CN109455714A - A kind of lignin porous structure carbon material and its preparation method and application - Google Patents
A kind of lignin porous structure carbon material and its preparation method and application Download PDFInfo
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- CN109455714A CN109455714A CN201811442118.4A CN201811442118A CN109455714A CN 109455714 A CN109455714 A CN 109455714A CN 201811442118 A CN201811442118 A CN 201811442118A CN 109455714 A CN109455714 A CN 109455714A
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- lignin
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- 229920005610 lignin Polymers 0.000 title claims abstract description 62
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000243 solution Substances 0.000 claims abstract description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000013049 sediment Substances 0.000 claims abstract description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003708 ampul Substances 0.000 claims abstract description 14
- 239000010453 quartz Substances 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 14
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 7
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 239000007772 electrode material Substances 0.000 claims abstract description 4
- 238000003763 carbonization Methods 0.000 claims abstract description 3
- 239000008367 deionised water Substances 0.000 claims abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 238000010792 warming Methods 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 229920001992 poloxamer 407 Polymers 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000011282 treatment Methods 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920001983 poloxamer Polymers 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229920001732 Lignosulfonate Polymers 0.000 claims 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 239000003463 adsorbent Substances 0.000 abstract description 2
- 238000010992 reflux Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
A kind of lignin porous structure carbon material and its preparation method and application, lignin is uniformly mixed with hydrochloric acid solution, is heated to reflux processing and is filtered and collect sediment, obtains precrosslink lignin；Precrosslink lignin and triblock copolymer are dissolved in tetrahydrofuran and obtain mixed solution, hydrochloric acid solution is added, dries after mixing evenly, collection obtains solid sediment；Above-mentioned solid sediment is placed in the quartz ampoule of tube furnace, inert gas and ammonia are passed through, heating carbonization is cooled to room temperature to obtain carbon material after reaction；It takes out carbon material to be uniformly mixed with chemical activating agent with mortar, and is again placed in quartz ampoule, heat, be cooled to room temperature under atmosphere of inert gases, rinsed with deionized water, obtain lignin porous carbon materials after dry.The present invention is with mantle plate method and ammonia is cooperated to handle, and the porous structure carbon material being prepared has high specific surface area, can be used as the electrode material of adsorbent material or supercapacitor.
Description
Technical field
The invention belongs to porous carbon materials field, in particular to a kind of lignin porous structure carbon material and preparation method thereof
And application.
Background technique
Carbon is that most important element in one of most commonly used element and life development is distributed on the earth.Carbon materials material
Physicochemical property stablize, and have excellent electric conductivity, by preparing porous carbon materials, by carbon material intrinsic advantage with it is porous
The features such as high-specific surface area of material, high porosity, combines, and can sufficiently promote carbon material in biomedicine, photoelectricity, change
Performance in the industrial circles such as work, food.But prepare the raw material of carbon material at present mostly from petrochemical materials, it is prepared into
This height.With the fast development of global economy, increasingly depleted fossil resource is replaced using reproducible biomass as carbon source
Have become new important development direction.Since biomass is cheap, from a wealth of sources, using biomass, especially discarded agriculture
Woods biomass is the research hotspot in the following porous carbon materials research field as carbon source.Lignin is that woods source activity substance is raw
The second rich renewable organic matter of amount in postpartum residue, but fail recycling always as " dregs of a decoction " and efficiently utilize.It has been reported that
The lignin residue for claiming global pulp and paper industry to generate about 70,000,000 tons every year, but only about 5% lignin residue
It is reused as Organic chemistry sources, remaining is utilized by directly burn-up as heat source, is resulted in waste of resources and environmental pollution.
Therefore using lignin be Material synthesis with high added value functional material, meet the strategy of sustainable development and Green Chemistry and
The requirement of market economy.
For lignin as the forest resourceies that can be widely available, abundance is cheap, and phenyl third is rich in strand
Alkane and unsaturated double-bond, aromatization degree is higher, carbon content with higher, is the ideal carbon source for synthesizing porous carbon materials.Mesh
The preceding research for preparing carbon fiber as raw material using lignin receives significant attention, but prepares porous structure carbon material using it as raw material
Research it is also fewer, especially leave much to be desired in terms of its pore structure regulation.The present invention comes therefrom.
