CN107527745A - The method that inorganic salts auxiliary prepares classifying porous biological carbon materials - Google Patents
The method that inorganic salts auxiliary prepares classifying porous biological carbon materials Download PDFInfo
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- inorganic salts
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- 150000003839 salts Chemical class 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 65
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 26
- 239000002028 Biomass Substances 0.000 claims abstract description 68
- 239000003610 charcoal Substances 0.000 claims abstract description 59
- 239000011148 porous material Substances 0.000 claims abstract description 19
- 230000008602 contraction Effects 0.000 claims abstract description 18
- 238000003763 carbonization Methods 0.000 claims abstract description 17
- 238000011049 filling Methods 0.000 claims abstract description 13
- 238000000197 pyrolysis Methods 0.000 claims abstract description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 46
- 230000008569 process Effects 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 24
- 239000011780 sodium chloride Substances 0.000 claims description 23
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 238000000354 decomposition reaction Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000012266 salt solution Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 238000005255 carburizing Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 230000003319 supportive effect Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 abstract description 13
- 239000003990 capacitor Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 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 21
- 239000011734 sodium Substances 0.000 description 21
- 229910052708 sodium Inorganic materials 0.000 description 21
- 238000012360 testing method Methods 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000007654 immersion Methods 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 208000018875 hypoxemia Diseases 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
- C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses the method that a kind of inorganic salts auxiliary prepares classifying porous biological carbon materials, electrode material for super capacitor preparing technical field is mainly used in.The drawbacks of present invention is directed to traditional biological charcoal mesopore and macropore limited amount so that the problem of electrolyte quickly transmits can not be met in electrode of super capacitor.The present invention is on the basis of original biomass direct carbonization prepares charcoal, and using inorganic salts filling biomass hole, the inorganic salts device to hole structure for support of solid-state acts on during heat resolve, alleviates the problem of hole thermal contraction is violent.The method that the present invention prepares charcoal is simple to operate, and yield is high, cost is low, and products obtained therefrom has abundant classification pore space structure, and charcoal prepared by the direct pyrolysis of pore volume ratio of especially mesopore and macropore is doubled.Multiporous biological Carbon Materials prepared by the present invention are used in the electrode material of ultracapacitor, can accelerate the speed of electric double layer reaction, improve the performance of ultracapacitor.
Description
Technical field
The present invention relates to a kind of preparation method of biological carbon materials, more particularly to a kind of classifying porous biological carbon materials
Preparation method, applied to electrode material for super capacitor preparing technical field.
Background technology
Ultracapacitor has that charge/discharge rates are fast, have extended cycle life, power density is high, green as a kind of energy storage device
The advantages that color cleans.Ultracapacitor is mainly made up of the part such as electrode, electrolyte, barrier film.Wherein electrode material is to super electricity
The performance impact of container is maximum, and the price relation of electrode is to the cost of whole capacitor.The electrode material of ultracapacitor, it is main
Need to meet following three points requirement：High-specific surface area, high conductivity, the passage for providing electrolyte transport, searching are provided simultaneously with
The electrode material of these conditions, the development to ultracapacitor are significant.The electrode material used now is mostly carbon materials
Material, charcoal is also one kind of carbon material.
Charcoal be bio-organic materials in hypoxemia or oxygen-free environment, the solid product that is generated after high temperature pyrolysis.
It is referred to as " charcoal " by scientists with fixing the charcoal based on carbon.Its theoretical foundation is：Biomass, whether plant
Or animal, burns, can form charcoal in the absence of oxygen.Charcoal is almost pure carbon, while is rich in hole
Hole, meet requirement of the ultracapacitor to electrode material, thus charcoal can as electrode material for super capacitor selection it
One.
During charcoal is prepared, with the rise of pyrolysis temperature, the graphitization journey of material on the one hand can be improved
Degree increases electrical conductivity；Another aspect high temperature can cause hole thermal contraction to reduce pore volume, be unfavorable for electric double layer reaction.
