CN108395490A - A kind of methods and applications of the nitrogen prepared as raw material using novel biomass base protonized ionic liquid/sulphur codope grading-hole Carbon Materials - Google Patents
A kind of methods and applications of the nitrogen prepared as raw material using novel biomass base protonized ionic liquid/sulphur codope grading-hole Carbon Materials Download PDFInfo
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- CN108395490A CN108395490A CN201810317057.2A CN201810317057A CN108395490A CN 108395490 A CN108395490 A CN 108395490A CN 201810317057 A CN201810317057 A CN 201810317057A CN 108395490 A CN108395490 A CN 108395490A
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 68
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 62
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000005864 Sulphur Substances 0.000 title claims abstract description 54
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 20
- 239000002028 Biomass Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000002994 raw material Substances 0.000 title claims abstract description 7
- 239000007772 electrode material Substances 0.000 claims abstract description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 10
- 229920001661 Chitosan Polymers 0.000 claims description 8
- 238000007711 solidification Methods 0.000 claims description 8
- 230000008023 solidification Effects 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000003303 reheating Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 5
- 238000004146 energy storage Methods 0.000 abstract description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 22
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 8
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000002336 sorption--desorption measurement Methods 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 239000007833 carbon precursor Substances 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- RZYKUPXRYIOEME-UHFFFAOYSA-N CCCCCCCCCCCC[S] Chemical compound CCCCCCCCCCCC[S] RZYKUPXRYIOEME-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
-
- 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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
-
- 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
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- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Biochemistry (AREA)
- Inorganic Chemistry (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
A kind of methods and applications of the nitrogen prepared as raw material using novel biomass base protonized ionic liquid/sulphur codope grading-hole Carbon Materials, belong to energy storage and switch technology field, the present invention, which provides a kind of novel biomass-based protonized ionic liquid, can simply, greenly prepare nitrogen/sulphur codope grading-hole Carbon Materials, and the Carbon Materials are provided simultaneously with microporous mesoporous macropore different pore structures, bigger serface, high nitrogen/sulphur atom content, high capacitive property and cyclical stability are not only presented as electrode material, but also possesses excellent resistance to mild flexible characteristic.
Description
Technical field
The invention belongs to energy storages and switch technology field, and in particular to one kind is with novel biomass base protonated ion
Liquid is the methods and applications of nitrogen/sulphur codope grading-hole Carbon Materials prepared by raw material.
Background technology
Heteroatom doping grading-hole Carbon Materials are due to micropore-mesopore-macropore different pore structures, excellent stability and big
Surface area, high content of heteroatoms is being catalyzed, and adsorbs, energy storage with convert etc. shown in each field it is huge
Potentiality.However, currently used carbon precursor and technology of preparing exist since process is cumbersome, high energy consumption, molecular composition are not fixed
A large amount of environmental pollution seriously limits the development and application of Carbon Materials.Therefore, excellent carbon precursor and rational skill are selected
Art prepares Heteroatom doping grading-hole Carbon Materials and has very important significance.
Invention content
For solve in the prior art Heteroatom doping grading-hole Carbon Materials carbon precursor and technology of preparing due to process is cumbersome,
The problems such as high energy consumption, molecular composition are not fixed, and there are a large amount of environmental pollutions.Present invention aims at provide a kind of novel life
Material matrix ionic liquid and simple, green method prepare nitrogen/sulphur codope grading-hole Carbon Materials, and the Carbon Materials are same
When have micropore-mesopore-macropore different pore structures, bigger serface, high nitrogen/sulphur atom content, not only as electrode material
High capacitive property and cyclical stability is presented, and possesses excellent resistance to mild flexible characteristic.
The above-mentioned purpose of the present invention is achieved through the following technical solutions：A kind of novel biomass base protonized ionic liquid,
For the sulfuric acid proton ionic liquid of chitosan, [Chit] [HSO can be named as4], there is following molecular structural formula：
A kind of preparation method of novel biomass base protonized ionic liquid, step are：
(1) chitosan of 10mmol (quality 1.61g) is dissolved in 40mL acetic acid, is stirred 30 minutes, make it completely
Dissolving, obtains sample A；
(2) in nitrogen protection and ice-water bath, 6mL dilute sulfuric acids are slowly added dropwise into step (1) sample A, stir 2 hours
Afterwards, it is dried in vacuo 12 hours for 60 DEG C.Obtain sulfuric acid proton ionic liquid i.e. [Chit] [HSO of chitosan4], it is at normal temperatures
Pale yellow powder shape.
