CN108010747A - A kind of preparation method of ultracapacitor nitrogen sulphur codope activated carbon - Google Patents
A kind of preparation method of ultracapacitor nitrogen sulphur codope activated carbon Download PDFInfo
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- CN108010747A CN108010747A CN201711113732.1A CN201711113732A CN108010747A CN 108010747 A CN108010747 A CN 108010747A CN 201711113732 A CN201711113732 A CN 201711113732A CN 108010747 A CN108010747 A CN 108010747A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
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- 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
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Abstract
A kind of preparation method the present invention relates to ultracapacitor with nitrogen sulphur codope activated carbon, is specially：(1) biomass cellulose and/or lignin powder are dried to obtain desciccate in sulfuric-urea solution after immersion treatment；(2) desciccate is pre-oxidized to 1h at 250 DEG C and obtains pre-oxidation product；(3) pre-oxidation product is placed in after tube furnace at 600 DEG C charing 2h in inert atmosphere and obtains carbonizing production；(4) carbonizing production is mixed with potassium hydroxide be placed in the inert atmosphere after tube furnace at 800 DEG C activate 1h obtain activation products；(5) activation products are placed in hydrochloric acid solution and stir 24h, be dried in vacuo 12h after then being cleaned with deionized water to neutrality at 60 DEG C, that is, obtain ultracapacitor nitrogen sulphur codope activated carbon.The method of the present invention is easy to operate, nitrogen element sulphur doping ratio easy-regulating, and the specific capacitance when yield of obtained activated carbon is high and it is used as capacitor electrode material is high.
Description
Technical field
The invention belongs to electrode material for super capacitor preparation field, is related to a kind of double-doped odd jobs of ultracapacitor nitrogen sulphur
The preparation method of property charcoal.
Background technology
Ultracapacitor has that power density is big, uses as a kind of new electrochemical energy conversion and energy storage device
The features such as temperature range is wide and has extended cycle life, is widely used in the range of commercial and industrial.Electrode material is as super
The core component of level capacitor, plays an important role the performance of ultracapacitor.The electrode material of ultracapacitor can divide
For transition metal oxide material, conducting polymer materials and carbon material.Compared with carbon material, transition metal oxide material into
This costliness, conducting polymer materials cycle performance is unstable, and then conductive energy is good, specific surface area is big, chemistry for carbon material
The advantages that property is stablized and source is wide, therefore, carbon material becomes the hot spot of electrode material for super capacitor research.In numerous carbon materials
In material, biomass has obtained very high concern due to its reproducible feature.
Patent CN104401992A disclose one kind using shell class as raw material, using alkali metal as activator, by charing and
Activated carbon for electrode material for super capacitor prepared by activation method.But this method prepare activated carbon yield it is relatively low and due to
Hetero atom (N and/or S etc.) doping is not carried out to carbon material, therefore, the specific capacitance of the ultracapacitor is not high, preparation
Maximum specific capacitance of the walnut based active carbon electrode in aqueous electrolyte is 241F/g.
Document 1 (Nano Energy, 2016,19:165-175.) with document 2 (Green Chemistry, 2015,17
(3):Although being prepared for nitrogen sulphur codope activated carbon in 1668-1674.), what they were utilized is that biomass contains in itself
Nitrogen and element sulphur, the nitrogen and the amount of element sulphur being finally doped on activated carbon are nonadjustable, by taking document 2 as an example, when selection one
During kind of material, finally make nitrogen sulphur codope activated carbon to obtain nitrogen and the ratio of the molar ratio of element sulphur be definite value 2.268.
Document 3 (Journal of Power Source, 331:373-381.) by the use of sodium thiosulfate as dopant,
In pyrolytic process, sodium thiosulfate not only prepared nitrogen sulphur codope porous flake carbon as dopant but also as explosive, but
Reaction is violent, is difficult to control, and the ratio of nitrogen and the molar ratio of element sulphur is definite value 3.649, and nitrogen, the amount of element sulphur are same
It can not regulate and control.
Therefore, a kind of high yield, nitrogen element sulphur doping ratio easy-regulating are studied and is used as capacitor electrode material when ratio
The preparation method tool of the high carbon material of capacitance is of great significance.
The content of the invention
The purpose of the invention is to overcome above-mentioned the problems of the prior art, there is provided a kind of yield is high, nitrogen element sulphur is mixed
Miscellaneous ratio easy-regulating and specific capacitance high ultracapacitor nitrogen sulphur codope activated carbon when being used as capacitor electrode material
Preparation method.The preparation method of a kind of ultracapacitor nitrogen sulphur codope activated carbon of the present invention, first by biomass fiber
Element and/or lignin powder are soaked in sulfuric acid-urea liquid, then by pre-oxidizing, carbonizing and activation prepares super capacitor
Device nitrogen sulphur codope activated carbon.The present invention advances with sulfuric acid-urea liquid to biomass cellulose and/or lignin powder
Immersion treatment is carried out, the yield for the raising activated carbon that can have not only prepared, but also can be as nitrogen and the dopant of element sulphur, effectively
Improve specific capacitance during its electrode material as ultracapacitor.
