CN104445144A - Nitrogen-sulfur double-doped mesoporous carbon electrode material as well as preparation method and application thereof - Google Patents

Nitrogen-sulfur double-doped mesoporous carbon electrode material as well as preparation method and application thereof Download PDF

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CN104445144A
CN104445144A CN201410647456.7A CN201410647456A CN104445144A CN 104445144 A CN104445144 A CN 104445144A CN 201410647456 A CN201410647456 A CN 201410647456A CN 104445144 A CN104445144 A CN 104445144A
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mesoporous carbon
carbon electrode
electrode material
nitrogen
sulphur codope
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乔锦丽
陈文照
石晶晶
朱泰山
王强
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Donghua University
State Grid Shanghai Electric Power Co Ltd
National Dong Hwa University
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Donghua University
State Grid Shanghai Electric Power Co Ltd
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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 nitrogen-sulfur double-doped mesoporous carbon electrode material as well as a preparation method and application thereof. A precursor of the electrode material comprises the following components in percentage by mass: 20%-85% of a template agent, 10%-75% of a nitrogen-containing compound and 5%-50% of a transition metal salt. The preparation method comprises the following steps: dissolving the template agent, the nitrogen-containing compound and the transition metal salt in a solvent, so as to obtain the precursor; carrying out calcination reduction on the precursor to obtain a primary carbonized material; carrying out acid pickling on the primary carbonized material to obtain a nitrogen-containing mesoporous carbon material; carrying out acid pickling and calcination reduction again, so as to obtain the nitrogen-sulfur double-doped mesoporous carbon electrode material. The application of the nitrogen-sulfur double-doped mesoporous carbon electrode material in a supercapacitor comprises the following steps: transferring a mixed solution of the electrode material, acetylene black, a binder and a dispersant to a glassy carbon electrode; carrying out three-electrode system testing in electrolyte solutions of different concentrations by virtue of an electrochemical workstation. The nitrogen-sulfur double-doped mesoporous carbon electrode material is of a hierarchical pore structure, has a high specific surface area and is an excellent supercapacitor material.

Description

A kind of nitrogen sulphur codope mesoporous carbon electrode material, preparation method and application
Technical field
The invention belongs to the preparation and application field of electrode material for super capacitor, particularly a kind of nitrogen sulphur codope mesoporous carbon electrode material for super capacitor, preparation method and application.
Background technology
Ultracapacitor have energy density high, have extended cycle life, the feature such as charge-discharge velocity is fast, be widely used in many fields as portable electric appts, the memory field such as standby system, uninterruptible power supply.Moreover, there are huge potentiality in the acceleration of hybrid vehicle with cooperating with fuel cell in braking ability conversion etc.According to the difference of energy storage principle, ultracapacitor can be divided into double layer capacitor and pseudocapacitors.The electrode materials mainly various high-specific surface area carbon material of double layer capacitor, the electrode materials of pseudocapacitors is mainly metal oxide and conductive polymers.Wherein carbon material has high-specific surface area, low cost, the advantage such as to have extended cycle life and be subject to extensive concern.But its pore structure mixed causes electrolyte ion to can not get effectively utilizing and limits the space of hole wall intermediate ion, thus limits its ratio capacitance and charge discharge performance.
It has been generally acknowledged that, high-specific surface area, suitable hole dimension and structure are conducive to the transmission of lyate ion, and then improve the catalytic activity of catalyzer, realize higher ratio capacitance.The inventive method utilizes template to obtain the carbon material of controlled architecture, specific morphology.Meso-porous carbon material further by Template synthesis carries out the codope of nitrogen sulphur, while the specific surface area greatly improving doping carbon, improve active site density and lattice imperfection, thus not only can improve the dispersiveness of water in mesoporous carbon, and mesoporous carbon local current densities can be changed, improve the electron transmission of mesoporous carbon, reduce specific resistance.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of super capacitor material nitrogen sulphur codope mesoporous carbon, be hierarchical porous structure and there is very high specific surface area by the method getable nitrogen sulphur codope mesoporous carbon electrode material, to improve ratio capacitance and cyclical stability.
In order to solve the problems of the technologies described above, the invention provides a kind of nitrogen sulphur codope mesoporous carbon electrode material, it is characterized in that, the presoma of described electrode materials comprise the template of by percentage to the quality 20 ~ 85% based on presoma total mass, the nitrogenous compound of 10 ~ 75% and 5 ~ 50% transition metal salt.
