CN109279603A - A kind of three doped porous carbon material of nitrogen oxygen sulphur and preparation method thereof - Google Patents
A kind of three doped porous carbon material of nitrogen oxygen sulphur and preparation method thereof Download PDFInfo
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- CN109279603A CN109279603A CN201811355957.2A CN201811355957A CN109279603A CN 109279603 A CN109279603 A CN 109279603A CN 201811355957 A CN201811355957 A CN 201811355957A CN 109279603 A CN109279603 A CN 109279603A
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- 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
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- 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
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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
- H01G11/24—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
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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
- H01G11/38—Carbon pastes or blends; Binders or additives therein
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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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- 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
- H01G11/84—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
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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
Abstract
The invention discloses a kind of three doped porous carbon materials of nitrogen oxygen sulphur and preparation method thereof, belong to new energy materials field, by selecting fungi tremella as presoma, select nitrate as activator, the mass ratio for controlling tremella and activator is 1:0.1~1:5, tremella-activating mixtures are obtained after carrying out relevant treatment, it is put into tube furnace, carbonization-activation is carried out under an inert atmosphere, further in dilute hydrochloric acid, sufficiently cleaning removes impurity in distilled water, it dries in an oven, obtain three doped porous carbon material of nitrogen oxygen sulphur, preparation method is simple for the invention, cost is relatively low, obtained nitrogen oxygen sulphur three adulterates carbon material and has the open pore structure of classification, big specific surface area, it can be applied to the electrode material of supercapacitor, all there is big specific capacitance in 0~60 DEG C of test, good high rate performance and height Energy density.
Description
Technical field
The invention belongs to new energy materials fields, and in particular to a kind of high-ratio surface, abundant nitrogen oxygen sulphur element doping are more
Hole carbon material and preparation method thereof, in terms of can be applied to supercapacitor.
Background technique
Fossil energy exhaustion and climate warming are the challenges of mankind's facing.Currently, global energy requirements to clean,
Diversified, renewableization, efficient direction are developed.Therefore, developing and utilizing renewable energy is the key that solve the problems, such as this.
In existing stored energy form, supercapacitor and lithium ion battery are aroused great concern.However, supercapacitor
Opposite lithium ion battery still has lower energy density.In order to improve the energy density of supercapacitor, carbon material is usual
It is used as electrode material, is that there is controllable microstructure and pattern and high security since it is easy to get.Unfortunate
It is that, as the business electrode material of supercapacitor, conventional carbon shows low specific capacitance (in water electrolysis liquid specific capacitance
<300 F g-1, 100 ~ 120 F g of specific capacitance in organic electrolyte-1) and poor high rate performance, this is because the distortion in its duct
Limit ion transmission dynamics.
In view of the limitation of traditional commerce absorbent charcoal material in practical applications, novel carbon material is designed and prepared
The chemical property for improving supercapacitor becomes very urgent.In general, increase the pore channel of carbon material to improve ratio
Surface area can effectively improve electrochemical kinetics process.Biomass material and chemical activating agent (such as KOH) are mixed
Afterwards, it heats in an inert atmosphere, by a series of reaction, high-specific surface area and classifying porous carbon material can be obtained.Carbon materials
Material is once with the pore structure of high-specific surface area and classification, so that it may shorten ion diffusion length, mention for charge transfer reaction
For active site abundant, and promote the intercalation/deintercalation of ion, and then improves the specific capacitance and high rate performance of supercapacitor.
Therefore, designing and preparing graded porous carbon is a kind of effective strategy.In recent years, the carbon material of heteroatom doping is as super
Electrode for capacitors causes extensive interest, this is because the electron donor property of the adjustable carbon material of heteroatom is introduced,
To adjust the electricity and chemical property on its surface, and then electric conductivity is improved, enhances surface wettability, and provide additional counterfeit electricity
Hold.
Representative heteroatom such as nitrogen (N), oxygen (O), sulphur (S) and phosphorus (P) can be in a manner of singly adulterating or adulterate more
Carbon material is mixed, to change carbon material performance.Compared with the single heteroatom doping for only improving material one aspect performance, two
Kind and the doping of two or more heteroatoms can improve the overall performance of material by synergistic effect.It usually will be enriched in heterogeneous
The biomass presoma of element carries out carbonization-activation in an inert atmosphere to realize the doping of a variety of heteroatoms.Due to heterogeneous original
Son is inherited from presoma, and the functional group of generation can be evenly distributed in the surface and inside of carbon base body.This energy letter
Single doping way for effectively obtaining heteroatom can effectively improve the energy stores of carbon material electrode.