Summary of the invention
The technical issues of solution: present invention aim to address prepare in the prior art porous structure carbon material it is at high cost,
Industrial applications are difficult and pore structure is difficult to the urgent problems to be solved such as Effective Regulation, propose a kind of lignin porous structure carbon
Material and its preparation method and application.
A kind of technical solution: preparation method of lignin porous structure carbon material, comprising the following steps: (1) first will be wooden
Quality is uniformly mixed with the hydrochloric acid solution that pH value is 1 ~ 4, and the mass ratio of lignin and hydrochloric acid solution is 1:(1 ~ 20), it is heated to
100 ~ 110 DEG C, reflow treatment 12 ~ filter and collect sediment afterwards for 24 hours, at 60 DEG C be dried in vacuo 12 ~ for 24 hours, obtain precrosslink
Lignin；(2) by precrosslink lignin and triblock copolymer 1:(0.5 ~ 5 in mass ratio) it is dissolved in tetrahydrofuran and is mixed
Solution is closed, the tetrahydrofuran is 10 ~ 20 times of precrosslink lignin and triblock copolymer gross mass, adds 6mol/L's
Hydrochloric acid solution, wherein hydrochloric acid solution additional amount accounts for the 0.1 ~ 1% of mixed solution total volume, stirs evenly and is placed on 40 ~ 70 DEG C of baking ovens
Middle 4 ~ 48h of drying is then collected and is obtained solid sediment；(3) above-mentioned solid sediment is placed in the quartz ampoule of tube furnace, is led to
Enter any than mixture of inert gas and ammonia, heating carbonization is cooled to room temperature to obtain carbon material after reaction；(4) it takes out
Carbon material and chemical activating agent 1:(1 ~ 3 in mass ratio) it is uniformly mixed with mortar, and be again placed in quartz ampoule, inert gas atmosphere
1000 DEG C are warming up to 5 ~ 20 DEG C/min rate under enclosing, 10 ~ 30min is kept, is cooled to room temperature, is rinsed with deionized water, it is dry
After obtain lignin porous carbon materials.
Preferably, lignin described in step (1) is alkali lignin, enzymolysis xylogen, lignin-sulphonate, sulfomethylated lignin
At least one of hydrochlorate.
Preferably, the mass ratio of lignin described in step (1) and hydrochloric acid solution is 1:(5 ~ 15).
Preferably, triblock copolymer described in step (2) is Pluronic F-127 or Pluronic F-123, point
Son amount distribution is 1100 ~ 14600.
Preferably, the volumetric mixture ratio of inert gas described in step (3) and ammonia is 1:(0.5 ~ 1), wherein indifferent gas
Body is nitrogen or argon gas.
Preferably, the specific surface area of carbon material, specific temperature-rise period are promoted in step (3) using the method for temperature programming
Are as follows: 100 ~ 350 DEG C are warming up to 5 ~ 20 DEG C/min, keeps 30 ~ 60min；500 ~ 1000 DEG C are warming up to 10 ~ 20 DEG C/min again,
Keep 0.5 ~ 4h.
Preferably, chemical activating agent described in step (4) is sodium hydroxide, potassium hydroxide, potassium carbonate, saleratus, carbon
At least one of sour hydrogen sodium, zinc carbonate, zinc sulfate.
The lignin porous structure carbon material that the above method is prepared.
Application of the above-mentioned lignin porous structure carbon material in the electrode material of preparation supercapacitor.
The utility model has the advantages that (1) using the lignin in agriculture and forestry organic waste material as raw material, has reproducibility, from a wealth of sources, price
It is cheap, it is nontoxic, it not can cause environmental pollution.(2) with mantle plate method and ammonia is cooperated to handle, the porous structure being prepared
Carbon material has high specific surface area, can be used as the electrode material of adsorbent material or supercapacitor.
Detailed description of the invention
Fig. 1 is that the performance of lignin porous structure carbon material obtained by embodiment 3 compares figure, wherein (a) is N2 adsorption-
Desorption isothermal chart (b) is graph of pore diameter distribution.The specific surface area of lignin porous structure carbon material reaches 972.02m2/g.From
It can be seen that gained carbon material has meso-hole structure in graph of pore diameter distribution.