Preferably, the nano silicon of described template to be diameter be 15-30nm or diameter are the calcium carbonate of 15-30nm.
Preferably, described transition metal salt is any one or a few in ferrous sulfate, ferric sulfate and iron nitrate.
Preferably, described nitrogenous compound is polymine, and its weight-average molecular weight is 1300-25000.
Present invention also offers a kind of preparation method of above-mentioned nitrogen sulphur codope mesoporous carbon electrode material, it is characterized in that, comprise the following steps:
Step 1): template, nitrogenous compound and transition metal salt are dissolved in solvent, ultrasonic 6 ~ 8h, dry, obtain presoma;
Step 2): by step 1) obtained presoma is warming up to 600 ~ 1000 DEG C of roasting reduction process 1 ~ 3h under inert gas atmosphere protection, obtains a char-forming material;
Step 3): by step 2) obtained char-forming material acid solution cleanup acid treatment 12 ~ 24h under room temperature, then dry after centrifugal, washed with de-ionized water, obtain nitrogenous meso-porous carbon material;
Step 4): by step 3) obtained nitrogenous meso-porous carbon material acid solution cleanup acid treatment 6 ~ 8h again at 80 DEG C; then centrifugal, the rear drying of deionization cleaning; and again under inert gas atmosphere protection, be warming up to 600 ~ 1000 DEG C of roasting reduction process 1 ~ 3h, obtain nitrogen sulphur codope mesoporous carbon electrode material.
Preferably, described step 1) in solvent be water, methyl alcohol or ethanol.
Preferably, described step 1), step 4) in rare gas element be nitrogen or argon gas.
Preferably, described step 3), step 4) in acid solution be any one or two or more mixing solutionss in sulfuric acid, hydrochloric acid and hydrofluoric acid.
Present invention also offers the application of a kind of nitrogen sulphur codope mesoporous carbon electrode material in ultracapacitor, it is characterized in that, adopt the step 1 in the preparation method of above-mentioned nitrogen sulphur codope mesoporous carbon electrode material) to step 4) obtained nitrogen sulphur codope mesoporous carbon electrode material, then carry out following steps:
Step 5): nitrogen sulphur codope mesoporous carbon electrode material and acetylene black, binding agent, dispersion agent are mixed in proportion, after ultrasonic, obtain mixing solutions; Mixing solutions is transferred on glass carbon (GC) electrode, naturally dry;
Step 6): use electrochemical workstation, three-electrode system test is carried out in the electrolyte solution of different concns, with step 5) obtained glass-carbon electrode is working electrode, platinum electrode is to electrode, saturated calomel electrode is reference electrode, carries out the cyclic voltammetry that difference sweeps speed under nitrogen atmosphere.
Preferably, described step 5) in binding agent be Nafion solution, PVA or PTFE.
Preferably, described step 5) in dispersion agent be ethanol, water or Virahol.
Preferably, described step 5) in nitrogen sulphur codope meso-porous carbon material and acetylene black, binding agent weight ratio be 80%: 10%: 10%, 85%: 5%: 10%, 85%: 10%: 5% or 90%: 5%: 5%.
Preferably, described step 6) in different concns electrolyte solution adopt 1M KOH, 3M KOH, 6M KOH, 0.5M H 2sO 4with 1M H 2sO 4.
Nitrogen sulphur codope mesoporous carbon electrode material provided by the invention is hierarchical porous structure, and it has very high specific surface area, significantly improves ratio capacitance and cyclical stability, is a kind of excellent super capacitor material.
Compared with prior art, the invention has the beneficial effects as follows:
Nitrogen sulphur codope meso-porous carbon material provided by the invention is orderly many meso-porous carbon materials and has very high specific surface area, nitrogen sulphur codope simultaneously not only improves the dispersiveness of water and can change mesoporous carbon local current densities, improve the electron transmission of mesoporous carbon, reducing specific resistance, is a kind of excellent super capacitor material.In addition, the present invention also have preparation method simple, with low cost, be easy to realize the advantages such as suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is at 0.5M H with the electrode materials of embodiment 1 preparation 2sO 4in electrolyte solution circulationvolt-ampere curve, wherein electrode carrying capacity is 0.5mg/cm;
Fig. 2 is at 0.5M H with the electrode materials of embodiment 1 preparation 2sO 4in electrolyte solution, ratio capacitance is with the curve of current density change, and wherein electrode carrying capacity is 0.5mg/cm 2;
Fig. 3 be with embodiment 1 prepare electrode materials with the current density of 50A/g at 0.5M H 2sO 4stable circulation linearity curve in electrolyte solution, wherein electrode carrying capacity is 0.5mg/cm 2;
Fig. 4 is the ratio capacitance of electrode materials in 3M KOH electrolyte solution prepared with embodiment 3 curve with scan speed change, and wherein electrode carrying capacity is 0.5mg/cm 2.