Summary of the invention
The object of the present invention is to provide a kind of three doped porous carbon materials of nitrogen oxygen sulphur and preparation method thereof, are applied to super
Grade capacitor, the biomass derived carbon electrode material are able to solve specific capacitance in the prior art and the inadequate great question of high rate performance,
It can also realize the high value added utilization of biomass, while solve the problems, such as the high production cost of electrode material for super capacitor.
To achieve the above object, the invention provides the following technical scheme:
A kind of preparation method of three doped porous carbon material of nitrogen oxygen sulphur, includes the following steps:
A) carbon matrix precursor and activator are selected: selecting fungi tremella as presoma, selects nitrate as activator；
B) it impregnates: tremella being cleaned first, is dried, then, dried tremella and nitrate are added to the water immersion 0
~48h, until activator is fully absorbed and is dispersed on tremella matrix, the mass ratio for controlling tremella and activator is 1:0.1
~1:5, is collected later, is put into -50~-10 DEG C of freeze drier and is dried, and tremella-activation is obtained
Agent composition；
C) carbonization-activation: tremella-activating mixtures that step b) is obtained are put into tube furnace, carry out carbon under an inert atmosphere
Change activation, the inert atmosphere is selected from one of argon gas or nitrogen；
D) it cleans: the sample after carbonization-activation is cleaned, sufficiently cleaning removes impurity in dilute hydrochloric acid, distilled water respectively,
It dries in an oven, obtains three doped porous carbon material of nitrogen oxygen sulphur.
Further, the activator nitrate in the step a) is LiNO3、NaNO3、KNO3、Mg(NO3)2、Ca(NO3)2
One of or it is a variety of.
Further, at 500~1300 DEG C, tube furnace heating rate controls the control of carbonization-activation temperature in the step a)
In 0.1~10 DEG C of min-1, inert gas flow is 10~100 mL min-1, soaking time is 0.5~10 h.
The present invention also proposes a kind of three doped porous carbon material of nitrogen oxygen sulphur according to made from above-mentioned preparation method, the nitrogen oxygen sulphur
Three doped porous carbon materials can be applied to the electrode material of supercapacitor.
Compared with the existing technology, beneficial effects of the present invention are as follows:
(1) using the presoma for being rich in nitrogen oxygen element sulphur, can be made by way of nitrate helper activity has the present invention
The porous carbon materials that bigger serface, abundant heteroatom adulterate, are highly suitable for the electrode material of supercapacitor；
(2) protein and thiamine that invention selects fungi tremella to contain as presoma can effectively realize nitrogen oxygen sulphur
The doping of element, and preparation method is simple for the invention, and cost is relatively low；
(3) present invention prepares three doped porous carbon material of tremella base nitrogen oxygen sulphur, the nitrogen made using nitrate helper activity method
Oxygen sulphur three adulterates carbon material and has the open pore structure of classification, big specific surface area, contains in the carbon material abundant micro-
Hole, meso-hole structure are very beneficial for the accumulation of charge and transporting for ion, this is conducive to shorten ion diffusion length, promote ion
Intercalation/deintercalation, provide active site abundant for charge transfer reaction, be the basis for obtaining good chemical property, with this
Meanwhile nitric acid salt activator can equally provide additional nitrogen-doping；
(4) present invention introducing nitrogen oxygen element sulphur in carbon material is beneficial to enhance the wetability of electrolyte, improves electric conductivity, mentions
For additional fake capacitance；
(5) three doped porous carbon material of nitrogen oxygen sulphur of the method for the present invention preparation is suitable for the electrode material of supercapacitor, 0
All there is big specific capacitance, good high rate performance and high energy density when~60 DEG C of tests.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) photo for three doped porous carbon material of nitrogen oxygen sulphur that embodiment 1 obtains.
Fig. 2 is scanning electron microscope (SEM) photo for three doped porous carbon material of nitrogen oxygen sulphur that embodiment 2 obtains.
Fig. 3 is scanning electron microscope (SEM) photo for three doped porous carbon material of nitrogen oxygen sulphur that embodiment 3 obtains.