The content of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
The method that inorganic salts auxiliary prepares classifying porous biological carbon materials, biomass is soaked by inorganic salt solution, hole is obtained after drying
The biomass of inorganic salt crystal, the method that reheating decomposition prepares multiporous biological Carbon Materials are filled with hole.The inventive method can
The pore structure of biological carbon electrode material is improved, particularly increases the ratio of mesopore and macropore, so as to improve the property of ultracapacitor
Energy.The present invention fills its hole on the basis of original biomass direct carbonization, using inorganic salts, and inorganic salts are not in heating process
It can melt and device to hole structure for support acts on, avoid the thermal contraction in hole, pore structure can be improved, especially increase mesopore and big
The quantity in hole.
To reach above-mentioned purpose, the present invention adopts the following technical scheme that：
A kind of method that inorganic salts auxiliary prepares classifying porous biological carbon materials, biomass is filled into solid inorganic salt
In hole, then heat resolve biomass is carried out, finally remove inorganic salts to obtain multiporous biological charcoal, and prepare in biomass pyrolytic
In the whole technical process of multiporous biological charcoal, inorganic salts do not occur to melt and play a supportive role to the pore structure of material, avoid
The thermal contraction in hole, and during the entire process of the technique that biomass pyrolytic prepares multiporous biological charcoal, solid inorganic salt and biomass
Neither chemically reacted with multiporous biological charcoal.
As currently preferred technical scheme, the melting temperature of used inorganic salts, which is higher than, prepares multiporous biological charcoal
The minimum heat decomposition temperature of biomass.
The technical scheme further preferred as the present invention, inorganic salts aid in preparing the side of classifying porous biological carbon materials
Method, comprise the following steps：
A. inorganic salts filling biomass hole process：
First biomass is dried and removes moisture, the biomass handled well is taken out, it is fully then soaked in inorganic salts
In solution, after 12-24h is soaked, the biomass impregnated of inorganic salt solution is taken out, after biomass is dried, makes biomass
Inorganic salts solid is formed in hole, repeated impregnations process and drying course, and inorganic salts are filled in the hole of biomass to increase
Amount, obtain the biomass of inorganic salts filling；As preferable technical scheme, before biomass is thermally decomposed, it is necessary to by biology
Matter is fully soaked in inorganic salt solution, solution is entered inside hole, by repeated impregnations process and drying course, is obtained
To the biomass for thering are inorganic salts to fill；
B. carbonization treatment technique process：
The biomass for being filled with inorganic salts into hole in the step a is placed in inert atmosphere, carries out heating point
Solution, control heat decomposition temperature are not higher than the fusing point of inorganic salts, while also to meet that biomass thermal decomposes carburizing temperature, are pyrolyzed herein
During, biomass is converted into charcoal, and make solid inorganic salt keep solid-state constant in hole, make solid inorganic salt pair
Pore structure plays a supportive role；When carrying out carbonization treatment technique, preferably control programming rate and cooling rate be at most 3 DEG C/
min；When carrying out carbonization treatment technique, heat decomposition temperature is preferably controlled, and makes heat decomposition temperature less than the fusing point temperature of inorganic salts
Degree.
C. end processing sequences：
The charcoal for preparing is cleaned in the step b with the solvent that can dissolve inorganic salts, by charcoal hole
Inorganic salts dissolve and removed, and finally reuse deionized water and charcoal is cleaned, dry, so as to obtain multiporous biological charcoal into
Product.
