CN103474253A - Porous carbon microsphere electrode materials based on surface function functional group, preparing method of materials, super capacitor of materials, and preparing method of super capacitor - Google Patents

Porous carbon microsphere electrode materials based on surface function functional group, preparing method of materials, super capacitor of materials, and preparing method of super capacitor Download PDF

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CN103474253A
CN103474253A CN2013104603817A CN201310460381A CN103474253A CN 103474253 A CN103474253 A CN 103474253A CN 2013104603817 A CN2013104603817 A CN 2013104603817A CN 201310460381 A CN201310460381 A CN 201310460381A CN 103474253 A CN103474253 A CN 103474253A
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porous carbon
carbon microsphere
functional group
deionized water
electrode material
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CN103474253B (en
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麦立强
阿米尔·明哈斯·可汗
瞿龙兵
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Wuhan University of Technology WUT
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Abstract

The invention relates to a porous carbon microsphere electrode materials based on a surface function functional group and a preparing method of the materials. The preparing method comprises the steps that 1) LiOH and Cl2CH-COOH are dissolved in deionized water, magnetic stirring is carried out, an obtained Cl2CH-COOLi precursor is subjected to ultrasound mist spray dissociation to form micro-droplets, the obtained micro-droplets are subjected to pyrolysis in nitrogen atmosphere, black powder is collected and obtained; 2) centrifugal separation and washing are carried out; 3) porous carbon microspheres are obtained by drying; 4) carbon fiber paper is soaked in an ethanol solution containing the porous carbon microspheres, then taking out and drying are carried out for three times repeatedly; 5) flushing is carried out with deionized water, and drying is carried out for 3 hours under the temperature of 80 DEG C. The materials have the advantages that raw materials are cheap, the technology is simple and environmentally friendly, and the electrochemical performance of the materials is great. Wide application prospect is achieved on a super capacitor or a lithium battery or other electrochemistry energy storage devices.