In order to achieve the above object, the technical solution adopted by the present invention is：
The preparation method of a kind of ultracapacitor nitrogen sulphur codope activated carbon, by biomass cellulose and/or lignin
Pre-oxidized, carbonized and activated after powder immersion sulfuric acid-urea liquid and ultracapacitor nitrogen sulphur codope activated carbon is made.
As preferable technical solution：
A kind of preparation method of ultracapacitor nitrogen sulphur codope activated carbon as described above, the ultracapacitor are used
Yield >=31.4% of nitrogen sulphur codope activated carbon.The present invention advance with sulfuric acid-urea liquid to biomass cellulose and/or
Lignin powder carries out immersion treatment, and sulfuric acid can effectively suppress the generation of left-handed core glycan in preoxidation process, and make pre-
Oxidation reaction shifts to an earlier date, and urea liquid can then effectively facilitate the decomposition of left-handed core glycan, prevents the generation of tar, reduces pyrolysis
The speed of reaction, both produce synergistic effect, improve the yield and quality of activated carbon, and the present invention obtains compared with the prior art
Significant progress.
A kind of ultracapacitor preparation method of nitrogen sulphur codope activated carbon as described above, is prepared using same materials
During nitrogen sulphur codope activated carbon, the ratio of nitrogen and the molar ratio of element sulphur is with sulfuric acid-urine in nitrogen sulphur codope activated carbon
The rise of sulfuric acid concentration in plain solution and reduce, the ratio minimum 1.256 of the molar ratio of nitrogen and element sulphur, far below existing
There is the ratio of technology, illustrate that the content of element sulphur in nitrogen sulphur codope activated carbon is significantly improved relative to the prior art；It is described super
The maximum that level capacitor is used as specific capacitance during the electrode material of ultracapacitor with nitrogen sulphur codope activated carbon is 393F/g.Nitrogen
The Cloud Distribution of carbon atom can be changed with the heteroatomic addition such as sulphur, increase the wetability etc. of carbon material and electrolyte solution
Characteristic, is conducive to increase the chemical property of carbon material, improves faraday's capacitance during the electrode material that it is used as capacitor.This
Invention, can be by adjusting the ratio of sulfuric acid and urea in solution, so as to fulfill right by the use of sulfuric acid-urea liquid as dopant
In the control of the ratio of the nitrogen element sulphur of doping, so that specific capacitance when it is used as the electrode material of ultracapacitor also may be used
Adjust within the specific limits, overcome the defects of ratios of two kinds of elements in the prior art is directly determined to adjust by material.
Element sulphur makes that the surface polarity of activated carbon is stronger, and electric conductivity is further improved with wetability in nitrogen sulphur codope activated carbon, electrification
Performance is learned to significantly improve.For the prior art due to biological material sulfur content itself is not high, the nitrogen sulphur of preparation is double-doped
The content of element sulphur is generally relatively low in miscellaneous activated carbon, and it is double that the higher nitrogen sulphur of sulfur content can be made in method using the present invention
Dopped activated carbon.
A kind of ultracapacitor preparation method of nitrogen sulphur codope activated carbon as described above, comprises the following steps that：
(1) taken out after biomass cellulose and/or lignin powder to be soaked to 48h in sulfuric acid-urea liquid at 60 DEG C
Lower vacuum drying 12h obtains desciccate, as long as ensureing that biomass cellulose and/or lignin powder can soak completely during immersion
Not；
(2) desciccate is pre-oxidized to 1h at 250 DEG C and obtains pre-oxidation product；
(3) pre-oxidation product is placed in tube furnace, carbonizing 2h in inert atmosphere at 600 DEG C obtains carbonizing production；
(4) carbonizing production is mixed with potassium hydroxide and be placed in tube furnace, 1h is activated in the inert atmosphere at 800 DEG C
Obtain activation products；
(5) activation products are placed in hydrochloric acid solution and stir 24h, activation products are totally submerged by hydrochloric acid solution, and hydrochloric acid is molten
The effect of liquid is neutralization procedure (4) remaining potassium hydroxide, and vacuum is done at 60 DEG C after then being cleaned with deionized water to neutrality
Dry 12h, that is, obtain ultracapacitor nitrogen sulphur codope activated carbon.
A kind of ultracapacitor preparation method of nitrogen sulphur codope activated carbon as described above, the biomass cellulose
And/or lignin is one or more of walnut shell, chestnut shell and apricot shell.Biomass cellulose and/or wood of the present invention
Quality includes but not limited to this, can be that the biomass being widely present in large nature discards shell class, it is common only to enumerate some here
Material.
A kind of preparation method of ultracapacitor nitrogen sulphur codope activated carbon as described above, the sulfuric acid-urea are molten
Liquid presses 2 for the sulfuric acid solution of mass concentration 10% and the urea liquid of mass concentration 10%:What 1~6 volume ratio mixed
Solution.The concentration of workable sulfuric acid solution and urea liquid and volume ratio include but not limited to this in the present invention, only arrange here
Lift a preferable scheme.