Above-mentioned inorganic salts preferably use sodium chloride.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage：
1. the present invention using inorganic salt solution immersion biomass, selects suitable pyrolysis temperature, pyrolysis temperature not above
The fusing point of inorganic salts, if above its fusing point, inorganic salts cannot be present in the hole of wood in solid form, also with regard to device to hole
Hole does not have supporting role；
2. the present invention is directed to traditional biological charcoal mesopore and macropore limited amount, electricity can not be met in electrode of super capacitor
The problem of solution matter is quickly transmitted, on the basis of original biomass direct carbonization, its hole, heating process are filled using inorganic salts
Middle inorganic salts will not melt and device to hole structure for support acts on, and avoid the thermal contraction in hole, can improve pore structure, especially increase
Add the quantity of mesopore and macropore；
3. the present invention alleviates the problem of material hole thermal contraction is violent, biomass is filled into using by solid inorganic salt
In hole, the excessive shrinkage of the hole avoided due to the supporting role of inorganic salts during heating, the fusing point of used inorganic salts is high
In the pyrolysis temperature of charcoal, it will not melt in heating process, pyrolysis can be with solution by the inorganic salts in hole after terminating
Dissolving removes, and obtains hierarchical porous structure charcoal sample, and filling process of the inorganic salts in biomass hole can be by by biology
Matter is soaked in the inorganic salt solution, inorganic salts solid is obtained after drying to realize, method is simple and easy；
4. the method that the present invention prepares charcoal is simple to operate, yield is high, cost is low, and products obtained therefrom has abundant classification
Charcoal prepared by the direct pyrolysis of pore volume ratio of pore space structure, especially mesopore and macropore is more than doubled, and is used in
In the electrode material of ultracapacitor, the speed of electric double layer reaction can be accelerated, improve the performance of ultracapacitor.
Brief description of the drawings
Fig. 1 is that the inorganic salts for the method that the inorganic salts of the embodiment of the present invention one auxiliary prepares classifying porous biological carbon materials are filled out
Fill the cleaning of-biomass thermal decomposition-inorganic salts and remove overall process schematic diagram.
Fig. 2 is the SEM of the SEM figures and the charcoal of pore filling inorganic salts of charcoal prepared by the embodiment of the present invention one
Figure.
Fig. 3 is the graph of pore diameter distribution of the nitrogen BET tests of charcoal prepared by the embodiment of the present invention one.
Fig. 4 is the graph of pore diameter distribution of the Mercury-injection test of charcoal prepared by the embodiment of the present invention one.
Embodiment
Details are as follows for the preferred embodiments of the present invention：
Embodiment one：
In the present embodiment, a kind of method for preparing classifying porous biological carbon materials referring to Fig. 1, inorganic salts auxiliary, including
Following steps：
(1) inorganic salts filling biomass hole process：
First the wood of bulk is positioned over to dry in common drying box and removes moisture, it is 100 DEG C to set temperature, dries 24h, this
The inorganic salts that example is chosen are sodium chloride；At 20 DEG C, the solubility of sodium chloride is that can dissolve 36g chlorinations per 100g distilled water
Sodium；The present embodiment first measures 200ml distilled water with volumetric flask, then weighs 80g sodium chloride crystals, and sodium chloride and distilled water are configured
Into sodium chloride solution；Dried wooden unit is cut into the strip that length, width and height are 5cm, 1cm, 1cm respectively；Because the meeting in cutting
Error be present, the specification of each batten can not be identical, so doing accurate measurement using slide measure, a sample qualities are
4.8g, volume 6.16cm3；B sample qualities are 5.61g, volume 7.94cm3；A samples do not process, and b samples are put into chlorination
24h is soaked in sodium solution, b samples are then taken out into drying, immersion-drying process process is repeated, to increase the hole of biomass
The amount of middle filling inorganic salts, obtains the b sample biomass of inorganic salts filling；
(2) carbonization treatment technique process：
A, b sample in the step (1) are positioned in two crucibles respectively, inserted in tube furnace, is carried out at twice
Carbonization treatment, nitrogen is passed through in thermal decomposition process, forms inert atmosphere, control and thermally decompose heating schedule and be：Heating rate is 3