Preferably, acetic acid volume ratio is 3% in step (2).
Preferably, a concentration of 1.7mol/L of dilute sulfuric acid described in step (2).
The nitrogen prepared as raw material using the novel biomass base protonized ionic liquid of above-mentioned preparation/sulphur codope grading-hole charcoal
The method of material, step are：
(1) by the sulfuric acid proton ionic liquid of chitosan, mesoporous soft template F127, macropore soft template dodecyl sulphate
Sodium is with 1:0.88:0.88 mass ratio is ground to uniformly, obtains sample B；
(2) sample B in step (1) is moved into 160 DEG C of solidifications in reaction kettle and for 24 hours, obtains sample C；
(3) sample C in step (2) is placed in tube furnace to heat up with 5 DEG C per minute, is pyrolyzed after being warming up to 600 DEG C 1 small
When, it is continuously heating to 1 hour of 900 DEG C of reheating solutions later, is cooled to room temperature, obtains nitrogen/sulphur codope grading-hole Carbon Materials.
Nitrogen/nitrogen of sulphur codope grading-hole Carbon Materials and the constituent content of sulphur prepared by the above method is respectively 5.07%~
5.31% and 2.91%~3.02%.
Nitrogen/sulphur codope grading-hole Carbon Materials prepared by the above method are -20 DEG C and 100 DEG C in temperature and curvature is
At 180 °, capacitive property remains unchanged substantially.
It is applied to ultracapacitor using the nitrogen of above-mentioned preparation/sulphur codope grading-hole Carbon Materials as electrode material.
Compared with prior art, beneficial effects of the present invention：
1, simple using novel biomass-based protonized ionic liquid, greenly prepare nitrogen/sulphur codope grading-hole charcoal
Material, the Carbon Materials are provided simultaneously with micropore-mesopore-macropore different pore structures, bigger serface, high nitrogen/sulphur atom content.Its
In, the constituent content of nitrogen and sulphur can respectively reach 5.31% and 3.02%；
2, nitrogen/sulphur codope grading-hole Carbon Materials prepared by the present invention are applied to ultracapacitor, tool as electrode material
It is 0.5A g to have higher capacitive property and cyclical stability, current density-1When, specific capacitance is up to 296F g-1, increase electric current
Density is to 20A g-1, specific capacitance is still positively retained at 170F g-1, and recycle 5000 times, capacitance loss rate is almost nil；
3 and the Carbon Materials possess excellent resistance to mild flexible characteristic, temperature be -20 DEG C and 100 DEG C and curvature
When being 180 °, capacitive property remains unchanged substantially.
Description of the drawings
The nitrogen that Fig. 1 is prepared the present invention provides embodiment 1/sulphur codope grading-hole Carbon Materials scanning electron microscope (SEM) photograph；
The nitrogen that Fig. 2 is prepared the present invention provides embodiment 1/sulphur codope grading-hole Carbon Materials transmission electron microscope picture；
The nitrogen that Fig. 3 is prepared the present invention provides embodiment 1/sulphur codope grading-hole Carbon Materials x-ray photoelectron spectroscopy figure；
The nitrogen that Fig. 4 is prepared the present invention provides embodiment 1/sulphur codope grading-hole Carbon Materials difference sweeps the cyclic voltammetric of speed
Curve spectrum；
The nitrogen that Fig. 5 is prepared the present invention provides embodiment 1/sulphur codope grading-hole Carbon Materials cyclical stability collection of illustrative plates；
The nitrogen that Fig. 6 is prepared the present invention provides embodiment 1/sulphur codope grading-hole Carbon Materials heat resistance test map；
The nitrogen that Fig. 7 is prepared the present invention provides embodiment 1/sulphur codope grading-hole Carbon Materials resistance to bend(ing) energy test chart
Spectrum；
The nitrogen adsorption desorption curve for the Carbon Materials that Fig. 8 is prepared the present invention provides embodiment 1, comparative example 1 and comparative example 2
(in figure：N/S-HPCM indicates that nitrogen/sulphur codope grading-hole Carbon Materials, N/S-PCM prepared by embodiment 1 indicate prepared by comparative example 1
Nitrogen sulphur codope porous carbon material, N/S-CM indicate comparative example 2 prepare nitrogen sulphur codope Carbon Materials)；
The present invention provides the cyclic voltammetry curve test charts that embodiment 1, comparative example 1 and comparative example 2 prepare Carbon Materials by Fig. 9
Spectrum is (in figure：N/S-HPCM indicates that nitrogen/sulphur codope grading-hole Carbon Materials, N/S-PCM prepared by embodiment 1 indicate that comparative example 1 is made
The nitrogen sulphur codope Carbon Materials of standby nitrogen sulphur codope porous carbon material, the N/S-CM expression preparations of comparative example 2).