A kind of preparation method of ultracapacitor nitrogen sulphur codope activated carbon as described above, step (3) and step (4)
In inert atmosphere be nitrogen.
A kind of preparation method of ultracapacitor nitrogen sulphur codope activated carbon as described above, in step (4), charing production
The mass ratio of thing and potassium hydroxide is 3:1.
A kind of preparation method of ultracapacitor nitrogen sulphur codope activated carbon as described above, in step (5), hydrochloric acid is molten
The concentration of liquid is 3mol/L.
Invention mechanism：
The biomass cellulose and/or lignin of the prior art were pre-oxidized in the stage, can produce left-handed core glycan, it is pre-
The oxidation later stage can resolve into inflammable material, can thus reduce the yield and quality of activated carbon.And one kind provided by the invention
The preparation method of ultracapacitor nitrogen sulphur codope activated carbon, first with sulfuric acid-urea liquid to biomass cellulose and/
Or lignin powder has carried out immersion treatment, then by pre-oxidizing, carbonizing and activate, in the process, on the one hand through over cure
Sulfuric acid in the biomass cellulose and/or lignin of acid-urea liquid immersion treatment can effectively suppress left-handed core glycan
Produce, and shift to an earlier date pre-oxidation, urea liquid can then effectively facilitate the decomposition of left-handed core glycan, prevent the production of tar
It is raw, the speed of pyrolytic reaction is reduced, both produce synergistic effect, improve the yield and quality of activated carbon, another aspect sulfuric acid-
Urea liquid can change the electron cloud point of carbon atom as the sulphur source adulterated with the hetero atom such as nitrogen source, the nitrogen and sulphur of doping
Cloth, increases the wetability of carbon material and electrolyte solution, is conducive to increase carbon material chemical property, so as to improve activated carbon
Specific capacitance during electrode material as ultracapacitor, further, since nitrogen element sulphur is by soaking sulfuric acid-urine in the present invention
What plain solution introduced is not material per se with, therefore, the ratio of two kinds of elements of nitrogen sulphur can also pass through tune in activated carbon
The concentration of section sulfuric acid-urea liquid is adjusted, the ratio for overcoming two kinds of elements in the prior art directly determined by material and
The defects of can not adjusting.
Beneficial effect：
(1) preparation method of a kind of ultracapacitor nitrogen sulphur codope activated carbon of the invention, easy to operate, raw material comes
Source is extensive, and cost is low, and can effectively improve the yield of obtained activated carbon, there is vast market prospect.
(2) preparation method of a kind of ultracapacitor nitrogen sulphur codope activated carbon of the invention, nitrogen element sulphur doping ratio
Example easy-regulating, and specific capacitance during electrode material of the obtained activated carbon as ultracapacitor is high, there is fabulous promotional value.
Brief description of the drawings
Fig. 1 is scanning electron microscope (SEM) image of nitrogen sulphur codope activated carbon prepared by the embodiment of the present invention 1；
Fig. 2 is that the x-ray photoelectron spectroscopy (XPS) of nitrogen sulphur codope nuclear activity charcoal prepared by the embodiment of the present invention 1 is composed entirely
Figure；
Fig. 3 be using the embodiment of the present invention 1 prepare nitrogen sulphur codope nuclear activity charcoal as working electrode, in three-electrode system
Under, the cyclic voltammogram under different scanning speed；
Fig. 4 be using the embodiment of the present invention 1 prepare nitrogen sulphur codope nuclear activity charcoal as working electrode, in three-electrode system
Under, the constant current charge-discharge diagram under different current densities.
Embodiment
The invention will be further elucidated with reference to specific embodiments.It is to be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed scope.
Embodiment 1
A kind of ultracapacitor preparation method of nitrogen sulphur codope activated carbon, comprises the following steps that：
(1) taking-up vacuum drying 12h at 60 DEG C is obtained after walnut shell powder to be soaked to 48h in sulfuric acid-urea liquid
Desciccate, as long as ensureing that walnut shell powder can be totally submerged during immersion, wherein sulfuric acid-urea liquid is mass concentration
10% sulfuric acid solution presses 2 with the urea liquid of mass concentration 10%:The solution that 3 volume ratio mixes；
(2) desciccate is pre-oxidized to 1h at 250 DEG C and obtains pre-oxidation product；
(3) pre-oxidation product is placed in tube furnace, carbonizing 2h in nitrogen atmosphere at 600 DEG C obtains carbonizing production；
(4) it is 3 by mass ratio:1 carbonizing production is mixed with potassium hydroxide to be placed in tube furnace, the nitrogen at 800 DEG C
1h is activated in gas atmosphere and obtains activation products；
(5) activation products are placed in the hydrochloric acid solution that concentration is 3mol/L and stir 24h, hydrochloric acid solution is complete by activation products
Full submergence, is dried in vacuo 12h at 60 DEG C after then being cleaned with deionized water to neutrality, that is, it is double to obtain ultracapacitor nitrogen sulphur
Dopped activated carbon.