Specific embodiment
Embodiment 1
Alkali lignin is uniformly mixed with the hydrochloric acid solution that pH value is 2 according to mass ratio 1:10,105 DEG C of reflow treatments are heated to
It is filtered after 12h, collects sediment and be dried in vacuo 12h at 60 DEG C, obtain precrosslink lignin；By precrosslink lignin with
Pluronic F-127 1:1.6 in mass ratio is dissolved in the tetrahydrofuran of both 10 times of quality and obtains mixed solution, is added
The hydrochloric acid solution of 6mol/L, wherein hydrochloric acid solution additional amount accounts for the 0.5% of mixed solution total volume, stirs evenly and is placed on 60 DEG C
Dry 48h, then collects and obtains solid sediment in baking oven；Above-mentioned solid sediment is placed in the quartz ampoule of tube furnace, is led to
Enter argon gas, be warming up to 350 DEG C first with 20 DEG C/min, keep 30min, be then warming up to 800 DEG C with 10 DEG C/min, keeps
30min is cooled to room temperature after reaction；It takes out carbon material to be uniformly mixed according to mass ratio 1:2 with mortar with KOH, and again
It is placed in quartz ampoule, is warming up to 1000 DEG C under argon gas atmosphere with 10 DEG C/min rate, keep 10min, be cooled to room temperature, use
A large amount of deionized waters are rinsed, and obtain lignin porous structure carbon material, specific surface area 649.13m after dry2/g.By the carbon materials
Material is uniformly mixed in a small amount of ethanol water with conductive agent acetylene black, binder PTFE according to mass ratio 85:10:5, is coated in
In nickel foam, working electrode is obtained after dry.In 0.05 Ag−1Current density under the electrode specific capacitance be 125Fg−1, and in 2 Ag−1Still there is after charge and discharge 10000 times excellent cyclical stability under current density.
Embodiment 2
Alkali lignin is uniformly mixed with the hydrochloric acid solution that pH value is 2 according to mass ratio 1:10, after being heated to 105 DEG C of processing 12h
Filtering collects sediment and is dried in vacuo 12h at 60 DEG C, obtains precrosslink lignin；By precrosslink lignin and Pluronic
F-127 1:1.6 in mass ratio is dissolved in the tetrahydrofuran of both 10 times of quality and obtains mixed solution, and the salt of 6mol/L is added
Acid solution, wherein hydrochloric acid solution additional amount accounts for the 0.5% of mixed solution total volume, stirs evenly and is placed on drying in 60 DEG C of baking ovens
48h is then collected and is obtained solid sediment；Above-mentioned solid sediment is placed in the quartz ampoule of tube furnace, argon gas and ammonia are passed through
Gas, wherein the volume ratio of argon gas and ammonia is 1:0.65, is warming up to 350 DEG C first with 20 DEG C/min, keeps 30min, then with
10 DEG C/min is warming up to 800 DEG C, keeps 30min, is cooled to room temperature after reaction；Carbon material and KOH are taken out according to mass ratio
1:2 is uniformly mixed with mortar, and is again placed in quartz ampoule, is warming up to 1000 DEG C under argon atmosphere with 10 DEG C/min rate, is protected
10min is held, is cooled to room temperature, is rinsed with a large amount of deionized waters, obtains lignin porous structure carbon material, specific surface area after dry
For 753.24m2/g.By the carbon material and conductive agent acetylene black, binder PTFE according to mass ratio 85:10:5 in a small amount of ethanol water
It is uniformly mixed in solution, coated in nickel foam, obtains working electrode after dry.In 0.05 Ag−1Current density under should
The specific capacitance of electrode is 172Fg−1, and in 2 Ag−1Still there is after charge and discharge 10000 times excellent follow under current density
Ring stability.