Embodiment
For making the present invention become apparent, hereby with preferred embodiment, and accompanying drawing is coordinated to be described in detail below.
Embodiment 1
A kind of nitrogen sulphur codope electrode materials, its presoma comprise mass content be 46% template diameter be the silicon-dioxide of 15nm, mass content be 20% nitrogenous compound PEI (polymine, Sigma-Aldrich (Shanghai) trade Co., Ltd, 408700-250ML, Mw=2000) and mass content be 34% transition metal salt ferrous sulfate (above-mentioned mass content with the total mass of presoma for benchmark).
The preparation method of above-mentioned nitrogen sulphur codope electrode materials is: polymine and silicon-dioxide are mixed with the PEI aqueous solution of 50% and the SiO of 20% 2the aqueous solution, takes 0.7448g FeSO 47H 2the PEI aqueous solution of O and 0.9g 50%, and by the SiO of itself and 5g 20% 2the aqueous solution mixes under the condition stirred, and spend the night in 85 DEG C of baking oven inner dryings after ultrasonic 8h, grinding powder, obtains presoma.Above-mentioned presoma is placed in quartz boat, at N 2be increased to roasting reduction process 1h under 800 DEG C of conditions with 20 DEG C/min temperature rise rate under atmosphere protection, obtain a carbonized product.By a carbonized product excessive 40%HF solution at room temperature pickling 24h, dry after centrifugal, washed with de-ionized water, obtain nitrogenous meso-porous carbon material.Be the sulfuric acid of 0.5M cleanup acid treatment 8h again at 80 DEG C by excessive concentration by above-mentioned nitrogenous meso-porous carbon material; centrifugal, the rear drying of deionization cleaning; secondary is warming up to 800 DEG C of roasting reduction process 1h under inert gas atmosphere protection, obtains nitrogen sulphur codope mesoporous carbon electrode material.
Electrode preparation and the test of meso-porous carbon material: by above-mentioned nitrogen sulphur codope meso-porous carbon material and acetylene black, Nafion solution (Sigma-Aldrich) be in mass ratio 9: 1: 3 mass mixing even, add 3.6ml Virahol ultrasonic, obtain mixing solutions; Pipette with micropipette rifle and point to pipette the above-mentioned catalyst solution of 55 μ l for 6 times to transfer to area be 0.2475cm 2gC electrode on, naturally dry.Catalyst loadings is 0.5mg/cm 2.Use electrochemical workstation, at 0.5M H 2sO 4three-electrode system test is carried out in electrolyte solution, with above-mentioned obtained electrode for working electrode, platinum electrode is to electrode, saturated calomel electrode is reference electrode, carries out cyclic voltammetry respectively obtain voltage stabilization window under different scanning speed and by the ratio capacitance of cyclic voltammetry curve and constant current charge-discharge curve calculation meso-porous carbon material at 3mv/s, 10mv/s, 25mv/s, 50mv/s, 100mv/s, 125mv/s.
Embodiment 2
A kind of nitrogen sulphur codope electrode materials, its presoma comprise mass content be 46% template diameter be the silicon-dioxide of 15nm, mass content be 20% nitrogenous compound PEI (polymine, Sigma-Aldrich (Shanghai) trade Co., Ltd, 408700-250ML, Mw=2000) and mass content be 34% transition metal salt ferrous sulfate (above-mentioned mass content with the total mass of presoma for benchmark).