Specific implementation mode：
In order to better understand the present invention, with reference to embodiment and description of the drawings in the present invention is further explained
Hold, but present disclosure is not limited only to following embodiments.
Embodiment 1
The preparation method of nitrogen/sulphur codope grading-hole Carbon Materials
The chitosan of 10mmol (quality 1.61g) is dissolved in the acetic acid that 40mL volume ratios are 3%, stirs 30 points
Clock makes it completely dissolved.In nitrogen protection and ice-water bath, it is a concentration of in the solution being completely dissolved 6mL to be slowly added dropwise
The dilute sulfuric acid of 1.7mol/L.After stirring 2 hours, 60 DEG C are dried in vacuo 12 hours, obtain [Chit] [HSO4].Molecular structural formula
It is as follows：
Then, by [Chit] [HSO4] with F127, lauryl sodium sulfate according to 1:0.88:The grinding of 0.088 mass ratio is equal
After even, 160 DEG C of 24 hours of solidification in reaction kettle are moved to.The sample that solidification obtains is placed in tube furnace to heat up with 5 DEG C per minute,
It is pyrolyzed 1 hour after being warming up to 600 DEG C, is continuously heating to 1 hour of 900 DEG C of reheating solutions later, is cooled to room temperature, obtains
Nitrogen/sulphur codope grading-hole Carbon Materials.
Nitrogen/sulphur codope grading-hole Carbon Materials prepared by the present embodiment 1 are scanned Electronic Speculum, transmission electron microscope and X-ray
Photoelectron Spectroscopy Experiment.
Nitrogen prepared by the present embodiment 1/sulphur codope grading-hole Carbon Materials are applied to ultracapacitor as electrode material,
The different cyclic voltammetry curves swept under speed and cyclical stability test are carried out, and to nitrogen manufactured in the present embodiment/sulphur codope point
Grade hole Carbon Materials heat resistance and resistance to bend(ing) can be tested.
Experimental result and its effect：
Fig. 1 is nitrogen/sulphur codope grading-hole Carbon Materials scanning electron microscope (SEM) photograph prepared by embodiment 1, the nitrogen/sulphur codope classification
Hole Carbon Materials show apparent cellular structures.
Fig. 2 is the transmission electron microscope picture of nitrogen/sulphur codope grading-hole Carbon Materials prepared by embodiment 1, the nitrogen/sulphur codope point
The transmission electron microscope picture of grade hole Carbon Materials shows unordered vermiform channel, shows that abundant hole exists.
Fig. 3 is the x-ray photoelectron spectroscopy figure of nitrogen/sulphur codope grading-hole Carbon Materials prepared by embodiment 1, the nitrogen/sulphur
The x-ray photoelectron spectroscopy of codope grading-hole Carbon Materials shows four apparent peaks in 283.9eV, 399.2eV, 162.5eV
And 531.9eV, corresponding C 1s, N 1s, S 2p and O 1s, show that carbon, nitrogen, oxygen, element sulphur are present in the nitrogen/sulphur codope classification
In the Carbon Materials of hole, the constituent content of nitrogen and sulphur can be up to 5.31% and 3.02% respectively.
