CN108455561A - A kind of preparation method of paper substrate mesoporous carbon electrode material and the preparation method of electrode - Google Patents
A kind of preparation method of paper substrate mesoporous carbon electrode material and the preparation method of electrode Download PDFInfo
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- CN108455561A CN108455561A CN201810410735.XA CN201810410735A CN108455561A CN 108455561 A CN108455561 A CN 108455561A CN 201810410735 A CN201810410735 A CN 201810410735A CN 108455561 A CN108455561 A CN 108455561A
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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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- 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
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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
A kind of preparation method of paper substrate mesoporous carbon electrode material and the preparation method of electrode, belong to the preparation method field of carbon material.The present invention weighs after a certain amount of industrial filter paper, F127,3 amino-phenols, hexamethylenetetramine, trimethylbenzene and water are uniformly mixed stirring and is transferred to reaction in reaction kettle, cleans, drying is placed in tube furnace, it is carbonized in nitrogen atmosphere, it is finally cooled to room temperature, it is washed with 0.1M HCl and deionized water is washed to neutrality, it is dry.Then weigh certain mass ratio i.e. sample：It after KOH activation, and is taken out after drying in an oven, i.e. resulting materials.For the present invention by one step hydro thermal method in the carbon carbon composite of its one layer of mesoporous carbosphere of area load, surface makes it have good wetability and better ion accessibility there are hetero atoms such as N, O.Pass through the activation method of KOH so that the specific surface area and pore structure of material have apparent improvement, and specific capacity is high, good cycle.
Description
Technical field
The invention belongs to the preparation method fields of carbon material；More particularly to a kind of preparation side of paper substrate mesoporous carbon electrode material
The preparation method of method and electrode.
Background technology
In recent years, with biomass materials such as bagasse, willows, ultracapacitor carbon is directly applicable for by high-temperature calcination
Electrode material.Therefore, using biomass-based bottom as raw material, develop novel porous carbon electrode material attracted many scholars concern and
Research.
Biomass has excellent multistage porous structure, and pore diameter range is big, and distribution of pores is wide, and cheap renewable.
Moreover, biomass fiber material, after carbonization, surface has abundant functional group, especially oxygen-containing functional group such as hydroxyl, carboxylic
Base etc. assigns the good wetability of biomass fiber material surface, is conducive to wetting and ion of the electrolyte solution in electrode surface
Accessibility.But since it is derived from a wealth of sources, otherness is larger so that the structure of biomass-based carbon electrode material especially pore structure pole
Its distributional difference is big, significantly limits its application in terms of electrode material.
Invention content
It is an object of the present invention to provide a kind of preparation method of paper substrate mesoporous carbon electrode material and the preparation methods of electrode.
The invention is realized by the following technical scheme：
A kind of preparation method of paper substrate mesoporous carbon electrode material, includes the following steps：
Step 1, the industrial filter paper for weighing certain mass, F127,3- amino-phenol, hexamethylenetetramine, 1,3,5- front threes
Load weighted substance is placed in beaker after stirring 1~2h, is transferred in reaction kettle by benzene and distilled water, and setting reaction temperature is
100~180 DEG C, the reaction time 12~for 24 hours, the mixture after reaction, for use；
Step 2, the mixture obtained after reacting step 1, are cleaned 3~5 times, after filtering with absolute ethyl alcohol and deionized water
Obtained filter paper is placed in baking oven dry 10~20h, obtains sample a, for use；The filter paper is to be attached with Red-brown powder to sink
The filter paper in shallow lake；
The sample a that step 2 obtains is placed in tube furnace by step 3, and temperature-programmed reaction is carried out under the protection of nitrogen,
With 1~3 DEG C/min heating rates from room temperature be heated to 350~400 DEG C and at a temperature of keep 2~3h, then from 350~400
It DEG C is warming up to 600~800 DEG C and is cooled to room temperature after reaction in 1~3h of this temperature, obtain sample b, for use；
Step 4 washs sample b hydrochloric acid solutions and deionized water that step 3 obtains to neutrality, and filtering is placed on baking oven
Middle 10~20h of drying, obtains sample c, for use；
Sample c, KOH, the distilled water that step 5, the step 4 for weighing certain mass obtain, be placed in beaker stirring 5~
After 20min, dry complete, obtained paper substrate mesoporous carbon electrode material is transferred in baking oven.