The preparation method of above-mentioned nitrogen sulphur codope electrode materials is: polymine and silicon-dioxide are mixed with the PEI aqueous solution of 50% and the SiO of 20% 2the aqueous solution, takes 0.7448g FeSO 47H 2the PEI aqueous solution of O and 0.9g 50%, and by the SiO of itself and 5g 20% 2the aqueous solution mixes under the condition stirred, and spends the night after ultrasonic 8h in 85 DEG C of baking oven inner dryings, and grinding powder, obtain presoma.Above-mentioned presoma is placed in quartz boat, at N 2be increased to roasting reduction process 1h under 800 DEG C of conditions with 20 DEG C/min temperature rise rate under atmosphere protection, obtain a carbonized product.By a carbonized product excessive 40%HF solution at room temperature pickling 24h, dry after centrifugal, washed with de-ionized water, obtain nitrogenous meso-porous carbon material.Be the sulfuric acid of 0.5M cleanup acid treatment 8h again at 80 DEG C by excessive concentration by above-mentioned nitrogenous meso-porous carbon material; centrifugal, the rear drying of deionization cleaning; secondary is warming up to 800 DEG C of roasting reduction process 1h under inert gas atmosphere protection, obtains nitrogen sulphur codope mesoporous carbon electrode material (FeSO 4/ PEI=1/3-800-800).
Electrode preparation and the test of meso-porous carbon material: by above-mentioned nitrogen sulphur codope meso-porous carbon material and acetylene black, Nafion solution (Sigma-Aldrich) be in mass ratio 8: 1: 3 mass mixing even, add 3.6ml EtOH Sonicate, obtain mixing solutions; Pipette with micropipette rifle and point to pipette the above-mentioned catalyst solution of 62 μ l for 8 times to transfer to an area be 0.2475cm 2gC electrode on, naturally dry.Catalyst loadings is 0.5mg/cm 2.Use electrochemical workstation, at 0.5M H 2sO 4three-electrode system test is carried out in electrolyte solution, with above-mentioned obtained electrode for working electrode, platinum electrode is to electrode, saturated calomel electrode is reference electrode, cyclic voltammetry is carried out respectively at 3mv/s, 10mv/s, 25mv/s, 50mv/s, 100mv/s, 125mv/s, and by the ratio capacitance of cyclic voltammetry curve and constant current charge-discharge curve calculation meso-porous carbon material.
Embodiment 3
A kind of nitrogen sulphur codope electrode materials, its presoma comprise mass content be 46% template diameter be the silicon-dioxide of 15nm, mass content be 20% nitrogenous compound PEI (polymine, Sigma-Aldrich (Shanghai) trade Co., Ltd, 408700-250ML, Mw=2000) and mass content be 34% transition metal salt ferrous sulfate.(above-mentioned mass content with the total mass of presoma for benchmark)
The preparation method of above-mentioned nitrogen sulphur codope electrode materials is: polymine and silicon-dioxide are mixed with the PEI aqueous solution of 50% and the SiO of 20% 2the aqueous solution, takes 0.7448g FeSO 47H 2the PEI aqueous solution of O and 0.9g 50%, and by the SiO of itself and 5g 20% 2the aqueous solution mixes under the condition stirred, and spends the night after ultrasonic 8h in 85 DEG C of baking oven inner dryings, and grinding powder, obtain presoma.Above-mentioned presoma is placed in quartz boat, at N 2be increased to roasting reduction process 1h under 800 DEG C of conditions with 20 DEG C/min temperature rise rate under atmosphere protection, obtain a carbonized product.By a carbonized product excessive 40%HF solution at room temperature pickling 24h, dry after centrifugal, washed with de-ionized water, obtain nitrogenous meso-porous carbon material.Be the hydrochloric acid of 1M cleanup acid treatment 8h again at 80 DEG C by excessive concentration by above-mentioned nitrogenous meso-porous carbon material; centrifugal, the rear drying of deionization cleaning; secondary is warming up to 800 DEG C of roasting reduction process 1h under inert gas atmosphere protection, obtains nitrogen sulphur codope mesoporous carbon electrode material (FeSO 4/ PEI=1/3-800-800).
Electrode preparation and the test of meso-porous carbon material: by above-mentioned nitrogen sulphur codope meso-porous carbon material and acetylene black, PTFE be in mass ratio 9: 1: 1 mass mixing even, add 3.9ml EtOH Sonicate, obtain mixing solutions; Pipette with micropipette rifle and point to pipette the above-mentioned catalyst solution of 621 μ l for 8 times to transfer to an area be 0.2475cm 2gC electrode on, naturally dry.Catalyst loadings is 0.5mg/cm 2.Use electrochemical workstation, three-electrode system test is carried out in 3M KOH electrolyte solution, with above-mentioned obtained electrode for working electrode, platinum electrode is to electrode, saturated calomel electrode is reference electrode, carry out cyclic voltammetry at 3mv/s, 10mv/s, 25mv/s, 50mv/s, 100mv/s, 125mv/s, and calculate the ratio capacitance of meso-porous carbon material by cyclic voltammetry curve.