Scanning electron microscope (SEM) figure of final obtained ultracapacitor nitrogen sulphur codope activated carbon, as shown in Figure 1, from
The surface of it can be seen from the figure that nitrogen sulphur codope walnut based active carbon is etched out the hole that substantial amounts of aperture is differed, and is conducive to
The activated carbon structure of high-specific surface area is formed, while is also beneficial to electrolyte ion and enters pore interior, improves chemical property.
The yield of ultracapacitor nitrogen sulphur codope activated carbon is 34.5%.Fig. 2 is that ultracapacitor prepared in embodiment 1 is used
X-ray photoelectron spectroscopy (XPS) full spectrogram of nitrogen sulphur codope activated carbon.As can be seen from the figure nitrogen, element sulphur successfully adulterate
Arrive in activated carbon, ultracapacitor is with the ratio of nitrogen and the molar ratio of element sulphur in nitrogen sulphur codope activated carbon
1.652。
By the ultracapacitor of preparation nitrogen sulphur codope activated carbon, carbon black and Kynoar according to mass ratio 8:1:1
Ratio be uniformly mixed in 1-Methyl-2-Pyrrolidone solvent, the wherein mass ratio of activated carbon and 1-Methyl-2-Pyrrolidone
For 1:20, dry 12h is equably applied on carbon paper in 60 DEG C of vacuum drying ovens using scraper, you can obtains working electrode piece.
In the KOH solution that concentration is 6mol/L, three-electrode system test, nitrogen sulphur codope activated carbon are carried out using electrochemical workstation
Electrode slice is working electrode, and platinum electrode is that mercury/mercuric oxide electrode is reference electrode, is circulated in the case where difference sweeps speed to electrode
Volt-ampere test, carries out constant current charge-discharge test under different current densities.Attached drawing 3 show prepared in embodiment 1 it is super
Cyclic voltammetry curve of the capacitor with nitrogen sulphur codope nuclear activity carbon resistance rod under different scanning rates, when sweep speed is from 5mV/
When s increases to 100mV/s, this kind of rectangular shape is still maintained, illustrates that there is good electric double layer capacitance performance.Attached drawing 4 is
Embodiment 1 is the relation for the current density and specific capacitance being calculated according to the constant current charge-discharge curve under different current densities
Curve, in 0.5A g-1Under current density, its specific capacitance is 358F/g, in 20A g-1Under high current density, specific capacitance remains as
0.5A g-1Under specific capacitance 86%, show that nitrogen sulphur codope activated carbon electrodes keep good high magnification capacitive property.Cause
This, the nitrogen sulphur codope activated carbon that the present invention obtains is a kind of fabulous super capacitance electrode material.
Comparative example 1
A kind of preparation method of activated carbon, step and embodiment 1 are basically identical, and used raw material is walnut shell powder,
But without sulfuric acid-urea liquid immersion treatment of step (1), step (2)~(5) technological parameter is consistent with embodiment 1, made
Yield for the activated carbon gone out is 23.6%, the yield for the activated carbon prepared less than the present invention.In addition, by with embodiment 1
In identical preparation work electrode slice process and test method same as Example 1 after measure its and be used as the electrode of capacitor
Specific capacitance during material is 215F/g, its specific capacitance achieves significant compared with the prior art far below the present invention, the present invention
It is progressive.
Embodiment 2~6
A kind of ultracapacitor preparation method of nitrogen sulphur codope activated carbon, substantially with embodiment 1, difference exists
In sulfuric acid-urea liquid presses different volumes for the sulfuric acid solution of mass concentration 10% from the urea liquid of mass concentration 10%
Than the solution mixed, the double-doped odd jobs of ultracapacitor nitrogen sulphur are tested after preparation according to the same manner as in Example 1
The specific capacitance of property charcoal.The volume of the sulfuric acid solution of mass concentration 10% and the urea liquid of mass concentration 10% in different embodiments
Than the ratio of the, molar ratio of the final obtained ultracapacitor yield of nitrogen sulphur codope activated carbon, nitrogen and element sulphur
It is as shown in the table with specific capacitance：
It can be seen that from the data in table when the raw material of selection is identical, can by the concentration for regulating and controlling sulfuric acid-urea liquid
To obtain the ultracapacitor nitrogen sulphur codope activated carbon of different nitrogens and element sulphur molar ratio, prior art system is overcome
The ratio of nitrogen and element sulphur molar ratio is the defects of definite value is unadjustable in standby nitrogen sulphur codope activated carbon, with sulphur
The raising of sulfuric acid concentration in acid-urea liquid, the ratio in nitrogen sulphur codope activated carbon shared by element sulphur molal quantity gradually increase,
Sulfur content is higher in nitrogen sulphur codope activated carbon, and activated carbon surface polarity is stronger, and the electric conductivity and wetability of activated carbon are got over
It is good.Sulfur content is non-adjustable in nitrogen sulphur codope activated carbon prepared by the prior art, and since element sulphur is in biological material
The reason for middle content is not high, thus in final product sulphur content it is relatively low, be unable to reach the content of the present invention.The present invention is not only real
The controllable adjustment of nitrogen sulphur codope activated carbon nitrogen and sulfur content is showed, element sulphur is also improved relative to the prior art
Content, be conducive to prepare the ultracapacitor of high specific capacitance.