A kind of preparation method of paper substrate mesoporous carbon electrode material of the present invention, industrial filter paper, F127,3- in step 1
The mass ratio of amino-phenol, hexamethylenetetramine, 1,3,5- trimethylbenzenes and distilled water is (0.5~1.5)：(0.5~1)：(0.4
~0.8)：(0.25~0.65)：(0.1~0.4)：18.
A kind of preparation method of paper substrate mesoporous carbon electrode material of the present invention, the oven drying temperature in step 2 are
50~100 DEG C.
A kind of preparation method of paper substrate mesoporous carbon electrode material of the present invention, step 3 Program Elevated Temperature Conditions are with 2
DEG C/min heating rates from room temperature be heated to 400 DEG C and at a temperature of keep 2.5h, be then warming up to from 400 DEG C 700 DEG C and
This temperature 2h.
A kind of preparation method of paper substrate mesoporous carbon electrode material of the present invention, hydrochloric acid solution is a concentration of in step 4
0.1M, oven drying temperature are 50~100 DEG C.
A kind of preparation method of paper substrate mesoporous carbon electrode material of the present invention, step 4 obtains in step 5 sample c,
KOH, distilled water mass ratio be 1：(2~6)：(4~10), 80~120 DEG C of oven drying temperature, drying time 12~for 24 hours.
The electrode preparation method of a kind of paper substrate mesoporous carbon electrode material of the present invention, by paper substrate mesoporous carbon electrode material
Material：Acetylene black：PTFE emulsion：Absolute ethyl alcohol is with mass ratio 8：1：1：3~5 are uniformly mixed, and obtained mixture is uniformly smeared
In foamed nickel current collector, it is placed in 100~120 DEG C of vacuum drying chamber dry 10~12h, is taken out after cooling, uses tabletting
Machine is suppressed, and working electrode is made.
A kind of electrode preparation method of paper substrate mesoporous carbon electrode material of the present invention, the quality percentage of PTFE emulsion are dense
Degree is 10%.
The smearing quality of a kind of electrode preparation method of paper substrate mesoporous carbon electrode material of the present invention, mixture is 2
~4mg/cm2。
The pressure of a kind of electrode preparation method of paper substrate mesoporous carbon electrode material of the present invention, tablet press machine is 10MPa.
The preparation method of a kind of paper substrate mesoporous carbon electrode material of the present invention, using industrial filter paper as biomass fiber original
Material, block copolymer F127 are soft template, and 3- amino-phenols are carbon source and nitrogen source, and using hydro-thermal method, one-step synthesis is made
Surface has the paper substrate mesoporous carbon electrode material of abundant meso-hole structure surface topography.
Fl27 is poloxamer, is polyoxyethylene poly-oxygen propylene aether block copolymer.
Electrode material prepared by a kind of preparation method of paper substrate mesoporous carbon electrode material of the present invention, surface is in random
Whole is powdered, and obtained paper substrate mesoporous carbon electrode material surface is coated with one layer of mesoporous carbosphere, mesoporous carbosphere
Size at 0.6~9 μm, mesoporous carbosphere and other irregular shapes form three-dimensional mutual perforative duct, duct be with
Machine is distributed and mutually runs through, and perforative duct can be conducive to the transmission of electronics, to real by carrying out surface pore structure regulation and control
Now increase the specific capacitance of electrode material.
Electrode material prepared by a kind of preparation method of paper substrate mesoporous carbon electrode material of the present invention, specific surface area can
Reach 1799m2/ g, high specific surface area make its obtain higher specific capacitance, and the application for being it on carbon electrode material provides
Basis, N-6 and N-5 account for the 67.4% of total content, and the nitrogen functional group in carbon skeleton can effectively provide fake capacitance.
Electrode prepared by a kind of paper substrate mesoporous carbon electrode material of the present invention, the capacitance of paper substrate mesoporous carbon electrode material
Come from electric double layer response and in electrode surface hetero atom nitrogen, the redox reaction of oxygen functional group, under the rate that exposes thoroughly
Also the curve that similar rectangle can be remain, showing paper substrate mesoporous carbon electrode material has the energy of quick ion-transfer-diffusion
Power and excellent high rate performance.