Embodiment 4
A kind of nitrogen sulphur codope electrode materials, its presoma comprise mass content be 46% template diameter be the silicon-dioxide of 15nm, mass content be 20% nitrogenous compound PEI (polymine, Sigma-Aldrich (Shanghai) trade Co., Ltd, 408700-250ML, Mw=2000) and mass content be 40% transition metal salt ferric sulfate (above-mentioned mass content with the total mass of presoma for benchmark).
The preparation method of above-mentioned nitrogen sulphur codope electrode materials is: polymine and silicon-dioxide are mixed with the PEI aqueous solution of 50% and the SiO of 20% 2the aqueous solution, takes 1.071g Fe 2(SO 4) 3with the PEI aqueous solution of 0.9g 50%, and by the SiO of itself and 5g 20% 2the aqueous solution mixes under the condition stirred, and spends the night after ultrasonic 8h in 85 DEG C of baking oven inner dryings, and grinding powder, obtain presoma.Above-mentioned presoma is placed in quartz boat, at N 2be increased to roasting reduction process 1h under 800 DEG C of conditions with 20 DEG C/min temperature rise rate under atmosphere protection, obtain a carbonized product.By a carbonized product excessive 40%HF solution at room temperature pickling 24h, dry after centrifugal, washed with de-ionized water, obtain nitrogenous meso-porous carbon material.Be the sulfuric acid of 0.5M cleanup acid treatment 8h again at 80 DEG C by excessive concentration by above-mentioned nitrogenous meso-porous carbon material; centrifugal, the rear drying of deionization cleaning; secondary is warming up to 800 DEG C of roasting reduction process 1h under inert gas atmosphere protection, obtains nitrogen sulphur codope mesoporous carbon electrode material (Fe 2(SO4) 3/ PEI=1/3-800-800).
Electrode preparation and the test of meso-porous carbon material: by above-mentioned nitrogen sulphur codope meso-porous carbon material and acetylene black, PTFE be in mass ratio 8: 1: 1 mass mixing even, add 3.9ml EtOH Sonicate, obtain mixing solutions; Pipette with micropipette rifle and point to pipette the above-mentioned catalyst solution of 62 μ l for 8 times to transfer to an area be 0.2475cm 2gC electrode on, naturally dry.Catalyst loadings is 0.5mg/cm 2.Use electrochemical workstation, three-electrode system test is carried out in 6M KOH electrolyte solution, with above-mentioned obtained electrode for working electrode, platinum electrode is to electrode, saturated calomel electrode is reference electrode, carry out cyclic voltammetry at 3mv/s, 10mv/s, 25mv/s, 50mv/s, 100mv/s, 125mv/s, and calculate the ratio capacitance of meso-porous carbon material by cyclic voltammetry curve.
Embodiment 5
A kind of nitrogen sulphur codope electrode materials, its presoma comprise mass content be 46% template diameter be the silicon-dioxide of 15nm, mass content be 20% nitrogenous compound PEI (polymine, Sigma-Aldrich (Shanghai) trade Co., Ltd, 408700-250ML, Mw=2000) and mass content be 43% transition-metal Fe (NO 3) 39H 2o (above-mentioned mass content with the total mass of presoma for benchmark).
The preparation method of above-mentioned nitrogen sulphur codope electrode materials is: polymine and silicon-dioxide are mixed with the PEI aqueous solution of 50% and the SiO of 20% 2the aqueous solution, takes 1.0821g Fe (NO 3) 3with the PEI aqueous solution of 0.9g 50%, and by the SiO of itself and 5g 20% 2the aqueous solution mixes under the condition stirred, and spends the night after ultrasonic 8h in 85 DEG C of baking oven inner dryings, and grinding powder, obtain presoma.Above-mentioned presoma is placed in quartz boat, at N 2be increased to roasting reduction process 1h under 800 DEG C of conditions with 20 DEG C/min temperature rise rate under atmosphere protection, obtain a carbonized product.By a carbonized product excessive 40%HF solution at room temperature pickling 24h, dry after centrifugal, washed with de-ionized water, obtain nitrogenous meso-porous carbon material.Be the sulfuric acid of 0.5M cleanup acid treatment 8h again at 80 DEG C by excessive concentration by above-mentioned nitrogenous meso-porous carbon material; centrifugal, the rear drying of deionization cleaning; and again under inert gas atmosphere protection, be warming up to 800 DEG C of roasting reduction process 1h, obtain nitrogen sulphur codope mesoporous carbon electrode material (Fe (NO 3) 3/ PEI=1/3-800-800).