DEG C/min, 50 DEG C are risen to, is incubated 60min；Then continue to heat up, heating rate is still 3 DEG C/min, rises to 750 DEG C, insulation
120min；Then cool, rate of temperature fall is 3 DEG C/min, is down to 600 DEG C；Then Temperature fall, it is down to room temperature and can be taken off sample
Product；In the pyrolytic process of whole carbonization treatment technique, sodium chloride a samples have been not filled by it and have been filled with the b samples life of sodium chloride
Material is placed in inert atmosphere all the time, carries out heat resolve, and control heat decomposition temperature is not higher than the fusing point of sodium chloride, while also
Meet that biomass thermal decomposes carburizing temperature, in this pyrolytic process, biomass is converted into charcoal；
(3) end processing sequences：
After thermal decomposition terminates, after tube furnace is down to room temperature, a, b sample are taken out, a samples are directly placed into 0.5mol/L
Dust technology in soak 24h；B samples are first cleaned 5 times with deionized water, places into 0.5mol/L dust technology and soaks 24h；
After immersion, two samples of a, b are taken out, then cleaned repeatedly with deionized water 5 times；Then a, b sample are positioned over common dry
Dried in dry case, it is 80 DEG C to set temperature, and 6h is dried, after drying, so as to obtain multiporous biological charcoal finished product, this implementation
Example cleans the b sample charcoals prepared in the step (2) with the solvent that can dissolve sodium chloride, can be by b sample charcoals hole
Sodium chloride in hole dissolves and removed, and finally reuses deionized water and charcoal is cleaned, and dries, so as to obtain porous life
Thing charcoal finished product.
Experimental test and analysis：
A, b sample multiporous biological charcoal finished product prepared by embodiment one carries out test analysis, not Ce Liang a, b sample quality
With volume.A mass is 1.57g, volume 2.14cm3.B sample qualities are 1.19g, volume 3.07cm3.Sample segment is ground
For powder, for characterization test.
The gained biological carbon materials of embodiment one are characterized and performance test is as follows：
1.SEM characterization tests：
SEM characterization tests are carried out to the charcoal of the gained of embodiment one, a figures are not soak superchlorination sodium solution in fig. 2
Sample characterization figure, b figures are not remove the sample characterization figure of sodium chloride crystal after carbonization, be can be seen that from the contrast of two width figures
There is pore space structure in the inside of two samples, but inorganic salt crystal is filled with the hole of b figures, and inorganic salts show compared with
Good crystallization structure, shows not melt in heating process, can play a part of supporting hole.
2. cubical contraction is tested with porosity：
The calculating of volume contraction and the test of porosity are carried out to the charcoal of the gained of embodiment one.Do not soak superchlorination
Cubical contraction is 65.3% before and after the sample carbonization of sodium.Cubical contraction is before and after the sample carbonization of immersion superchlorination sodium solution
61.4%.By the comparison to cubical contraction, the sample volume of immersion superchlorination sodium shrinks smaller.In addition, pass through
Porosity is measured, the porosity for not soaking superchlorination sodium solution sample is 65.54%, soaks superchlorination sodium solution sample
The porosity of product is 74.62%.According to the test of cubical contraction and porosity, it can illustrate sodium chloride crystal in material
The hole in portion serves supporting role, prevents the thermal contraction of hole.
3.BET is tested：
BET tests are carried out to the charcoal of the gained of embodiment one, main results include：Specific surface area, pore-size distribution.
The specific surface area that the sample for not soaking superchlorination sodium solution is drawn by test is 311.28m2/ g, soak superchlorination sodium solution
The specific surface area of sample be 430.17m2/ g, the contribution of quantitative comparison's surface area of micropore is maximum, can be obtained by test result
Go out, unsoaked sample will be more than by soaking the micropore quantity of the sample interior of superchlorination sodium solution, and this can also illustrate due to chlorine
Change sodium crystal to be present in micropore so that in heat treatment, micropore is no too big decay because of thermal contraction.By Fig. 3 hole
Footpath distribution can be seen that the sample of immersion superchlorination sodium solution under each aperture, and the quantity in hole, which will be significantly more than, not soak
Sample.Tested by BET, can intuitively show that sodium chloride crystal serves supporting role to the hole of material internal.