Embodiment 7
A kind of ultracapacitor preparation method of nitrogen sulphur codope activated carbon, comprises the following steps that：
(1) taking-up vacuum drying 12h at 60 DEG C is obtained after chestnut shell powder to be soaked to 48h in sulfuric acid-urea liquid
Desciccate, as long as ensureing that chestnut shell powder can be totally submerged during immersion, wherein sulfuric acid-urea liquid is mass concentration
10% sulfuric acid solution presses 2 with the urea liquid of mass concentration 10%:The solution that 3 volume ratio mixes；
(2) desciccate is pre-oxidized to 1h at 250 DEG C and obtains pre-oxidation product；
(3) pre-oxidation product is placed in tube furnace, carbonizing 2h in nitrogen atmosphere at 600 DEG C obtains carbonizing production；
(4) it is 3 by mass ratio:1 carbonizing production is mixed with potassium hydroxide to be placed in tube furnace, the nitrogen at 800 DEG C
1h is activated in gas atmosphere and obtains activation products；
(5) activation products are placed in the hydrochloric acid solution that concentration is 3mol/L and stir 24h, hydrochloric acid solution is complete by activation products
Full submergence, is dried in vacuo 12h at 60 DEG C after then being cleaned with deionized water to neutrality, that is, it is double to obtain ultracapacitor nitrogen sulphur
Dopped activated carbon.
The yield of final obtained ultracapacitor nitrogen sulphur codope activated carbon is 32.4%, ultracapacitor nitrogen sulphur
The ratio of nitrogen and the molar ratio of element sulphur is 1.612 in codope activated carbon, and the process of working electrode piece is made using it
Same as Example 1 with the test method of its specific capacitance, specific capacitance is 345F/g during electrode material as ultracapacitor.
Comparative example 2
A kind of preparation method of nitrogen sulphur codope activated carbon, step and embodiment 7 are basically identical, and used raw material is plate
Chestnut shell, but without sulfuric acid-urea liquid immersion treatment of step (1), step (2)~(5) technological parameter and embodiment 7 one
Cause, the yield of prepared activated carbon is 18.5%, the yield for the activated carbon prepared less than the present invention.In addition, by with
It is measured after the process of identical preparation work electrode slice and test method same as Example 7 be used as capacitance in embodiment 7
The specific capacitance during electrode material of device is 226F/g, its specific capacitance obtains compared with the prior art far below the present invention, the present invention
Significant progress.
Embodiment 8~12
A kind of ultracapacitor preparation method of nitrogen sulphur codope activated carbon, substantially with embodiment 7, difference exists
In sulfuric acid-urea liquid presses different volumes for the sulfuric acid solution of mass concentration 10% from the urea liquid of mass concentration 10%
Than the solution mixed, the double-doped odd jobs of ultracapacitor nitrogen sulphur are tested after preparation according to the same manner as in Example 7
The specific capacitance of property charcoal.The volume of the sulfuric acid solution of mass concentration 10% and the urea liquid of mass concentration 10% in different embodiments
Than the ratio of the, molar ratio of the final obtained ultracapacitor yield of nitrogen sulphur codope activated carbon, nitrogen and element sulphur
It is as shown in the table with specific capacitance：
It can be seen that from the data in table when the raw material of selection is identical, can by the concentration for regulating and controlling sulfuric acid-urea liquid
To obtain the ultracapacitor nitrogen sulphur codope activated carbon of different nitrogens and element sulphur molar ratio, prior art system is overcome
The ratio of nitrogen and element sulphur molar ratio is the defects of definite value is unadjustable in standby nitrogen sulphur codope activated carbon, with sulphur
The raising of sulfuric acid concentration in acid-urea liquid, the ratio in nitrogen sulphur codope activated carbon shared by element sulphur molal quantity gradually increase,
Sulfur content is higher in nitrogen sulphur codope activated carbon, and activated carbon surface polarity is stronger, and the electric conductivity and wetability of activated carbon are got over
Good, sulfur content is non-adjustable in nitrogen sulphur codope activated carbon prepared by the prior art, and due to biological material sulphur member itself
The reason for cellulose content is not high, final product sulfur content is relatively low, is unable to reach the content of the present invention.The present invention not only realizes
The controllable adjustment of nitrogen sulphur codope activated carbon nitrogen and sulfur content, containing for element sulphur is also improved relative to the prior art
Amount, is conducive to prepare the ultracapacitor of high specific capacitance.