Electrode preparation and the test of meso-porous carbon material: by above-mentioned nitrogen sulphur codope meso-porous carbon material and acetylene black, PTFE be in mass ratio 8: 1: 1 mass mixing even, add 3.9ml EtOH Sonicate, obtain mixing solutions; Pipette with micropipette rifle and point to pipette the above-mentioned catalyst solution of 62 μ l for 8 times to transfer to an area be 0.2475cm 2gC electrode on, naturally dry.Catalyst loadings is 0.5mg/cm 2.Use electrochemical workstation, three-electrode system test is carried out in 6M KOH electrolyte solution, with above-mentioned obtained electrode for working electrode, platinum electrode is to electrode, saturated calomel electrode is reference electrode, carry out cyclic voltammetry at 3mv/s, 10mv/s, 25mv/s, 50mv/s, 100mv/s, 125mv/s, and calculate the ratio capacitance of meso-porous carbon material by cyclic voltammetry curve.
In Fig. 1-4, all potential values are the current potential relative to saturated calomel electrode.Can find that nitrogen sulphur codope mesoporous carbon electrode shows good ultracapacitor performance, at 0.5M H from Fig. 1 2sO 4in electrolyte solution, when sweep velocity reaches 150mV/s, CV curve still keeps good rectangular characteristic.Fig. 2 is that nitrogen sulphur codope mesoporous carbon electrode ratio capacitance is at 0.5M H 2sO 4with current density change curve in electrolyte solution.When current density is 1A/g, its ratio capacitance reaches 279F/g, when current density increase reaches 100A/g, still maintains 232F/g, i.e. the capability retention of about 83%.Fig. 3 is the cyclical stability of nitrogen sulphur codope mesoporous carbon electrode, when under high magnification current density 50A/g, material after circulation 5000 is enclosed capacity without any decay.Fig. 4 be nitrogen sulphur codope mesoporous carbon electrode ratio capacitance when ionogen changes into 3M KOH with scan speed change curve.When sweep velocity is 3mv/s, its ratio capacitance is 258F/g, and when sweep velocity is elevated to 100mv/s, its ratio capacitance still remains on 213F/g.Show no matter nitrogen sulphur codope meso-porous carbon material of the present invention is the supercapacitor applications be all conducive in acidity or alkaline electrolyte as high magnification and high stability.

Claims (13)

1. a nitrogen sulphur codope mesoporous carbon electrode material, it is characterized in that, the presoma of described electrode materials comprise the template of by percentage to the quality 20 ~ 85% based on presoma total mass, the nitrogenous compound of 10 ~ 75% and 5 ~ 50% transition metal salt.
2. nitrogen sulphur codope mesoporous carbon electrode material as claimed in claim 1, is characterized in that, nano silicon or the diameter of described template to be diameter be 15-30nm are the calcium carbonate of 15-30nm.
3. nitrogen sulphur codope mesoporous carbon electrode material as claimed in claim 1, is characterized in that, described transition metal salt is any one or a few in ferrous sulfate, ferric sulfate and iron nitrate.
4. nitrogen sulphur codope mesoporous carbon electrode material as claimed in claim 1, it is characterized in that, described nitrogenous compound is polymine, and its weight-average molecular weight is 1300-25000.