4. mercury injection method is tested：
Mercury-injection test is carried out to the charcoal of the gained of embodiment one, what mercury injection method was mainly tested is the number of material internal macropore
Amount.The macropore volume of the sample interior of superchlorination sodium solution is soaked as seen in Figure 4 apparently higher than not soaking superchlorination sodium
The sample of solution, illustrate that sodium chloride serves supporting role to material internal hole.
The method that a kind of inorganic salts auxiliary prepared by embodiment one prepares classifying porous biological carbon materials, uses solid inorganic salt
It is filled into the hole of biomass, then carries out heat resolve biomass, inorganic salts finally is removed to obtain multiporous biological charcoal, and
Biomass pyrolytic is prepared in the whole technical process of multiporous biological charcoal, and inorganic salts do not occur to melt and play branch to the pore structure of material
Support acts on, and avoids the thermal contraction of hole, and in biomass pyrolytic prepares the whole technical process of multiporous biological charcoal, solid inorganic
Salt neither chemically reacts with biomass and multiporous biological charcoal.The melting temperature of used inorganic salts, which is higher than, prepares porous life
The minimum heat decomposition temperature of the biomass of thing charcoal.
Embodiment two：
The present embodiment and embodiment one are essentially identical, are particular in that：
In the present embodiment, a kind of method that inorganic salts auxiliary prepares classifying porous biological carbon materials, comprises the following steps：
(1) inorganic salts filling biomass hole process：
First the wood of bulk is positioned over to dry in common drying box and removes moisture, it is 100 DEG C to set temperature, dries 24h, this
The inorganic salts that example is chosen are sodium chloride；At 20 DEG C, the solubility of sodium chloride is that can dissolve 36g chlorinations per 100g distilled water
Sodium；The present embodiment first measures 200ml distilled water with volumetric flask, then weighs 80g sodium chloride crystals, and sodium chloride and distilled water are configured
Into sodium chloride solution；Dried wooden unit is cut into the strip that length, width and height are 5cm, 1cm, 1cm respectively；Because the meeting in cutting
Error be present, the specification of each batten can not be identical, so doing accurate measurement using slide measure, a sample qualities are
4.8g, volume 6.16cm3；B sample qualities are 5.61g, volume 7.94cm3；A samples do not process, and b samples are put into chlorination
12h is soaked in sodium solution, b samples are then taken out into drying, immersion-drying process process is repeated, to increase the hole of biomass
The amount of middle filling inorganic salts, obtains the b sample biomass of inorganic salts filling；
(2) carbonization treatment technique process：This step is identical with embodiment one；
(3) end processing sequences：This step is identical with embodiment one.
The result that comprehensive above example of the present invention prepares biological carbon electrode material test analysis shows：
By the research of the present embodiment, when the heat decomposition temperature of biomass is less than sodium chloride fusing point, sodium chloride can be brilliant
The state of body is present with biomass hole, being played a supporting role to hole.In biomass thermal decomposable process, if without chlorine
Change the presence of sodium crystal, no material is supported to hole, can cause the contraction of hole, passes through some signs and test side
Method, we can draw the pore structure of the sample interior of immersion superchlorination sodium solution substantially than no immersion superchlorination sodium solution
Sample it is flourishing, while by electro-chemical test, the properties of sample for soaking superchlorination sodium solution is more preferable.
The above embodiment of the present invention is directed to traditional biological charcoal mesopore and macropore limited amount, in electrode of super capacitor not
The problem of electrolyte quickly transmits can be met.Above-described embodiment on the basis of original biomass direct carbonization prepares charcoal,
Using inorganic salts filling biomass hole, the inorganic salts device to hole structure for support of solid-state acts on during heat resolve, alleviates
The problem of hole thermal contraction is violent.The method that above-described embodiment prepares charcoal is simple to operate, and yield is high, cost is low, gained production
Product have abundant classification pore space structure, and charcoal prepared by the direct pyrolysis of pore volume ratio of especially mesopore and macropore improves
One times.Multiporous biological Carbon Materials prepared by above-described embodiment are used in the electrode material of ultracapacitor, can accelerate electric double layer
The speed of reaction, improve the performance of ultracapacitor.