Embodiment 13
A kind of ultracapacitor preparation method of nitrogen sulphur codope activated carbon, comprises the following steps that：
(1) taking-up vacuum drying 12h at 60 DEG C is done after apricot shell powder to be soaked to 48h in sulfuric acid-urea liquid
Dry product, as long as ensureing that apricot shell powder can be totally submerged during immersion, wherein sulfuric acid-urea liquid is mass concentration 10%
The urea liquid of sulfuric acid solution and mass concentration 10% press 2:The solution that 3 volume ratio mixes；
(2) desciccate is pre-oxidized to 1h at 250 DEG C and obtains pre-oxidation product；
(3) pre-oxidation product is placed in tube furnace, carbonizing 2h in nitrogen atmosphere at 600 DEG C obtains carbonizing production；
(4) it is 3 by mass ratio:1 carbonizing production is mixed with potassium hydroxide to be placed in tube furnace, the nitrogen at 800 DEG C
1h is activated in gas atmosphere and obtains activation products；
(5) activation products are placed in the hydrochloric acid solution that concentration is 3mol/L and stir 24h, hydrochloric acid solution is complete by activation products
Full submergence, is dried in vacuo 12h at 60 DEG C after then being cleaned with deionized water to neutrality, that is, it is double to obtain ultracapacitor nitrogen sulphur
Dopped activated carbon.
The yield of final obtained ultracapacitor nitrogen sulphur codope activated carbon is 37.8%, ultracapacitor nitrogen sulphur
The ratio of nitrogen and the molar ratio of element sulphur is 1.555 in codope activated carbon, and the process of working electrode piece is made using it
Same as Example 1 with the test method of its specific capacitance, specific capacitance is 335F/g during electrode material as ultracapacitor.
Comparative example 3
A kind of preparation method of nitrogen sulphur codope activated carbon, step and embodiment 13 are basically identical, and used raw material is
Apricot shell, but without sulfuric acid-urea liquid immersion treatment of step (1), step (2)~(5) technological parameter and embodiment 13 1
Cause, the yield of prepared activated carbon is 29.3%, the yield for the activated carbon prepared less than the present invention.In addition, by with
It is measured as electricity after the process of identical preparation work electrode slice and the test method identical with embodiment 13 in embodiment 13
The specific capacitance during electrode material of container is 234F/g, its specific capacitance takes compared with the prior art far below the present invention, the present invention
Obtained significant progress.
Embodiment 14~18
A kind of ultracapacitor preparation method of nitrogen sulphur codope activated carbon, substantially with embodiment 13, difference exists
In sulfuric acid-urea liquid presses different volumes for the sulfuric acid solution of mass concentration 10% from the urea liquid of mass concentration 10%
Than the solution mixed, by the method test ultracapacitor nitrogen sulphur double-doped odd jobs identical with embodiment 13 after preparation
The specific capacitance of property charcoal.The volume of the sulfuric acid solution of mass concentration 10% and the urea liquid of mass concentration 10% in different embodiments
Than the ratio of the, molar ratio of the final obtained ultracapacitor yield of nitrogen sulphur codope activated carbon, nitrogen and element sulphur
It is as shown in the table with specific capacitance：
It can be seen that from the data in table when the raw material of selection is identical, can by the concentration for regulating and controlling sulfuric acid-urea liquid
To obtain the ultracapacitor nitrogen sulphur codope activated carbon of different nitrogens and element sulphur molar ratio, prior art system is overcome
The ratio of nitrogen and element sulphur molar ratio is the defects of definite value is unadjustable in standby nitrogen sulphur codope activated carbon, with sulphur
The raising of sulfuric acid concentration in acid-urea liquid, the ratio in nitrogen sulphur codope activated carbon shared by element sulphur molal quantity gradually increase,
Sulfur content is higher in nitrogen sulphur codope activated carbon, and activated carbon surface polarity is stronger, and the electric conductivity and wetability of activated carbon are got over
It is good, sulfur content is non-adjustable in nitrogen sulphur codope activated carbon prepared by the prior art, and due to biological material sulphur member itself
The reason for cellulose content is low, thus it is finally relatively low to sulfur content in product, it is unable to reach the content of the present invention.The present invention is not only
The controllable adjustment of nitrogen sulphur codope activated carbon nitrogen and sulfur content is realized, sulphur member is also improved relative to the prior art
The content of element, is conducive to prepare the ultracapacitor of high specific capacitance.