Embodiment 3
Alkali lignin is uniformly mixed with the hydrochloric acid solution that pH value is 2 according to mass ratio 1:10, after being heated to 105 DEG C of processing 12h
Filtering collects sediment and is dried in vacuo 12h at 60 DEG C, obtains precrosslink lignin；By precrosslink lignin and Pluronic
F-127 1:1.6 in mass ratio is dissolved in the tetrahydrofuran of both 10 times of quality and obtains mixed solution, and the salt of 6mol/L is added
Acid solution, wherein hydrochloric acid solution additional amount accounts for the 0.5% of mixed solution total volume, stirs evenly and is placed on drying in 60 DEG C of baking ovens
48h is then collected and is obtained solid sediment；Above-mentioned solid sediment is placed in the quartz ampoule of tube furnace, argon gas and ammonia are passed through
Gas, wherein the volume ratio of argon gas and ammonia is 1:0.65, is warming up to 350 DEG C first with 20 DEG C/min, keeps 30min, then with
10 DEG C/min is warming up to 800 DEG C, keeps 1 h, is cooled to room temperature after reaction；Carbon material and KOH are taken out according to mass ratio 1:2
It is uniformly mixed, and is again placed in quartz ampoule with mortar, be warming up to 1000 DEG C under argon atmosphere with 10 DEG C/min rate, kept
10min is cooled to room temperature, and is rinsed with a large amount of deionized waters, obtains lignin porous structure carbon material after dry, specific surface area is
972.02m2/g.The carbon material is water-soluble in a small amount of ethyl alcohol according to mass ratio 85:10:5 with conductive agent acetylene black, binder PTFE
It is uniformly mixed in liquid, coated in nickel foam, obtains working electrode after dry.In 0.05 Ag−1Current density under the electricity
The specific capacitance of pole is 247 Fg−1, and in 2 Ag−1Still there is after charge and discharge 10000 times excellent follow under current density
Ring stability.
Embodiment 4
Alkali lignin is uniformly mixed with the hydrochloric acid solution that pH value is 2 according to mass ratio 1:10, filters, receives after reflow treatment 12h
Collection sediment is dried in vacuo 12h at 60 DEG C, obtains precrosslink lignin；Precrosslink lignin and Pluronic F-127 are pressed
Mass ratio 1:1.6 is dissolved in the tetrahydrofuran of both 10 times of quality and obtains mixed solution, and the hydrochloric acid solution of 6mol/L is added,
Wherein hydrochloric acid solution additional amount accounts for the 0.5% of mixed solution total volume, stirs evenly and is placed in 60 DEG C of baking ovens dry 48h, then
Collection obtains solid sediment；Above-mentioned solid sediment is placed in the quartz ampoule of tube furnace, is passed through argon gas and ammonia, wherein argon
The volume ratio of gas and ammonia is 1:0.65, is warming up to 350 DEG C first with 20 DEG C/min, 30min is kept, then with 10 DEG C/min liter
Temperature keeps 2 h, is cooled to room temperature after reaction to 800 DEG C；Carbon material is taken out to be mixed according to mass ratio 1:2 with mortar with KOH
Uniformly, it and is again placed in quartz ampoule, is warming up to 1000 DEG C under argon atmosphere with 10 DEG C/min rate, keep 10min, be cooled to
Room temperature is rinsed with a large amount of deionized waters, obtains lignin porous structure carbon material, specific surface area 898.51m after dry2/g。
The carbon material is mixed in a small amount of ethanol water with conductive agent acetylene black, binder PTFE according to mass ratio 85:10:5
It is even, coated in nickel foam, working electrode is obtained after dry.In 0.05 Ag−1Current density under the electrode specific capacitance
For 208 Fg−1, and in 2 Ag−1Still there is after charge and discharge 10000 times excellent cyclical stability under current density.
Claims (9)
1. a kind of preparation method of lignin porous structure carbon material, it is characterised in that the following steps are included: (1) first will be wooden
Element is uniformly mixed with the hydrochloric acid solution that pH value is 1 ~ 4, and the mass ratio of lignin and hydrochloric acid solution is 1:(1 ~ 20), it is heated to 100 ~
110 DEG C, reflow treatment 12 ~ filter and collect sediment afterwards for 24 hours, at 60 DEG C be dried in vacuo 12 ~ for 24 hours, it is wooden to obtain precrosslink
Element；(2) by precrosslink lignin and triblock copolymer 1:(0.5 ~ 5 in mass ratio) be dissolved in tetrahydrofuran obtain mixing it is molten
Liquid, the tetrahydrofuran are 10 ~ 20 times of precrosslink lignin and triblock copolymer gross mass, add the hydrochloric acid of 6mol/L
Solution, wherein hydrochloric acid solution additional amount accounts for the 0.1 ~ 1% of mixed solution total volume, stirs evenly to be placed in 40 ~ 70 DEG C of baking ovens and do
Dry 4 ~ 48h is then collected and is obtained solid sediment；(3) above-mentioned solid sediment is placed in the quartz ampoule of tube furnace, is passed through lazy
Property gas and ammonia any than mixture, heating carbonization, be cooled to room temperature to obtain carbon material after reaction；(4) carbon materials are taken out
Expect and chemical activating agent 1:(1 ~ 3 in mass ratio) it is uniformly mixed with mortar, and be again placed in quartz ampoule, under atmosphere of inert gases
1000 DEG C are warming up to 5 ~ 20 DEG C/min rate, 10 ~ 30min is kept, is cooled to room temperature, is rinsed with deionized water, is obtained after dry
To lignin porous carbon materials.
