reduced afterwards,
Reach maximum value when 60min.This is because KOH is reacted with pyrolytic carbon based on poration process when activation time is lower than 60min,
A large amount of micropore is generated, so that the specific surface area of active carbon is continuously increased；It is with reaming procedure when activation time is greater than 60min
Main, gas that activation process generates etc. enters micropore, forms a small amount of mesoporous and macropore, and overlong time under 900 DEG C of high temperature, leads
The ablation of pore collapses, and active carbon specific surface area is caused to decline.
7. the influence of activation temperature
Test uses alkali charcoal ratio 4:1, and activation time 60min, activation temperature is at 500~900 DEG C to active carbon specific surface
Long-pending and yield influence, the results are shown in Figure 10.As shown in Figure 10, as the temperature rises, active carbon yield persistently reduces, by
52.2% at 500 DEG C is down to 26.8% at 900 DEG C.Specific surface area persistently increases, it is contemplated that activating cost, highest is living
Change temperature and be selected as 900 DEG C, specific surface area reaches maximum value 1470.89m at this temperature2/g.This is because pyrolytic carbon itself is deposited
Some organic substances not being pyrolyzed completely, can further volatilize spilling as the temperature rises in activation process, formed
Pore structure；KOH+C → K+H in another aspect activation process2+K2CO3；K2CO3→K2O+CO2；K2CO3+C→K2O+CO；K2O+
C→K+CO；K+CO2→K2The series reactions such as O+CO are occurred under different temperature sections.400 DEG C or so KOH and C start
It reacts, generates H2Start to carry out pore-creating to carbonized material；700℃[13]Left and right K2CO3→K2O+CO2Reaction occurs, generation
CO2Conducive to pore-creating；Temperature is greater than after 710 DEG C, and the reaction for generating CO takes place, and temperature is greater than after 762 DEG C, potassium list
Matter participates in pore-creating in the form of a vapor, and as the temperature rises, the gaseous matter generated successively participates in the pore-creating to carbonized material
In the process, so that specific surface area constantly increases.
7. different pyrolysis temperatures are to the specific surface area of carbonized material and the influence in aperture
Test is by the revolving speed control of pressure feeding spiral in 15r/min, and thermal cracking temperature is controlled in 15min, and thermal cracking temperature is
To the influence of the specific surface area of carbonized material and aperture at 300-700 DEG C, as a result as shown in table 3 and Fig. 1-5.
The specific surface area and pore-size distribution table of carbonized material are prepared under 3 different temperatures of table
By table 3 and Fig. 1-5 it is found that thermal-cracking method of the present invention preparation carbonized stock has pore structure abundant, level compares
It is more, contain macropore, mesoporous, micropore.
At 300 DEG C of thermal cracking temperature, gained pyrolytic carbon specific surface area is minimum, microporosity 20%, is with mesoporous and macropore
Based on incomplete pyrolytic carbon, since pyrolysis temperature is lower, many volatile materials it is non-volatile come out, the micropore knot of formation
Structure is less.
At 700 DEG C of thermal cracking temperature, gained active carbon specific surface area is lower, and microporosity is only 32%, is based on mesoporous
Excessive pyrolytic carbon, excessively high pyrolysis temperature makes resulting micropore ablation collapse, forms mesoporous and macropore, cause specific surface area and
The reduction of microporosity.
At 500 DEG C of thermal cracking temperature, the specific surface area highest of gained pyrolytic carbon, it is with micropore that microporosity, which reaches 65.6%,
For main pyrolytic carbon, suitable temperature make pyrolytic carbon original macropore or it is mesoporous on the basis of continue pore-creating, formed abundant complicated
Hierarchical pore structure.
Claims (2)
1. be used for electrode material pine nut based active carbon, it is characterised in that pine nut based active carbon be using pine nut shell as raw material,
Hot cracked to obtain made of carbonized material post activation, the activation is that deionization is added after mixing potassium hydroxide and carbonized material
Water, then successively impregnated, filtered, being dried and high temperature under be activated；
Wherein, in the pine nut based active carbon preparation process, the carbonized material is to crush the sub- shell of Korean pine, under the conditions of 75 DEG C
It is dry to be placed in continuous biomass pyrolysis device to constant weight, temperature is 500 DEG C, the revolving speed of pressure feeding spiral is 15r/min condition
Lower thermal cracking 15min is obtained after taking out after cooling；The activation is to clean above-mentioned carbonized material with distilled water, at 105 DEG C
Under the conditions of drying to constant weight, cross the sieve of 8mm, then by potassium hydroxide and carbonized material mass ratio be 4:1 match potassium hydroxide and
Carbonized material mixing after sieving, is added 100ml deionized water, impregnates at room temperature for 24 hours, filtering, drying to constant weight, places into earthenware
Crucible is built in Muffle furnace, is warming up to 900 DEG C of activation 60min, is cooled to room temperature, and is washed to neutrality, drying to constant weight；
The hole of the active carbon is flourishing, and aperture multiplicity, arrangement is random, generates a large amount of micropore or is distributed in active carbon table
Face, or be nested in mesoporous and macropore, the hierarchical pore structure for having both macropore, mesoporous and micropore is formed, specific surface area is
1470.89m2/ g, total pore volume 0.919mL/g, average pore diameter 2.6nm, Micropore volume 0.629mL/g, mesoporous
31.56%, mesoporous is distributed in 0.5-0.9nm in 2-4nm, micropore.
2. the preparation method for the pine nut based active carbon of electrode material as described in claim 1, it is characterised in that pine nut
The preparation method of based active carbon is realized by following step:
Step 1: the sub- shell of Korean pine is crushed, dries under the conditions of 75 DEG C to constant weight, be placed in continuous biomass pyrolysis device,
Thermal cracking 15min under the conditions of temperature is 500 DEG C, the revolving speed of pressure feeding spiral is 15r/min, takes out after cooling, obtains carbonized material；
Step 2: the carbonized material that step 1 obtains is cleaned with distilled water, drying to constant weight under the conditions of 105 DEG C, crosses 8mm's
Then sieve is matched for 4:1 by potassium hydroxide and carbonized material mass ratio and mixes the carbonized material after potassium hydroxide and sieving, addition
100ml deionized water impregnates for 24 hours at room temperature, and filtering, drying to constant weight, places into crucible and is built in Muffle furnace, is warming up to
60min is activated at 900 DEG C, is cooled to room temperature, washing to neutrality, drying to constant weight to get pine nut based active carbon is arrived.
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