5. a preparation method for nitrogen sulphur codope mesoporous carbon electrode material according to claim 1, is characterized in that, comprise the following steps:
Step 1): template, nitrogenous compound and transition metal salt are dissolved in solvent, ultrasonic 6 ~ 8h, dry, obtain presoma;
Step 2): by step 1) obtained presoma is warming up to 600 ~ 1000 DEG C of roasting reduction process 1 ~ 3h under inert gas atmosphere protection, obtains a char-forming material;
Step 3): by step 2) obtained char-forming material acid solution cleanup acid treatment 12 ~ 24h under room temperature, then dry after centrifugal, washed with de-ionized water, obtain nitrogenous meso-porous carbon material;
Step 4): by step 3) obtained nitrogenous meso-porous carbon material acid solution cleanup acid treatment 6 ~ 8h again at 80 DEG C; then centrifugal, the rear drying of deionization cleaning; and again under inert gas atmosphere protection, be warming up to 600 ~ 1000 DEG C of roasting reduction process 1 ~ 3h, obtain nitrogen sulphur codope mesoporous carbon electrode material.
6. the preparation method of nitrogen sulphur codope mesoporous carbon electrode material as claimed in claim 5, is characterized in that, described step 1) in solvent be water, methyl alcohol or ethanol.
7. the preparation method of nitrogen sulphur codope mesoporous carbon electrode material as claimed in claim 5, is characterized in that, described step 1), step 4) in rare gas element be nitrogen or argon gas.
8. the preparation method of nitrogen sulphur codope mesoporous carbon electrode material as claimed in claim 5, is characterized in that, described step 3), step 4) in acid solution be any one or two or more mixing solutionss in sulfuric acid, hydrochloric acid and hydrofluoric acid.
9. the application of a nitrogen sulphur codope mesoporous carbon electrode material in ultracapacitor, it is characterized in that, adopt the step 1 in the preparation method of nitrogen sulphur codope mesoporous carbon electrode material according to claim 5) to step 4) obtained nitrogen sulphur codope mesoporous carbon electrode material, then carry out following steps:
Step 5): nitrogen sulphur codope mesoporous carbon electrode material and acetylene black, binding agent, dispersion agent are mixed in proportion, after ultrasonic, obtain mixing solutions; Mixing solutions is transferred on glass-carbon electrode, naturally dry;
Step 6): use electrochemical workstation, three-electrode system test is carried out in the electrolyte solution of different concns, with step 5) obtained glass-carbon electrode is working electrode, platinum electrode is to electrode, saturated calomel electrode is reference electrode, carries out the cyclic voltammetry that difference sweeps speed under nitrogen atmosphere.
10. nitrogen sulphur codope mesoporous carbon electrode material as claimed in claim 9 is in the application in ultracapacitor field, it is characterized in that, described step 5) in binding agent be Nafion solution, PVA or PTFE.
11. nitrogen sulphur codope mesoporous carbon electrode materials as claimed in claim 9, in the application in ultracapacitor field, is characterized in that, described step 5) in dispersion agent be ethanol, water or Virahol.
12. as the application of nitrogen sulphur codope mesoporous carbon electrode material in ultracapacitor field in claim 9-11 as described in any one, it is characterized in that, described step 5) in nitrogen sulphur codope meso-porous carbon material and acetylene black, binding agent weight ratio be 80%: 10%: 10%, 85%: 5%: 10%, 85%: 10%: 5% or 90%: 5%: 5%.
13. nitrogen sulphur codope mesoporous carbon electrode materials as claimed in claim 9, in the application in ultracapacitor field, is characterized in that, described step 6) in different concns electrolyte solution adopt 1M KOH, 3M KOH, 6M KOH, 0.5M H 2sO 4with 1M H 2sO 4.