Fig. 4 is scanning electron microscope (SEM) photo for three doped porous carbon material of nitrogen oxygen sulphur that embodiment 4 obtains.
Fig. 5 is scanning electron microscope (SEM) photo for three doped porous carbon material of nitrogen oxygen sulphur that embodiment 5 obtains.
Fig. 6 is three doped porous carbon material of nitrogen oxygen sulphur of the preparation of the embodiment of the present invention 1~5 0 oC, 100mV s-1Scanning
Cyclic voltammetry curve under rate.
Fig. 7 is three doped porous carbon material of nitrogen oxygen sulphur of the preparation of the embodiment of the present invention 1~5 0 oC, 10A g-1Electric current is close
Constant current charge-discharge curve under degree.
Fig. 8 is three doped porous carbon material of nitrogen oxygen sulphur of the preparation of the embodiment of the present invention 1~5 0 oCSpecific capacitance with electric current
The curve of variable density.
Fig. 9 is three doped porous carbon material of nitrogen oxygen sulphur of the preparation of the embodiment of the present invention 1~5 0 oCEnergy-power it is close
It writes music line.
Figure 10 is three doped porous carbon material of nitrogen oxygen sulphur of the preparation of the embodiment of the present invention 1~5 20 oC, 100 mV s-1It sweeps
Retouch the cyclic voltammetry curve under rate.
Figure 11 is three doped porous carbon material of nitrogen oxygen sulphur of the preparation of the embodiment of the present invention 1~5 20 oC, 10A g-1Electric current
Constant current charge-discharge curve under density.
Figure 12 is three doped porous carbon material of nitrogen oxygen sulphur of the preparation of the embodiment of the present invention 1~5 20 oCSpecific capacitance with electricity
The curve of current density variation.
Figure 13 is three doped porous carbon material of nitrogen oxygen sulphur of the preparation of the embodiment of the present invention 1~5 20 oCEnergy-power
Density curve.
Figure 14 is three doped porous carbon material of nitrogen oxygen sulphur of the preparation of the embodiment of the present invention 1~5 60 oC, 100mV s-1It sweeps
Retouch the cyclic voltammetry curve under rate.
Figure 15 is three doped porous carbon material of nitrogen oxygen sulphur of the preparation of the embodiment of the present invention 1~5 60 oC, 10A g-1Electric current
Constant current charge-discharge curve under density.
Figure 16 is three doped porous carbon material of nitrogen oxygen sulphur of the preparation of the embodiment of the present invention 1~5 60 oCSpecific capacitance with electricity
The curve of current density variation.
Figure 17 is three doped porous carbon material of nitrogen oxygen sulphur of the preparation of the embodiment of the present invention 1~5 60 oCEnergy-power
Density curve.
Specific embodiment
It is right below with reference to attached drawing of the invention in order to make those skilled in the art more fully understand technical solution of the present invention
Technical solution of the present invention carries out clear, complete description, and based on the embodiment in the application, those of ordinary skill in the art exist
Other similar embodiments obtained under the premise of creative work are not made, shall fall within the protection scope of the present application.
Embodiment 1: we are wash with distilled water and dry by tremella first.By dried tremella and KNO3According to quality
It is weighed than 1:1, then by KNO3It is configured to solution with 100 mL distilled water, then tremella is put into and is wherein mixed, 12 h is impregnated, puts
Enter and be dried in -30 DEG C of freeze drier, obtains dry tremella-KNO after freeze-drying3Presoma mixing
Object.Later, mixture is put into tube furnace, in 30 mL min-1N2With 3 in atmosphereoC min-1Rate be warming up to 800oC, and keep the temperature 1 h at such a temperature, etc. after cooling downs, the product of acquisition is cleaned into 12 h with the hydrochloric acid of 2 M, then with distillation
Water washing 5 times, sample is put into 80 lateroDry 12 h or more in C vacuum oven, obtain nitrogen oxygen sulphur three and adulterate porous carbon
Material.By obtained carbon material and conductive black (Super P) and adhesive (Kynoar) according to the mass ratio of 8:1:1
Mixing stirs evenly, and is mixed into muddy with 1-Methyl-2-Pyrrolidone solvent, coated on smooth electrode slice, and puts it into
To 80oIt is dry in the baking oven of C, obtain electrode for super capacitor piece.Later by two quality in the glove box full of argon gas
Identical electrode slice is assembled into symmetrical supercapacitor, and wherein electrolyte is ionic liquid (1- ethyl-3-methylimidazole tetrafluoro
Borate, EMIM BF4).