Electrode prepared by a kind of paper substrate mesoporous carbon electrode material of the present invention, under the current density of 0.5A g-1,
Specific capacitance can reach 396F g-1, excellent chemical property is shown, even if in 20A g-1High current density under,
215F g can be remain-1Specific capacitance, show better high rate performance.20A g-1Charge and discharge under constant current density
After 10000 circles, capacitance loss rate only has 2%.It additionally is able to find out that the coulomb rate of the material maintains essentially in 100%, has
Good electrochemical reversibility.
A kind of a kind of preparation method of paper substrate mesoporous carbon electrode material of the present invention, it is proposed that biomass material surface
The technical concept of pore structure regulation and control：Using MOLECULE DESIGN, using Self-Assembling of Block Copolymer characteristic, by hydro-thermal method in biomass
It, be carbonized by the order mesoporous assembling performed polymer of raw material (paper) surface construction at high temperature later, and block copolymer is being removed
Meanwhile micro/meso porous compound multi-stage biological matter base composite carbon electrode material is constructed, the side of chemical activation is further used later
Method can also increase the specific capacitance of electrode material while increasing its specific surface area；It is successfully prepared for paper substrate as wooden fibre
Wiki bottom material, by one step hydro thermal method its one layer of mesoporous carbosphere of area load carbon-carbon composite, surface there are N,
The hetero atoms such as O make it have good wetability and better ion accessibility.Pass through the activation method of KOH so that material
Specific surface area and pore structure have apparent improvement, obtain the carbon electrode material of high specific capacitance, high circulation stability
Material can make it have certain application prospect on electrode material for super capacitor.
A kind of preparation method of paper substrate mesoporous carbon electrode material of the present invention is carrying out surface pore structure regulation and control
Meanwhile the introducing hetero-atoms nitrogen in carbon material structure simultaneously is gone back, the doping for passing through nitrogen in surface mesoporous structure improves
The capacitance of carbon material, improves the surface wettability of carbon material, improves the chemical property of electrode material.
A kind of preparation method of paper substrate mesoporous carbon electrode material of the present invention, reaction condition is mild, and step is simple, and
It is of low cost, it lays a good foundation for its large-scale application in electrochemical electrode field.
Description of the drawings
Fig. 1 is a kind of 800 times of SEM photograph of paper substrate mesoporous carbon electrode material prepared by one method of specific implementation mode；
Fig. 2 is a kind of 4500 times of SEM photograph of paper substrate mesoporous carbon electrode material prepared by one method of specific implementation mode；
Fig. 3 is a kind of 100,000 times of TEM photos of paper substrate mesoporous carbon electrode material prepared by one method of specific implementation mode；
Fig. 4 is a kind of surface analysis curve of paper substrate mesoporous carbon electrode material prepared by one method of specific implementation mode；
Fig. 5 is a kind of 200,000 times of TEM photos of paper substrate mesoporous carbon electrode material prepared by two method of specific implementation mode；
Fig. 6 is a kind of small angle XRD curves of paper substrate mesoporous carbon electrode material prepared by two method of specific implementation mode；
Fig. 7 is a kind of big angle XRD curves of paper substrate mesoporous carbon electrode material prepared by two method of specific implementation mode；
Fig. 8 is a kind of XPS full scan collection of illustrative plates of paper substrate mesoporous carbon electrode material prepared by two method of specific implementation mode；
Fig. 9 is the N1s analytical spectras of the XPS of paper substrate mesoporous carbon electrode material prepared by two method of specific implementation mode a kind of
Figure；
Figure 10 is the N1s contents hundred of the XPS of paper substrate mesoporous carbon electrode material prepared by two method of specific implementation mode a kind of
Component；
Figure 11 is a kind of cyclic voltammetry curve of paper substrate mesoporous carbon electrode prepared by specific implementation mode tripartite's method；
Figure 12 is that a kind of low current constant current of paper substrate mesoporous carbon electrode prepared by four method method of specific implementation mode fills
Discharge curve；
Figure 13 is that a kind of high current constant current of paper substrate mesoporous carbon electrode prepared by four method method of specific implementation mode fills
Discharge curve；
Figure 14 is a kind of specific capacitance curve of paper substrate mesoporous carbon electrode prepared by four method method of specific implementation mode；
Figure 15 is a kind of cycle performance curve of paper substrate mesoporous carbon electrode prepared by four method method of specific implementation mode.