2. the preparation method of lignin porous structure carbon material according to claim 1, it is characterised in that described in step (1)
Lignin is at least one of alkali lignin, enzymolysis xylogen, lignin-sulphonate, lignosulfonates.
3. the preparation method of lignin porous structure carbon material according to claim 1, it is characterised in that described in step (1)
The mass ratio of lignin and hydrochloric acid solution is 1:(5 ~ 15).
4. the preparation method of lignin porous structure carbon material according to claim 1, it is characterised in that described in step (2)
Triblock copolymer is Pluronic F-127 or Pluronic F-123, and range of molecular weight distributions is 1100 ~ 14600.
5. the preparation method of lignin porous structure carbon material according to claim 1, it is characterised in that described in step (3)
The volumetric mixture ratio of inert gas and ammonia is 1:(0.5 ~ 1), wherein inert gas is nitrogen or argon gas.
6. the preparation method of lignin porous structure carbon material according to claim 1, it is characterised in that used in step (3)
The method of temperature programming promotes the specific surface area of carbon material, specific temperature-rise period are as follows: be warming up to 100 ~ 350 with 5 ~ 20 DEG C/min
DEG C, keep 30 ~ 60min；500 ~ 1000 DEG C are warming up to 10 ~ 20 DEG C/min again, keeps 0.5 ~ 4h.
7. the preparation method of lignin porous structure carbon material according to claim 1, it is characterised in that described in step (4)
Chemical activating agent be sodium hydroxide, potassium hydroxide, potassium carbonate, saleratus, sodium bicarbonate, zinc carbonate, in zinc sulfate at least
It is a kind of.
8. the lignin porous structure carbon material of claim 1 ~ 7 either method preparation.
9. application of the lignin porous structure carbon material described in claim 8 in the electrode material of preparation supercapacitor.
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| CN110862077A (en) * | 2019-11-19 | 2020-03-06 | 东华大学 | Preparation method of hierarchical porous carbon material rich in mesopores for supercapacitor |
| CN111747408A (en) * | 2020-07-06 | 2020-10-09 | 南京林业大学 | Processing technology for improving quality of activated carbon through sulfuric acid pretreatment |
| CN111747406A (en) * | 2020-07-06 | 2020-10-09 | 南京林业大学 | Processing technology for improving specific surface area of activated carbon through baking pretreatment |
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| CN114604870A (en) * | 2022-02-24 | 2022-06-10 | 南京智汇环境气象产业研究院有限公司 | Method for preparing foam carbon material from wood block |
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| DIPENDU SAHA等: ""Studies on Supercapacitor Electrode Material from Activated Lignin-Derived Mesoporous Carbon"", 《LANGMUIR》 * |
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| CN110862077A (en) * | 2019-11-19 | 2020-03-06 | 东华大学 | Preparation method of hierarchical porous carbon material rich in mesopores for supercapacitor |
| CN111747408A (en) * | 2020-07-06 | 2020-10-09 | 南京林业大学 | Processing technology for improving quality of activated carbon through sulfuric acid pretreatment |
| CN111747406A (en) * | 2020-07-06 | 2020-10-09 | 南京林业大学 | Processing technology for improving specific surface area of activated carbon through baking pretreatment |
| CN111747406B (en) * | 2020-07-06 | 2022-02-15 | 南京林业大学 | Processing technology for improving specific surface area of activated carbon through baking pretreatment |
| CN112216526A (en) * | 2020-09-25 | 2021-01-12 | 贵港益乐科技发展有限公司 | Biomass-based porous carbon aerogel supercapacitor electrode material and preparation method thereof |
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| CN115418002A (en) * | 2022-09-26 | 2022-12-02 | 江西师范大学 | Hydroxyl-rich lignin, preparation method and application thereof in selective adsorption and separation of ammonia |
| CN115418002B (en) * | 2022-09-26 | 2024-03-29 | 江西师范大学 | Hydroxyl-rich lignin, preparation method and application thereof in selective adsorption separation of ammonia gas |
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