The microscopic appearance of three doped porous carbon material of tremella base nitrogen oxygen sulphur is observed in selection scanning electron microscope (SEM),
Nitrogen adsorption desorption tests its texture feature, its chemical component of X-ray photoelectron spectroscopic analysis, with 5000 electricity of Gamry in 77 K
Chem workstation tests its chemical property as electrode of super capacitor, tests 0oC、20 oC and 60oC is carried out.Fig. 1
The SEM picture of three doped porous carbon material of nitrogen oxygen sulphur is illustrated, showing the carbon material has open graded porous structure.
Fig. 6, Figure 10, Figure 14 respectively show three doped porous carbon material of nitrogen oxygen sulphur 0oC、20 oC and 60oSuper electricity is used as under C
Container electrode is in 100 mV s-1Cyclic voltammetry curve under sweep speed is in class rectangle.But with traditional electric double layer capacitance row
To exist compared to, the curve at the peak of 1.4 V or so, illustrate that the carbon material is provided simultaneously with electric double layer capacitance and fake capacitance performance,
And under this sweep speed, the cyclic voltammetry curve area of three doped porous carbon material of nitrogen oxygen sulphur is maximum, illustrates its specific capacitance
It is maximum.Fig. 7, Figure 11, Figure 15 respectively show three doped porous carbon material of tremella base nitrogen oxygen sulphur 0oC、20 oC and 60oC
It is lower to be used as electrode of super capacitor in 10 A g-1Constant current charge-discharge curve under current density, in the symmetric triangular slightly deformed
Shape shows that the material is provided simultaneously with electric double layer capacitance and fake capacitance performance, and under this current density, which adulterates more
Hole carbon material has longest discharge time, illustrates it with maximum specific capacitance.Fig. 8, Figure 12, Figure 16 respectively show the nitrogen
Three doped porous carbon material of oxygen sulphur is 0oC、20 oC and 60oUnder C as electrode of super capacitor under different current densities
Specific capacitance variation, it can be seen that three doped porous carbon material of nitrogen oxygen sulphur has good high rate performance and capacity retention ratio.Figure
9, Figure 13, Figure 17 respectively show three doped porous carbon material of nitrogen oxygen sulphur 0oC、20 oC and 60oSuper capacitor is used as under C
The energy-power density curve of device electrode, it can be seen that three doped porous carbon material of tremella base nitrogen oxygen sulphur has maximum energy
Metric density.The specific test result of the electrode material is listed in Tables 1 and 2.
Embodiment 2: the method for the present embodiment is substantially the same manner as Example 1, except that: carbonization-activation temperature becomes
500 oC, the control of tube furnace heating rate is in 0.1 DEG C of min-1, N2Atmosphere flow is 10 mL min-1, soaking time is 10 h.It should
The SEM picture of electrode material is reflected in Fig. 2.0oC、20 oC and 60oFor electrode of super capacitor in 100 mV under C
s-1Cyclic voltammetry curve under sweep speed is equally reflected in Fig. 6, Figure 10, Tu14Zhong.0oC、20 oC and 60oIt is used under C
Electrode of super capacitor is in 10 A g-1Constant current charge-discharge curve under current density is equally reflected in Fig. 7, Figure 11, Tu15Zhong.?
0 oC、20 oC and 60oFigure is equally reflected in for electrode of super capacitor variation of specific capacitance under different current densities under C
8, Figure 12, Tu16Zhong.0oC、20 oC and 60oEnergy-power density curve under C for electrode of super capacitor is equally anti-
It reflects in Fig. 9, Figure 13, Tu17Zhong.The specific test result of the electrode material is listed in Tables 1 and 2.