The embodiment of the present invention is illustrated above in conjunction with accompanying drawing, but the invention is not restricted to above-described embodiment, can be with
A variety of changes are made according to the purpose of the innovation and creation of the present invention, under all Spirit Essence and principle according to technical solution of the present invention
Change, modification, replacement, combination or the simplification made, should be equivalent substitute mode, as long as meeting the goal of the invention of the present invention,
Technical principle and the inventive concept of the method for classifying porous biological carbon materials are prepared without departing from inorganic salts of the present invention auxiliary, all
Belong to protection scope of the present invention.
Claims (7)
1. a kind of method that inorganic salts auxiliary prepares classifying porous biological carbon materials, it is characterised in that：Filled with solid inorganic salt
Into the hole of biomass, then heat resolve biomass is carried out, finally remove inorganic salts to obtain multiporous biological charcoal, and in biology
Matter pyrolysis is prepared in the whole technical process of multiporous biological charcoal, and inorganic salts do not occur to melt and play support work to the pore structure of material
With, avoid the thermal contraction of hole, and in biomass pyrolytic prepares the whole technical process of multiporous biological charcoal, solid inorganic salt with
Biomass and multiporous biological charcoal neither chemically react.
2. the method that inorganic salts auxiliary prepares classifying porous biological carbon materials according to claim 1, it is characterised in that：Adopted
The melting temperature of inorganic salts is higher than the minimum heat decomposition temperature for the biomass for preparing multiporous biological charcoal.
3. the method that inorganic salts auxiliary prepares classifying porous biological carbon materials according to claim 2, it is characterised in that including
Following steps：
A. inorganic salts filling biomass hole process：
First biomass is dried and removes moisture, the biomass handled well is taken out, it is fully then soaked in inorganic salt solution
In, after 12-24h is soaked, the biomass impregnated of inorganic salt solution is taken out, after biomass is dried, makes the hole of biomass
Middle inorganic salts solid is formed, repeated impregnations process and drying course, to increase the amount that inorganic salts are filled in the hole of biomass, is obtained
To the biomass for thering are inorganic salts to fill；
B. carbonization treatment technique process：
The biomass for being filled with inorganic salts into hole in the step a is placed in inert atmosphere, carries out heat resolve, control
Heat decomposition temperature and be not higher than the fusing point of inorganic salts, while also to meet that biomass thermal decomposes carburizing temperature, in this pyrolytic process
In, biomass is converted into charcoal, and make solid inorganic salt keep solid-state constant in hole, make solid inorganic salt device to hole knot
Structure plays a supportive role；
C. end processing sequences：
The charcoal for preparing is cleaned in the step b with the solvent of dissolvable inorganic salts, by the inorganic salts in charcoal hole
Dissolve and remove, finally reuse deionized water and charcoal is cleaned, dry, so as to obtain multiporous biological charcoal finished product.
4. the method that inorganic salts auxiliary prepares classifying porous biological carbon materials according to claim 3, it is characterised in that：Institute
State in step a, it is necessary to which biomass is fully soaked in inorganic salt solution before biomass is thermally decomposed, make solution
Into inside hole, by repeated impregnations process and drying course, the biomass of inorganic salts filling is obtained.
5. the method that the inorganic salts auxiliary according to any one in Claims 1 to 4 prepares classifying porous biological carbon materials, its
It is characterised by：The inorganic salts use sodium chloride.
6. the method that classifying porous biological carbon materials are prepared according to the inorganic salts auxiliary of claim 3 or 4, it is characterised in that：
When carbonization treatment technique is carried out in the step b, it is at most 3 DEG C/min to control programming rate and cooling rate.
7. the method that classifying porous biological carbon materials are prepared according to the inorganic salts auxiliary of claim 3 or 4, it is characterised in that：
When carbonization treatment technique is carried out in the step b, heat decomposition temperature is controlled, and makes heat decomposition temperature less than the fusing point of inorganic salts
Temperature.
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