Fig. 4 is that the nitrogen/sulphur codope grading-hole Carbon Materials for preparing embodiment 1 are applied to super capacitor as electrode material
Device, difference sweep the cyclic voltammetry curve under speed, the feature of class rectangle are showed under speed in small sweep, even if sweep speed increases
To 100mv s-1, only there is small variation, shows ideal electric double layer capacitance behavior in cyclic voltammetry curve class rectangle feature.
Fig. 5 is that the nitrogen/sulphur codope grading-hole Carbon Materials for preparing embodiment 1 are applied to super capacitor as electrode material
Device, difference sweep cyclical stability test map under speed, when sweep speed is 100mv s-1When, continuous cycle 5000 times, electricity
It is almost nil to hold loss late, it is meant that remarkable stability.
Fig. 6 and Fig. 7 is that the nitrogen/sulphur codope grading-hole Carbon Materials for preparing embodiment 1 are applied to surpass as electrode material
Grade capacitor, when temperature is -20 DEG C, 100 DEG C and when curvature is 180 °, capacitive property only has small variation, performance
Go out remarkable resistance to mild flexible characteristic.
Comparative example 1
[Chit][HSO4] preparation method is identical with embodiment 1, only lauryl sodium sulfate in embodiment 1 is gone
Fall, by [Chit] [HSO4] with F127 according to 1:After the grinding uniformly of 0.88 mass ratio, it is 24 small to move to 160 DEG C of solidifications in reaction kettle
When.The obtained sample of solidification is placed in tube furnace to heat up with 5 DEG C per minute, 1 hour is pyrolyzed after being warming up to 600 DEG C, it is subsequent
It is continuous to be warming up to 1 hour of 900 DEG C of reheating solutions, it is cooled to room temperature, obtained nitrogen sulphur codope porous carbon material.
Comparative example 2
[Chit][HSO4] preparation method is identical with embodiment 1, only by F127 in embodiment 1 and dodecyl sulphur
Sour sodium removes, and takes [Chit] [HSO4] 160 DEG C of 24 hours of solidification in reaction kettle are moved to, wherein [Chit] [HSO4] and embodiment 1
In [Chit] [HSO4] identical.The sample that solidification obtains is placed in tube furnace to heat up with 5 DEG C per minute, it is hot after being warming up to 600 DEG C
1 hour is solved, 1 hour of 900 DEG C of reheating solutions is continuously heating to later, is cooled to room temperature, obtained nitrogen sulphur codope raw material of wood-charcoal
Material.
According to embodiment 1, comparative example 1 and comparative example 2 it is found that there is no F127 or F127 and lauryl sodium sulfate
When be only capable of obtaining that nitrogen sulphur codope is porous or micropore carbon material, cannot obtain being provided simultaneously with micropore-mesopore-macropore three-level hole
Nitrogen/sulphur codope grading-hole Carbon Materials.
Carbon Materials prepared by embodiment 1, comparative example 1 and comparative example 2 carry out nitrogen adsorption desorption characterization, and as electrode material
Material is applied to ultracapacitor and carries out cyclic voltammetry curve test.
Experimental result and its effect：Fig. 8 is the nitrogen adsorption desorption that embodiment 1, comparative example 1 and comparative example 2 prepare Carbon Materials
The nitrogen adsorption desorption curve of curve, embodiment 1 shows IV type thermoisopleths, and carries apparent H4 types hysteresis loop, and adsorbance
It is higher, show that nitrogen sulphur codope Carbon Materials prepared by embodiment 1 have apparent classifying porous feature and big specific surface area, and it is right
The nitrogen adsorption desorption curve of 1 comparative example 2 of ratio shows unconspicuous classification hole characteristic and pore characteristics respectively, and adsorbance compared with
Low specific surface area is smaller.
Fig. 9 is that Carbon Materials prepared by embodiment 1, comparative example 1 and comparative example 2 are applied to super electricity respectively as electrode material
Container is 50mv s in sweep speed-1When, embodiment 1, comparative example 1 and 2 cyclic voltammetry curve show different shapes and
Region area.Nitrogen/sulphur codope grading-hole Carbon Materials that simultaneously prepared by embodiment 1, show apparent class rectangle cyclic voltammetric
Curve, and region area is maximum, shows best electrochemical behavior.