Embodiment 3: the method for the present embodiment is substantially the same manner as Example 1, except that: carbonization-activation temperature becomes
900 oC, the control of tube furnace heating rate is in 7 DEG C of min-1, N2Atmosphere flow is 50 mL min-1, soaking time is 2 h.The electricity
The SEM picture of pole material is reflected in Fig. 3,0oC、20 oC and 60oFor electrode of super capacitor in 100 mV s under C-1
Cyclic voltammetry curve under sweep speed is equally reflected in Fig. 6, Figure 10, Tu14Zhong, 0oC、20 oC and 60oFor surpassing under C
Grade electrode for capacitors is in 10 A g-1Constant current charge-discharge curve under current density is equally reflected in Fig. 7, Figure 11, Tu15Zhong, 0oC、20 oC and 60oUnder C for electrode of super capacitor specific capacitance under different current densities variation be equally reflected in Fig. 8,
Figure 12, Tu16Zhong, 0oC、20 oC and 60oEnergy-power density curve under C for electrode of super capacitor equally reflects
In Fig. 9, Figure 13, Tu17Zhong.The specific test result of the electrode material is listed in Tables 1 and 2.
Embodiment 4: the method for the present embodiment is substantially the same manner as Example 1, and different is simply that tremella and KNO3Quality
Than becoming 2:1, carbonization-activation temperature becomes 1000 oC, the control of tube furnace heating rate is in 10 DEG C of min-1, N2Atmosphere flow is
100 mL min-1, soaking time 0.5h.The SEM picture of the electrode material is reflected in Fig. 4,0oC、20 oC and 60oC
Down for electrode of super capacitor in 100 mV s-1Cyclic voltammetry curve under sweep speed is equally reflected in Fig. 6, Figure 10, figure
In 14,0oC、20 oC and 60oFor electrode of super capacitor in 10 A g under C-1Constant current charge-discharge under current density is bent
Line is equally reflected in Fig. 7, Figure 11, Tu15Zhong, 0oC、20 oC and 60oFor electrode of super capacitor in different electric currents under C
The variation of specific capacitance is equally reflected in Fig. 8, Figure 12, Tu16Zhong under density, 0oC、20 oC and 60oSuper capacitor is used under C
The energy-power density curve of device electrode is equally reflected in Fig. 9, Figure 13, Tu17Zhong.The electrode material is listed in Tables 1 and 2
Specific test result.
Embodiment 5: the method for the present embodiment is substantially the same manner as Example 1, and different is simply that tremella and KNO3Quality
Than becoming 2:3, carbonization-activation temperature becomes 800 oC.The SEM picture of the electrode material is reflected in Fig. 5,0oC、20 oC and
60 oFor electrode of super capacitor in 100 mV s under C-1Cyclic voltammetry curve under sweep speed is equally reflected in Fig. 6, figure
10, Tu14Zhong, 0oC、20 oC and 60oFor electrode of super capacitor in 10 A g under C-1Constant current charge and discharge under current density
Electric curve is equally reflected in Fig. 7, Figure 11, Tu15Zhong, 0oC、20 oC and 60oFor electrode of super capacitor in difference under C
The variation of specific capacitance is equally reflected in Fig. 8, Figure 12, Tu16Zhong under current density, 0oC、20 oC and 60oFor super under C
The energy-power density curve of electrode for capacitors is equally reflected in Fig. 9, Figure 13, Tu17Zhong.The electrode is listed in Tables 1 and 2
The specific test result of material.
From table 1, it is apparent that three doped porous carbon material of nitrogen oxygen sulphur of the invention has high specific surface area (up to
2590 m2 g-1), high Kong Rong (up to 1.30 cm3 g-1), the hole in structure is mainly micropore and mesoporous.So high ratio table
Area and the porous structure of layering are conducive to shorten ion diffusion length, provide active site abundant for charge transfer reaction,
And promote the intercalation/deintercalation of ion, and then improve the specific capacitance and high rate performance of supercapacitor.In addition, the carbon material has
High high nitrogen content (1.21-4.05 at%), oxygen content (4.32-7.86 at%), sulfur content (0.83-5.24 at%).This
The high heteroatom content of sample is conducive to improve the electric conductivity of carbon material, enhances carbon material surface wetability, increases additional counterfeit
Capacitor.And with the raising of carbonization-activation temperature or KNO3Content increases, and the content of heteroatom is gradually reduced, shows to realize
The auto-dope and adjustable heteroatom doping of nitrogen oxygen sulphur heteroatom.The carbon material is as super electricity as can be seen from Table 2
Container electrode is 0oC、20 oC and 60oChemical property under C.According to 0.5 A g-1Charging and discharging curve meter under current density
Calculation obtains the value of specific capacity；According to 100 A g-1Specific capacity and 0.5 A g under current density-1Specific capacity under current density
Ratio calculation obtains capacity retention ratio.Capacity retention ratio is higher, illustrate influence of the current density to electrode material with regard to smaller, it is super
The high rate performance of capacitor is better.It follows that it is a kind of ideal super that nitrogen oxygen sulphur three prepared by the present invention, which adulterates carbon material,
Grade capacitor electrode material, in EMIM BF4Specific capacitance in electrolyte is 0o0.5 A g under C-1It is high when current density is tested
Up to 165 F g-1, 20o0.5 A g under C-1Up to 170 F g when current density is tested-1, 60o0.5 A g under C-1Electric current
Up to 173 F g when density measurement-1, and there is good capacity retention ratio.Maximum energy-density is 0oUp to 50.5 W when C
h kg-1, 20oUp to 52.8 W h kg when C-1, 60oUp to 53.7 W h kg when C-1。
Table 1
Table 2
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment only includes one
A independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should will say
As a whole, the technical solutions in the various embodiments may also be suitably combined for bright book, and forming those skilled in the art can be with
The other embodiments of understanding.