Specific implementation mode
Specific implementation mode one：
A kind of preparation method of paper substrate mesoporous carbon electrode material, includes the following steps：
Step 1, the industrial filter paper for weighing certain mass, F127,3- amino-phenol, hexamethylenetetramine, 1,3,5- front threes
Load weighted substance is placed in beaker after stirring 1h, is transferred in reaction kettle by benzene and distilled water, and setting reaction temperature is 180
DEG C, reaction time 12h, the mixture after reaction, for use；
Step 2, the mixture obtained after reacting step 1, are cleaned 5 times with absolute ethyl alcohol and deionized water, after filtering
It is placed in baking oven dry 15h to the powdered filter paper of reddish-brown precipitation is attached with, obtains sample a, for use；
The sample a that step 2 obtains is placed in tube furnace by step 3, and temperature-programmed reaction is carried out under the protection of nitrogen,
With 2 DEG C/min heating rates from room temperature be heated to 400 DEG C and at a temperature of keep 2h, be then warming up to from 400 DEG C 600 DEG C and
This temperature 2h is cooled to room temperature after reaction, obtains sample b, for use；
Step 4 washs sample b hydrochloric acid solutions and deionized water that step 3 obtains to neutrality, and filtering is placed on baking oven
Middle dry 15h, obtains sample c, for use；
Sample c, KOH, the distilled water that step 5, the step 4 for weighing certain mass obtain are placed in beaker after stirring 5min,
Dry complete, obtained paper substrate mesoporous carbon electrode material is transferred in baking oven.
A kind of preparation method of paper substrate mesoporous carbon electrode material described in present embodiment, industrial filter paper in step 1,
The mass ratio of F127,3- amino-phenol, hexamethylenetetramine, 1,3,5- trimethylbenzenes and distilled water is 1：0.75：0.5：0.5：
0.2：18.
A kind of preparation method of paper substrate mesoporous carbon electrode material described in present embodiment, the oven drying temperature in step 2
Degree is 100 DEG C.
A kind of preparation method of paper substrate mesoporous carbon electrode material described in present embodiment, hydrochloric acid solution is dense in step 4
Degree is 0.1M, and oven drying temperature is 100 DEG C.
A kind of preparation method of paper substrate mesoporous carbon electrode material described in present embodiment, the sample that step 4 obtains in step 5
Product c, KOH, distilled water mass ratio be 1：5：5,100 DEG C of oven drying temperature, drying time is for 24 hours.
Paper substrate mesoporous carbon electrode prepared by a kind of preparation method of paper substrate mesoporous carbon electrode material described in present embodiment
Material, for SEM pictures as shown in attached drawing 1, attached drawing 2, TEM pictures are as shown in Fig. 3：It is that 800 times of SEM scheme, attached drawing 2 is from attached drawing 1
4500 times of SEM figure is and made, it can be seen that obtained paper substrate mesoporous carbon electrode material surface is in random powder shape
The paper substrate mesoporous carbon electrode material surface obtained is coated with one layer of mesoporous carbosphere, and the size of mesoporous carbosphere is situated between at 0.6~9 μm
Hole carbosphere forms three-dimensional mutual perforative duct with other irregular shapes.
By 100,000 times in Fig. 3 of TEM figures it can be seen that mesoporous carbosphere forms the mutual of three-dimensional with other irregular shapes
Perforative duct is random distribution and mutually runs through that perforative duct can be conducive to the transmission of electronics, to by carrying out surface
The specific capacitance for increasing electrode material is realized in pore structure regulation and control.