Embodiment 1 is obtained nitrogen/sulphur codope grading-hole Carbon Materials to test applied to ultracapacitor, performance is in electric current
Density is 1A g-1When, specific capacitance is up to 228F g-1.And the Carbon Materials that comparative example 1 and comparative example 2 obtain are applied to super electricity
Container tests its performance, is 1A g in current density-1, specific capacitance is respectively 141F g-1With 86F g-1.Its performance far away from
Nitrogen/sulphur codope grading-hole Carbon Materials are applied to ultracapacitor.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should all cover in protection scope of the present invention.
Claims (8)
1. a kind of novel biomass base protonized ionic liquid, which is characterized in that it is the sulfuric acid proton ionic liquid of chitosan,
With following molecular structural formula：
2. a kind of preparation method of novel biomass base protonized ionic liquid described in claim 1, which is characterized in that it is walked
Suddenly it is：
(1) chitosan of 10mmol is dissolved in 40mL acetic acid, stirs 30 minutes, makes it completely dissolved, obtain sample A；
(2) in nitrogen protection and ice-water bath, 6mL dilute sulfuric acids are slowly added dropwise into step (1) sample A, after stirring 2 hours,
60 DEG C are dried in vacuo 12 hours, obtain the sulfuric acid proton ionic liquid of chitosan.
3. a kind of preparation method of novel biomass base protonized ionic liquid according to claim 2, which is characterized in that
Acetic acid volume ratio is 3% in step (2).
4. a kind of preparation method of novel biomass base protonized ionic liquid according to claim 2, which is characterized in that
A concentration of 1.7mol/L of dilute sulfuric acid described in step (2).
5. using a kind of nitrogen/sulphur codope that novel biomass base protonized ionic liquid is prepared as raw material described in claim 1
The method of grading-hole Carbon Materials, which is characterized in that its step is：
(1) by the sulfuric acid proton ionic liquid of chitosan, mesoporous soft template F127, macropore soft template lauryl sodium sulfate with
1:0.88:0.88 mass ratio is ground to uniformly, obtains sample B；
(2) sample B in step (1) is moved into 160 DEG C of solidifications in reaction kettle and for 24 hours, obtains sample C；
(3) the sample C in step (2) is placed in tube furnace to heat up with 5 DEG C per minute, 1 hour is pyrolyzed after being warming up to 600 DEG C,
It is continuously heating to 1 hour of 900 DEG C of reheating solutions later, is cooled to room temperature, obtains nitrogen/sulphur codope grading-hole Carbon Materials.
6. nitrogen/sulphur codope grading-hole Carbon Materials prepared by claim 5 method, which is characterized in that the nitrogen/sulphur codope point
The nitrogen of grade hole Carbon Materials and the constituent content of sulphur are respectively 5.07%~5.31% and 2.91%~3.02%.
7. nitrogen/sulphur codope grading-hole Carbon Materials prepared by claim 5 method, which is characterized in that the nitrogen/sulphur codope point
Grade hole Carbon Materials possess excellent resistance to mild flexible characteristic, when temperature is -20 DEG C and 100 DEG C and curvature is 180 °, electricity
Capacitive can remain unchanged substantially.
8. the application of nitrogen/sulphur codope grading-hole Carbon Materials described in claim 5, which is characterized in that the nitrogen/sulphur to be co-doped with
Miscellaneous grading-hole Carbon Materials are applied to ultracapacitor as electrode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810317057.2A CN108395490B (en) | 2018-04-10 | 2018-04-10 | Method for preparing nitrogen/sulfur co-doped hierarchical porous carbon material by taking biomass-based protonated ionic liquid as raw material and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810317057.2A CN108395490B (en) | 2018-04-10 | 2018-04-10 | Method for preparing nitrogen/sulfur co-doped hierarchical porous carbon material by taking biomass-based protonated ionic liquid as raw material and application |
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| CN110759326A (en) * | 2019-10-10 | 2020-02-07 | 延边大学 | Doped porous carbon material, preparation method thereof and porous carbon-based electrode material |
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| CN110828838A (en) * | 2019-11-22 | 2020-02-21 | 河北师范大学 | Preparation method of palladium-based catalyst with particle size larger than 10 microns and snowflake ball morphology |
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