Claims (5)
1. a kind of preparation method of three doped porous carbon material of nitrogen oxygen sulphur, which comprises the steps of:
A) carbon matrix precursor and activator are selected: selecting fungi tremella as presoma, selects nitrate as activator；
B) it impregnates: tremella being cleaned first, is dried, then, dried tremella and nitrate are added to the water immersion 0
~48h, until activator is fully absorbed and is dispersed on tremella matrix, the mass ratio for controlling tremella and activator is 1:0.1
~1:5, is collected later, is put into -50~-10 DEG C of freeze drier and is dried, and tremella-activation is obtained
Agent composition；
C) carbonization-activation: tremella-activating mixtures that step b) is obtained are put into tube furnace, carry out carbon under an inert atmosphere
Change activation, the inert atmosphere is selected from one of argon gas or nitrogen；
D) it cleans: the sample after carbonization-activation is cleaned, sufficiently cleaning removes impurity in dilute hydrochloric acid, distilled water respectively,
It dries in an oven, obtains three doped porous carbon material of nitrogen oxygen sulphur.
2. preparation method as described in claim 1, feature with the activator nitrate in the step a) is LiNO3、
NaNO3、KNO3、Mg(NO3)2、Ca(NO3)2One of or it is a variety of.
3. preparation method as described in claim 1, feature with the control of carbonization-activation temperature is 500 in the step c)
~1300 DEG C, tube furnace heating rate is controlled in 0.1~10 DEG C of min-1, inert gas flow is 10~100 mL min-1, protect
The warm time is 0.5~10 h.
4. three doped porous carbon material of nitrogen oxygen sulphur made from a kind of any one of -3 preparation methods according to claim 1.
5. three doped porous carbon material of nitrogen oxygen sulphur as claimed in claim 4, which is characterized in that can be applied to supercapacitor
Electrode material.
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| CN109994319A (en) * | 2019-04-11 | 2019-07-09 | 合肥工业大学 | The biomass derived carbon material and its synthetic method of a kind of nitrogen sulphur codope and application |
| CN110600713A (en) * | 2019-10-09 | 2019-12-20 | 中国科学技术大学 | Porous carbon doped anode material, preparation method thereof and alkali metal ion battery |
| CN111161904A (en) * | 2020-01-04 | 2020-05-15 | 浙江大学 | Preparation method of light high-conductivity porous conductive agent and application of light high-conductivity porous conductive agent in battery electrode |
| CN113148972A (en) * | 2021-03-03 | 2021-07-23 | 成都理工大学 | Preparation method of tremella-derived light layered porous carbonaceous wave-absorbing material |
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| CN113148972A (en) * | 2021-03-03 | 2021-07-23 | 成都理工大学 | Preparation method of tremella-derived light layered porous carbonaceous wave-absorbing material |
| CN114914098A (en) * | 2022-06-14 | 2022-08-16 | 湘潭大学 | Preparation method and application of nitrogen-oxygen-sulfur co-doped flexible carbon cloth derived from waste wet tissue |
| CN115140734A (en) * | 2022-06-22 | 2022-10-04 | 长江师范学院 | Preparation method and application of heteroatom-doped biomass porous carbon material |
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