Embodiment 19
A kind of ultracapacitor preparation method of nitrogen sulphur codope activated carbon, comprises the following steps that：
(1) by walnut shell and chestnut shell powder (mass ratio 1:2) taken out after 48h is soaked in sulfuric acid-urea liquid
12h is dried in vacuo at 60 DEG C and obtains desciccate, as long as ensureing that walnut shell and chestnut shell powder can be totally submerged i.e. during immersion
Can, wherein sulfuric acid-urea liquid presses 2 for the sulfuric acid solution of mass concentration 10% and the urea liquid of mass concentration 10%:3 body
The solution that product ratio mixes；
(2) desciccate is pre-oxidized to 1h at 250 DEG C and obtains pre-oxidation product；
(3) pre-oxidation product is placed in tube furnace, carbonizing 2h in nitrogen atmosphere at 600 DEG C obtains carbonizing production；
(4) it is 3 by mass ratio:1 carbonizing production is mixed with potassium hydroxide to be placed in tube furnace, the nitrogen at 800 DEG C
1h is activated in gas atmosphere and obtains activation products；
(5) activation products are placed in the hydrochloric acid solution that concentration is 3mol/L and stir 24h, hydrochloric acid solution is complete by activation products
Full submergence, is dried in vacuo 12h at 60 DEG C after then being cleaned with deionized water to neutrality, that is, it is double to obtain ultracapacitor nitrogen sulphur
Dopped activated carbon.
The yield of final obtained ultracapacitor nitrogen sulphur codope activated carbon is 33.2%, ultracapacitor nitrogen sulphur
The ratio of nitrogen and the molar ratio of element sulphur is 1.622 in codope activated carbon, and the process of working electrode piece is made using it
Same as Example 1 with the test method of its specific capacitance, specific capacitance is 352F/g during electrode material as ultracapacitor.
Embodiment 20
A kind of ultracapacitor preparation method of nitrogen sulphur codope activated carbon, comprises the following steps that：
(1) by walnut shell and apricot shell powder (mass ratio 1:1) taken out after 48h is soaked in sulfuric acid-urea liquid 60
12h is dried in vacuo at DEG C and obtains desciccate, as long as ensureing that walnut shell and apricot shell powder can be totally submerged during immersion, its
Middle sulfuric acid-urea liquid presses 2 for the sulfuric acid solution of mass concentration 10% and the urea liquid of mass concentration 10%:3 volume ratio
The solution mixed；
(2) desciccate is pre-oxidized to 1h at 250 DEG C and obtains pre-oxidation product；
(3) pre-oxidation product is placed in tube furnace, carbonizing 2h in nitrogen atmosphere at 600 DEG C obtains carbonizing production；
(4) it is 3 by mass ratio:1 carbonizing production is mixed with potassium hydroxide to be placed in tube furnace, the nitrogen at 800 DEG C
1h is activated in gas atmosphere and obtains activation products；
(5) activation products are placed in the hydrochloric acid solution that concentration is 3mol/L and stir 24h, hydrochloric acid solution is complete by activation products
Full submergence, is dried in vacuo 12h at 60 DEG C after then being cleaned with deionized water to neutrality, that is, it is double to obtain ultracapacitor nitrogen sulphur
Dopped activated carbon.
The yield of final obtained ultracapacitor nitrogen sulphur codope activated carbon is 36.8%, ultracapacitor nitrogen sulphur
The ratio of nitrogen and the molar ratio of element sulphur is 1.592 in codope activated carbon, and the process of working electrode piece is made using it
Same as Example 1 with 2 test methods of its specific capacitance, specific capacitance is 348F/g during electrode material as ultracapacitor.
Embodiment 21
A kind of ultracapacitor preparation method of nitrogen sulphur codope activated carbon, comprises the following steps that：
(1) by chestnut shell and apricot shell powder (mass ratio 3:2) taken out after 48h is soaked in sulfuric acid-urea liquid 60
12h is dried in vacuo at DEG C and obtains desciccate, as long as ensureing that chestnut shell and apricot shell powder can be totally submerged during immersion, its
Middle sulfuric acid-urea liquid presses 2 for the sulfuric acid solution of mass concentration 10% and the urea liquid of mass concentration 10%:3 volume ratio
The solution mixed；
(2) desciccate is pre-oxidized to 1h at 250 DEG C and obtains pre-oxidation product；
(3) pre-oxidation product is placed in tube furnace, carbonizing 2h in nitrogen atmosphere at 600 DEG C obtains carbonizing production；
(4) it is 3 by mass ratio:1 carbonizing production is mixed with potassium hydroxide to be placed in tube furnace, the nitrogen at 800 DEG C
1h is activated in gas atmosphere and obtains activation products；
(5) activation products are placed in the hydrochloric acid solution that concentration is 3mol/L and stir 24h, hydrochloric acid solution is complete by activation products
Full submergence, is dried in vacuo 12h at 60 DEG C after then being cleaned with deionized water to neutrality, that is, it is double to obtain ultracapacitor nitrogen sulphur
Dopped activated carbon.
The yield of final obtained ultracapacitor nitrogen sulphur codope activated carbon is 35.9%, ultracapacitor nitrogen sulphur
The ratio of nitrogen and the molar ratio of element sulphur is 1.604 in codope activated carbon, and the process of working electrode piece is made using it
Same as Example 1 with the test method of its specific capacitance, specific capacitance is 333F/g during electrode material as ultracapacitor.