Attached drawing 4 is a kind of surface analysis curve of paper substrate mesoporous carbon electrode material prepared by this embodiment party method, is utilized
N2Adsorption desorption detection method further studies its surface pore.As can be seen that Adsorption and desorption isotherms are from attached drawing 5
The combination of I type familial combined hyperlipidemia.In P/P0<Nitrogen adsorption capacity steeply rises at 0.1, this is because the process of filling micropore, in P/P0
At=0.4~0.9, nitrogen adsorption capacity continues to increase, it was demonstrated that the presence of micropore/mesoporous, and its specific surface area can reach
1799m2/ g, high specific surface area make it obtain higher specific capacitance, provide the foundation for its application on carbon electrode material.
A kind of hole parameter of paper substrate mesoporous carbon electrode material of 1 present embodiment of table
Table 1 be a kind of hole parameter of paper substrate mesoporous carbon electrode material of present embodiment, from table 1, it can be seen that material it is micro-
Hole and mesoporous volume can reach 0.73cm respectively3g-1And 0.14cm3g-1, big pore volume is advantageous to the biography of electronics
It is defeated.
Specific implementation mode two：
A kind of preparation method of paper substrate mesoporous carbon electrode material, includes the following steps：
Step 1, the industrial filter paper for weighing certain mass, F127,3- amino-phenol, hexamethylenetetramine, 1,3,5- front threes
Load weighted substance is placed in beaker after stirring 2h, is transferred in reaction kettle by benzene and distilled water, and setting reaction temperature is 150
DEG C, the reaction time for 24 hours, the mixture after reaction, for use；
Step 2, the mixture obtained after reacting step 1, are cleaned 4 times with absolute ethyl alcohol and deionized water, after filtering
It is placed in baking oven dry 15h to the powdered filter paper of reddish-brown precipitation is attached with, obtains sample a, for use；
The sample a that step 2 obtains is placed in tube furnace by step 3, and temperature-programmed reaction is carried out under the protection of nitrogen,
With 3 DEG C/min heating rates from room temperature be heated to 350 DEG C and at a temperature of keep 3h, be then warming up to from 350 DEG C 800 DEG C and
This temperature 1h is cooled to room temperature after reaction, obtains sample b, for use；
Step 4 washs sample b hydrochloric acid solutions and deionized water that step 3 obtains to neutrality, and filtering is placed on baking oven
Middle dry 15h, obtains sample c, for use；
Sample c, KOH, the distilled water that step 5, the step 4 for weighing certain mass obtain, are placed in beaker and stir 10min
Afterwards, dry complete, obtained paper substrate mesoporous carbon electrode material is transferred in baking oven.
A kind of preparation method of paper substrate mesoporous carbon electrode material described in present embodiment, industrial filter paper in step 1,
The mass ratio of F127,3- amino-phenol, hexamethylenetetramine, 1,3,5- trimethylbenzenes and distilled water is 1.5：1：0.7：0.3：0.2：
18。
A kind of preparation method of paper substrate mesoporous carbon electrode material described in present embodiment, the oven drying temperature in step 2
Degree is 80 DEG C.
A kind of preparation method of paper substrate mesoporous carbon electrode material described in present embodiment, hydrochloric acid solution is dense in step 4
Degree is 0.1M, and oven drying temperature is 100 DEG C.
A kind of preparation method of paper substrate mesoporous carbon electrode material described in present embodiment, the sample that step 4 obtains in step 5
Product c, KOH, distilled water mass ratio be 1：3：7,100 DEG C of oven drying temperature, drying time is for 24 hours.
Paper substrate mesoporous carbon electrode prepared by a kind of preparation method of paper substrate mesoporous carbon electrode material described in present embodiment
Material, 200,000 times of TEM pictures are as shown in Fig. 5：By Fig. 5 it can be seen that mesoporous carbosphere forms three-dimensional with other irregular shapes
Mutual perforative duct be random distribution and mutually to run through, perforative duct can be conducive to the transmission of electronics, to by into
The specific capacitance for increasing electrode material is realized in the regulation and control of row surface pore structure.