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CN105206845A (en) * 2015-08-20 2015-12-30 浙江工业大学 Method for synthesizing an S and N synergistic mesoporous carbon material with excellent ORR and lithium-ion electric performance through one-step method
CN105304913A (en) * 2015-11-12 2016-02-03 东华大学 Nitrogen/transition metal-codoped hierarchical-pore carbon oxygen reduction catalyst, and preparation method and application thereof
CN106207204A (en) * 2016-09-19 2016-12-07 青岛科技大学 Nitrogen sulfur difunctional VPO catalysts of codope material with carbon element and its preparation method and application
CN107117595A (en) * 2017-05-18 2017-09-01 齐鲁工业大学 A kind of preparation method and application of Heteroatom doping graded porous carbon electrode material for super capacitor
CN107689303A (en) * 2017-09-06 2018-02-13 温州大学 Electrode for capacitors based on nitrogen sulphur codope porous carbon microsphere composite and preparation method thereof
CN108410953A (en) * 2018-03-09 2018-08-17 湖南大学 It is a kind of to be used to detect biosensor of mercury and its preparation method and application
CN108455557A (en) * 2018-03-09 2018-08-28 中南林业科技大学 Nitrogen sulphur codope ordered mesoporous carbon material and its preparation method and application
CN109133276A (en) * 2018-10-08 2019-01-04 天津科技大学 A kind of functionalization mesoporous carbon electrode material and preparation method thereof
CN110364705A (en) * 2019-06-20 2019-10-22 华南理工大学 A kind of transition metals cobalt is monatomic/cluster insertion nitrogen-doped carbon framework material and its preparation method and application
CN112357901A (en) * 2020-09-09 2021-02-12 温州大学新材料与产业技术研究院 Preparation method of nitrogen-sulfur co-doped micro-mesoporous carbon sphere/sheet material, product and application thereof
CN112837947A (en) * 2020-12-30 2021-05-25 上海应用技术大学 Nitrogen and sulfur co-doped layered porous carbon hybrid material prepared from inorganic-cellulose raw material, and preparation and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103566961A (en) * 2013-10-30 2014-02-12 东华大学 Metal-free nitrogen-doped functionalized mesoporous carbon catalyst and preparation method and applications thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103566961A (en) * 2013-10-30 2014-02-12 东华大学 Metal-free nitrogen-doped functionalized mesoporous carbon catalyst and preparation method and applications thereof

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CN104777201A (en) * 2015-04-16 2015-07-15 湖北民族学院 Method for preparing electrochemical sensor for detecting parathion
CN104777201B (en) * 2015-04-16 2017-07-11 湖北民族学院 A kind of preparation method for the electrochemical sensor for detecting parathion
CN105206845A (en) * 2015-08-20 2015-12-30 浙江工业大学 Method for synthesizing an S and N synergistic mesoporous carbon material with excellent ORR and lithium-ion electric performance through one-step method
CN105206845B (en) * 2015-08-20 2017-07-07 浙江工业大学 One-step synthesis method has the S of excellent ORR and lithium electrical property, the meso-porous carbon material method of N synergies
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CN105304913A (en) * 2015-11-12 2016-02-03 东华大学 Nitrogen/transition metal-codoped hierarchical-pore carbon oxygen reduction catalyst, and preparation method and application thereof
CN106207204A (en) * 2016-09-19 2016-12-07 青岛科技大学 Nitrogen sulfur difunctional VPO catalysts of codope material with carbon element and its preparation method and application
CN107117595A (en) * 2017-05-18 2017-09-01 齐鲁工业大学 A kind of preparation method and application of Heteroatom doping graded porous carbon electrode material for super capacitor
CN107689303A (en) * 2017-09-06 2018-02-13 温州大学 Electrode for capacitors based on nitrogen sulphur codope porous carbon microsphere composite and preparation method thereof
CN108410953A (en) * 2018-03-09 2018-08-17 湖南大学 It is a kind of to be used to detect biosensor of mercury and its preparation method and application
CN108455557A (en) * 2018-03-09 2018-08-28 中南林业科技大学 Nitrogen sulphur codope ordered mesoporous carbon material and its preparation method and application
CN108410953B (en) * 2018-03-09 2020-11-13 湖南大学 Biosensor for detecting mercury and preparation method and application thereof
CN109133276A (en) * 2018-10-08 2019-01-04 天津科技大学 A kind of functionalization mesoporous carbon electrode material and preparation method thereof
CN109133276B (en) * 2018-10-08 2021-09-07 天津科技大学 Functionalized mesoporous carbon electrode material and preparation method thereof
CN110364705A (en) * 2019-06-20 2019-10-22 华南理工大学 A kind of transition metals cobalt is monatomic/cluster insertion nitrogen-doped carbon framework material and its preparation method and application
CN112357901A (en) * 2020-09-09 2021-02-12 温州大学新材料与产业技术研究院 Preparation method of nitrogen-sulfur co-doped micro-mesoporous carbon sphere/sheet material, product and application thereof
CN112357901B (en) * 2020-09-09 2022-07-19 温州大学新材料与产业技术研究院 Preparation method of nitrogen-sulfur co-doped micro-mesoporous carbon sphere/sheet material, product and application thereof
CN112837947A (en) * 2020-12-30 2021-05-25 上海应用技术大学 Nitrogen and sulfur co-doped layered porous carbon hybrid material prepared from inorganic-cellulose raw material, and preparation and application thereof

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