Embodiment 22
A kind of ultracapacitor preparation method of nitrogen sulphur codope activated carbon, comprises the following steps that：
(1) by walnut shell, chestnut shell and apricot shell powder (mass ratio 1:2:1) after soaking 48h in sulfuric acid-urea liquid
Take out the vacuum drying 12h at 60 DEG C and obtain desciccate, as long as ensureing that walnut shell, chestnut shell and apricot shell powder can during immersion
It is totally submerged, wherein sulfuric acid-urea liquid is molten for the sulfuric acid solution and the urea of mass concentration 10% of mass concentration 10%
Liquid presses 2:The solution that 3 volume ratio mixes；
(2) desciccate is pre-oxidized to 1h at 250 DEG C and obtains pre-oxidation product；
(3) pre-oxidation product is placed in tube furnace, carbonizing 2h in nitrogen atmosphere at 600 DEG C obtains carbonizing production；
(4) it is 3 by mass ratio:1 carbonizing production is mixed with potassium hydroxide to be placed in tube furnace, the nitrogen at 800 DEG C
1h is activated in gas atmosphere and obtains activation products；
(5) activation products are placed in the hydrochloric acid solution that concentration is 3mol/L and stir 24h, hydrochloric acid solution is complete by activation products
Full submergence, is dried in vacuo 12h at 60 DEG C after then being cleaned with deionized water to neutrality, that is, it is double to obtain ultracapacitor nitrogen sulphur
Dopped activated carbon.
The yield of final obtained ultracapacitor nitrogen sulphur codope activated carbon is 33.5%, ultracapacitor nitrogen sulphur
The ratio of nitrogen and the molar ratio of element sulphur is 1.663 in codope activated carbon, and the process of working electrode piece is made using it
Same as Example 1 with the test method of its specific capacitance, specific capacitance is 348F/g during electrode material as ultracapacitor.
Claims (9)
1. a kind of ultracapacitor preparation method of nitrogen sulphur codope activated carbon, it is characterized in that：By biomass cellulose and/or
Pre-oxidized, carbonized and activated after lignin powder immersion sulfuric acid-urea liquid and ultracapacitor nitrogen sulphur codope is made
Activated carbon.
2. a kind of ultracapacitor according to claim 1 preparation method of nitrogen sulphur codope activated carbon, its feature exist
In yield >=31.4% of ultracapacitor nitrogen sulphur codope activated carbon.
3. a kind of ultracapacitor according to claim 1 or 2 preparation method of nitrogen sulphur codope activated carbon, its feature
It is, when preparing nitrogen sulphur codope activated carbon using same materials, nitrogen and element sulphur rubs in nitrogen sulphur codope activated carbon
You reduce, the ratio of the molar ratio of nitrogen and element sulphur the ratio of ratio with the rise of sulfuric acid concentration in sulfuric acid-urea liquid
It is worth minimum 1.256；The ultracapacitor is used as comparing electricity during the electrode material of ultracapacitor with nitrogen sulphur codope activated carbon
The maximum of appearance is 393F/g.
4. a kind of ultracapacitor according to claim 3 preparation method of nitrogen sulphur codope activated carbon, its feature exist
In comprising the following steps that：
(1) taken out after biomass cellulose and/or lignin powder to be soaked to 48h in sulfuric acid-urea liquid at 60 DEG C very
The dry 12h of sky obtains desciccate；
(2) desciccate is pre-oxidized to 1h at 250 DEG C and obtains pre-oxidation product；
(3) pre-oxidation product is placed in tube furnace, carbonizing 2h in inert atmosphere at 600 DEG C obtains carbonizing production；
(4) carbonizing production is mixed with potassium hydroxide and be placed in tube furnace, 1h is activated in the inert atmosphere at 800 DEG C and is obtained
Activation products；
(5) activation products are placed in hydrochloric acid solution and stir 24h, after then being cleaned with deionized water to neutrality at 60 DEG C vacuum
Dry 12h, that is, obtain ultracapacitor nitrogen sulphur codope activated carbon.
5. a kind of preparation method of ultracapacitor nitrogen sulphur codope activated carbon according to claim 1,2 or 4, it is special
Sign is that the biomass cellulose and/or lignin are one or more of walnut shell, chestnut shell and apricot shell.
6. a kind of preparation method of ultracapacitor nitrogen sulphur codope activated carbon according to claim 1,2 or 4, it is special
Sign is that the sulfuric acid-urea liquid presses 2 for the sulfuric acid solution of mass concentration 10% and the urea liquid of mass concentration 10%:1
The solution that~6 volume ratio mixes.
7. a kind of ultracapacitor according to claim 4 preparation method of nitrogen sulphur codope activated carbon, its feature exist
In the inert atmosphere in step (3) and step (4) is nitrogen.
8. a kind of ultracapacitor according to claim 7 preparation method of nitrogen sulphur codope activated carbon, its feature exist
In in step (4), the mass ratio of carbonizing production and potassium hydroxide is 3:1.
9. a kind of ultracapacitor according to claim 4 preparation method of nitrogen sulphur codope activated carbon, its feature exist
In in step (5), the concentration of hydrochloric acid solution is 3mol/L.
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