Paper substrate mesoporous carbon electrode prepared by a kind of preparation method of paper substrate mesoporous carbon electrode material described in present embodiment
Material, small angle XRD curves are as shown in Fig. 6：As can be seen from the figure nearby there is the diffraction maximum differentiated very well in 2 θ=0.76 °
And 2 θ=1.0~1.8 ° nearby there is broad peak, these characteristic peaks illustrate that prepared paper substrate mesoporous carbon electrode material is
Two-dimentional hexagonal phase mesoscopic structure (p6m)-.
Paper substrate mesoporous carbon electrode prepared by a kind of preparation method of paper substrate mesoporous carbon electrode material described in present embodiment
Material, big angle XRD curves are as shown in Fig. 7：As can be seen from Figure 7 in 2 θ ≈ 22 and 43 °, nearby left and right has and significantly spreads out
Peak is penetrated, agraphitic carbon (002) and (100) lattice plane are corresponded respectively to, illustrates that prepared paper substrate mesoporous carbon electrode material is deposited
In unformed shape structure.
Paper substrate mesoporous carbon electrode prepared by a kind of preparation method of paper substrate mesoporous carbon electrode material described in present embodiment
Material, XPS full scan collection of illustrative plates are as shown in Fig. 8：From Fig. 8 it can be seen that the full scan collection of illustrative plates of the sample of material is combine can be
All show three absorption peaks at 285eV, 400eV, 532eV, correspond to the peak of C1s, N1s, O1s respectively, this show nitrogen at
The doping of work(enters in a kind of paper substrate mesoporous carbon electrode material.
Paper substrate mesoporous carbon electrode prepared by a kind of preparation method of paper substrate mesoporous carbon electrode material described in present embodiment
The N1s analysis of spectra of material, XPS is as shown in Fig. 9：Attached drawing 9 further analyzes N1s spectrograms, for N1s spectrograms,
Be observed that four characteristic absorption peaks, in conjunction with can concentrate on 397.5 ± 0.2eV, 400.1 ± 0.2eV, 401.2 ± 0.3eV,
404.2+0.4eV, corresponding respectively to correspond to pyridine nitrogen (N-6) respectively, pyrroles's nitrogen/pyridone nitrogen (N-5), graphite nitrogen (N-Q) and
Oxidation of methylpyridine nitrogen (N-X), and wherein N-6 and N-5 for improve carbon material specific capacitance play critical effect, this be because
It is located at the edge of graphene layer for the nitrogen-atoms part in N-6 and N-5 structures, faraday's reaction can be promoted to generate fake capacitance.
Paper substrate mesoporous carbon electrode prepared by a kind of preparation method of paper substrate mesoporous carbon electrode material described in present embodiment
The N1s content pie graphs of material, XPS are as shown in Fig. 10：It can be seen that N-6 and N-5 account for the 67.4% of total content from figure,
It shows in a kind of paper substrate mesoporous carbon electrode material carbon skeleton of preparation method preparation of paper substrate mesoporous carbon electrode material
Nitrogen functional group fake capacitance can be effectively provided.
Paper substrate mesoporous carbon electrode prepared by a kind of preparation method of paper substrate mesoporous carbon electrode material described in present embodiment
Material,
Specific implementation mode three：
Electrode material prepared by a kind of preparation method of paper substrate mesoporous carbon electrode material according to specific implementation mode one
The electrode preparation method of material, by paper substrate mesoporous carbon electrode material：Acetylene black：PTFE emulsion：Absolute ethyl alcohol is with mass ratio 8：1：1：5
It is uniformly mixed, obtained mixture is uniformly applied in foamed nickel current collector, is placed in 120 DEG C of vacuum drying chamber dry
10h takes out after cooling, is suppressed with tablet press machine, working electrode is made.
A kind of electrode preparation method of paper substrate mesoporous carbon electrode material described in present embodiment, the quality hundred of PTFE emulsion
Divide a concentration of 10%.
A kind of electrode preparation method of paper substrate mesoporous carbon electrode material described in present embodiment, the smearing quality of mixture
For 2mg/cm2。
A kind of electrode preparation method of paper substrate mesoporous carbon electrode material described in present embodiment, the pressure of tablet press machine are
10MPa。
Electrode prepared by a kind of electrode preparation method of paper substrate mesoporous carbon electrode material described in present embodiment, 10mV
S-1 to 200mV s-1Cyclic voltammetry curve it is as shown in Fig. 11, as can be seen from Figure 11 curve is similar to rectangle, and
There is a broad peak in low potential area, comes from electric double layer response this demonstrate the capacitance of paper substrate mesoporous carbon electrode material and in electrode
Surface hetero atom nitrogen, oxygen functional group redox reaction, and from figure it can be seen that can also be kept under the rate that exposes thoroughly
The curve for similar rectangle shows ability of the paper substrate mesoporous carbon electrode material with quick ion-transfer-diffusion and excellent
High rate performance.
Specific implementation mode four：
Electrode material prepared by a kind of preparation method of paper substrate mesoporous carbon electrode material according to specific implementation mode two
The electrode preparation method of material, by paper substrate mesoporous carbon electrode material：Acetylene black：PTFE emulsion：Absolute ethyl alcohol is with mass ratio 8：1：1：5
It is uniformly mixed, obtained mixture is uniformly applied in foamed nickel current collector, is placed in 120 DEG C of vacuum drying chamber dry
10h takes out after cooling, is suppressed with tablet press machine, working electrode is made.
A kind of electrode preparation method of paper substrate mesoporous carbon electrode material described in present embodiment, the quality hundred of PTFE emulsion
Divide a concentration of 10%.
A kind of electrode preparation method of paper substrate mesoporous carbon electrode material described in present embodiment, the smearing quality of mixture
For 2mg/cm2。
A kind of electrode preparation method of paper substrate mesoporous carbon electrode material described in present embodiment, the pressure of tablet press machine are
10MPa。
Electrode prepared by a kind of electrode preparation method of paper substrate mesoporous carbon electrode material described in present embodiment, low current
Constant current charge-discharge curve is as shown in Fig. 12, it can be seen that the electrode preparation method system of paper substrate mesoporous carbon electrode material from figure
Standby electrode is in 0.5-5A g-1Under constant current charge-discharge performance, significantly it can be seen that paper substrate mesoporous carbon electrode material from figure
The constant current charge-discharge curve of electrode prepared by the electrode preparation method of material shows almost symmetrical triangular shaped, shows
The electrode material has good electrochemical reversibility.
Electrode prepared by a kind of electrode preparation method of paper substrate mesoporous carbon electrode material described in present embodiment, high current
Constant current charge-discharge curve is as shown in Fig. 13, it can be seen that the electrode preparation method system of paper substrate mesoporous carbon electrode material from figure
Standby electrode is in 10-5 0A g-1Under constant current charge-discharge performance, significantly it can be seen that paper substrate mesoporous carbon electrode material from figure
The constant current charge-discharge curve of electrode prepared by the electrode preparation method of material shows almost symmetrical triangular shaped, shows
The electrode material has good electrochemical reversibility, even if in high current density 50A g-1Under, curve also keeps good electricity
Gesture-linearly relationship shows the typical capacitance characteristic of material and good high rate performance.
Electrode prepared by a kind of electrode preparation method of paper substrate mesoporous carbon electrode material described in present embodiment, according to not
It is as shown in Fig. 14 with the specific capacitance being calculated under current density, as can be seen from the figure in the current density of 0.5A g-1
Under, the specific capacitance of material can reach 396F g-1, excellent chemical property is shown, even if in 20A g-1High current
Under density, which can also remain 215F g-1Specific capacitance, show better high rate performance.
Electrode prepared by a kind of electrode preparation method of paper substrate mesoporous carbon electrode material described in present embodiment, 20Ag-1
The cycle performance curve that charge and discharge 10000 are enclosed under constant current density is as shown in Fig. 15, it can be seen that a kind of paper substrate is situated between from figure
Hole carbon electrode material has excellent stable circulation performance, remains good capacity retention, and charge and discharge are enclosed 10000
Afterwards, capacitance loss rate only has 2%.It additionally is able to find out that the coulomb worry of the material maintains essentially in 100%, there is good electricity
Chemical invertibity.
Claims (10)
1. a kind of preparation method of paper substrate mesoporous carbon electrode material, it is characterised in that：Include the following steps：
Step 1, the industrial filter paper for weighing certain mass, F127,3- amino-phenol, hexamethylenetetramine, 1,3,5- trimethylbenzenes and
Distilled water, by load weighted substance be placed in beaker stir 1~2h after, be transferred in reaction kettle, setting reaction temperature be 100~
180 DEG C, the reaction time 12~for 24 hours, the mixture after reaction, for use；
Step 2, the mixture obtained after reacting step 1, are cleaned 3~5 times with absolute ethyl alcohol and deionized water, are obtained after filtering
Filter paper be placed in baking oven dry 10~20h, obtain sample a, for use；
The sample a that step 2 obtains is placed in tube furnace by step 3, and temperature-programmed reaction is carried out under the protection of nitrogen, with 1~
3 DEG C/min heating rates from room temperature be heated to 350~400 DEG C and at a temperature of keep 2~3h, then from 350~400 DEG C heat up
It is cooled to room temperature after reaction to 600~800 DEG C and in 1~3h of this temperature, obtains sample b, for use；
Step 4 washs sample b hydrochloric acid solutions and deionized water that step 3 obtains to neutrality, and filtering is placed in baking oven and does
Dry 10~20h obtains sample c, for use；
Sample c, KOH, the distilled water that step 5, the step 4 for weighing certain mass obtain are placed in beaker after stirring 5~20min,
Dry complete, obtained paper substrate mesoporous carbon electrode material is transferred in baking oven.
2. a kind of preparation method of paper substrate mesoporous carbon electrode material according to claim 1, it is characterised in that：In step 1
Industrial filter paper, F127,3- amino-phenol, hexamethylenetetramine, 1,3,5- trimethylbenzenes and distilled water mass ratio be (0.5~
1.5)：(0.5~1)：(0.4~0.8)：(0.25~0.65)：(0.1~0.4)：18.
3. a kind of preparation method of paper substrate mesoporous carbon electrode material according to claim 1, it is characterised in that：In step 2
Oven drying temperature be 50~100 DEG C.
4. a kind of preparation method of paper substrate mesoporous carbon electrode material according to claim 1, it is characterised in that：In step 3
Temperature programming condition be with 2 DEG C/min heating rates from room temperature be heated to 400 DEG C and at a temperature of keep 2.5h, then from 400
DEG C it is warming up to 700 DEG C and in this temperature 2h.
5. a kind of preparation method of paper substrate mesoporous carbon electrode material according to claim 1, it is characterised in that：In step 4
A concentration of 0.1M of hydrochloric acid solution, oven drying temperature are 50~100 DEG C.
6. a kind of preparation method of paper substrate mesoporous carbon electrode material according to claim 1, it is characterised in that：In step 5
The mass ratio of sample c, KOH, distilled water that step 4 obtains are 1：(2~6)：(4~10), 80~120 DEG C of oven drying temperature,
Drying time 12~for 24 hours.
7. a kind of electrode preparation method of paper substrate mesoporous carbon electrode material described in a kind of one of claim 1-6, feature exist
In：By paper substrate mesoporous carbon electrode material：Acetylene black：PTFE emulsion：Absolute ethyl alcohol is with mass ratio 8：1：1：3~5 are uniformly mixed, and obtain
To mixture be uniformly applied in foamed nickel current collector, be placed in 100~120 DEG C of vacuum drying chamber dry 10~
12h takes out after cooling, is suppressed with tablet press machine, working electrode is made.
8. a kind of electrode preparation method of paper substrate mesoporous carbon electrode material according to claim 7, it is characterised in that：PTFE
The mass percentage concentration of lotion is 10%.
9. a kind of electrode preparation method of paper substrate mesoporous carbon electrode material according to claim 7, it is characterised in that：Mixing
The smearing quality of object is 2~4mg/cm2。
10. a kind of electrode preparation method of paper substrate mesoporous carbon electrode material according to claim 7, it is characterised in that：Pressure
The pressure of piece machine is 10MPa.
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| CN109304143A (en) * | 2018-11-21 | 2019-02-05 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of meso-porous carbon material of load iron and products thereof and application |
| CN113135569A (en) * | 2021-05-31 | 2021-07-20 | 东北林业大学 | Biomass-derived grade porous carbon electrode material and preparation method thereof |
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