Description

Based on function of surface functional group porous carbon microsphere electrode material and preparation method thereof, its ultracapacitor and preparation method
Technical field
The invention belongs to nano material and technical field of electrochemistry, be specifically related to a kind of based on function of surface functional group porous carbon microsphere electrode material and preparation method thereof, its ultracapacitor and preparation method.
Background technology
Electric chemical super capacitor can more provide energy under high magnification with respect to battery, can in long time, guaranteed output density not reduce simultaneously.But its low energy densities has limited it at high-energy-density, high power density, the application in extra long life field.Carbon-based material is due to they low costs, high conductivity, high-specific surface area, the characteristics of fast charging and discharging and generally be applied in the ultracapacitor field.Their energy storage mechanism is the quick faraday's reaction due to electric double layer effect and surface functional group, is mainly the functional group of oxygen and the nitrogen at electrode/electrolyte interface.In addition, the polarization of carbon-based material surface functional group can improve the surface wettability of porous carbon microsphere in aqueous electrolyte, has reduced impedance, has therefore reduced the requirement of these materials to very high permeability.But unconspicuous faraday's reaction and their instability modes in cyclic process of different surfaces functional group have hindered the application of carbon-based material as super capacitor material.
Recently bibliographical information having been arranged accelerates faraday by active carbon electrode material with electrolyte generation redox reaction and reacts.For example, by introduce hydroquinones in sulfuric acid electrolyte, can be so that the specific discharge capacity of active carbon electrode material be brought up to 901F/g from 320F/g.Same adds KI in sulfuric acid electrolyte, and specific discharge capacity is increased to 912F/g from 472F/g.The raising of specific capacity is mainly because improved the faraday's reaction fast of electrode/electrolyte interface by introducing associated media in electrolyte.But the specific discharge capacity that on the document of report, this method obtains is no more than 940F/g.
Summary of the invention
The object of the present invention is to provide that a kind of technique is simple, the requirement that meets Green Chemistry, have the good electric chemical property based on function of surface functional group porous carbon microsphere electrode material, its ultracapacitor and preparation method thereof.
The present invention solves the problems of the technologies described above adopted technical scheme: based on function of surface functional group porous carbon microsphere electrode material, it is following preparation method's products therefrom, includes following steps:
1) by 1.5molLiOH and 1.5molCl 2cH-COOH is dissolved in the 100ml deionized water, and magnetic agitation, to without bulky grain, forms Cl 2the CH-COOLi presoma, by the Cl obtained 2the CH-COOLi presoma forms micro-drop by the ullrasonic spraying cracking, and micro-drop of gained carries out pyrolysis under 800 ℃ at nitrogen atmosphere, collects and obtains black powder;
2) with ethanol and the centrifugation of deionized water difference, wash three times;
3) under 80 ℃, dry 6-12 hour obtains porous carbon microsphere;
4) carbon fiber paper is cut into to 2*3cm 2be immersed in the 5ml ethanolic solution that contains the 0.1g porous carbon microsphere 30 seconds, then take out, under high-pressure sodium lamp dry 1 minute, triplicate, to guarantee that on carbon fiber paper, load has appropriate porous carbon microsphere;
5) with deionized water, rinsed, under 80 ℃, drying is 3 hours, obtains the porous carbon microsphere electrode material based on function of surface functional group.
The described preparation method based on function of surface functional group porous carbon microsphere electrode material includes following steps:
1) by 1.5molLiOH and 1.5molCl 2cH-COOH is dissolved in the 100ml deionized water, and magnetic agitation, to without bulky grain, forms Cl 2the CH-COOLi presoma, by the Cl obtained 2the CH-COOLi presoma forms micro-drop by the ullrasonic spraying cracking, and micro-drop of gained carries out pyrolysis under 800 ℃ at nitrogen atmosphere, collects and obtains black powder;
2) with ethanol and the centrifugation of deionized water difference, wash three times;
3) under 80 ℃, dry 6-12 hour obtains porous carbon microsphere;
4) carbon fiber paper is cut into to 2*3cm 2be immersed in the 5ml ethanolic solution that contains the 0.1g porous carbon microsphere 30 seconds, then take out, under high-pressure sodium lamp dry 1 minute, triplicate, to guarantee that on carbon fiber paper, load has appropriate porous carbon microsphere;
5) with deionized water, rinsed, under 80 ℃, drying is 3 hours, obtains the porous carbon microsphere electrode material based on function of surface functional group.
A kind ofly include the ultracapacitor based on function of surface functional group porous carbon microsphere electrode material claimed in claim 1.
The preparation method of the described ultracapacitor based on function of surface functional group porous carbon microsphere electrode material includes following steps:
1) by 1.5molLiOH and 1.5molCl 2cH-COOH is dissolved in the 100ml deionized water, and magnetic agitation, to without bulky grain, forms Cl 2the CH-COOLi presoma, by the Cl obtained 2the CH-COOLi presoma forms micro-drop by the ullrasonic spraying cracking, and micro-drop of gained carries out pyrolysis under 800 ℃ at nitrogen atmosphere, collects and obtains black powder;
2) with ethanol and the centrifugation of deionized water difference, wash three times;
3) under 80 ℃, dry 6-12 hour obtains porous carbon microsphere;
4) carbon fiber paper is cut into to 2*3cm 2be immersed in the 5ml ethanolic solution that contains the 0.1g porous carbon microsphere 30 seconds, then take out, under high-pressure sodium lamp dry 1 minute,, triplicate, to guarantee that on carbon fiber paper, load has appropriate porous carbon microsphere;
5) with deionized water, rinsed, under 80 ℃, drying is 3 hours, obtains the porous carbon microsphere electrode material based on function of surface functional group;
6) by CuCl 2join HNO 3in solution, CuCl wherein 2concentration change from 0.0001 to 1mol/L, obtain the electrolyte material of porous carbon microsphere ultracapacitor;
7) assemble ultracapacitor with three-electrode method, wherein, using the electrode material of step 5) gained as work electrode, platinum electrode is as to electrode, and calomel electrode is as reference electrode, usings the electrolyte of step 6) gained as the electrolyte material of ultracapacitor.
Press such scheme, CuCl in described electrolyte material 2concentration be 0.06～0.09mol/L.
The present invention has designed the ultracapacitor of a kind of porous carbon microsphere surface functional group and electrolyte generation redox reaction, by CuCl 2join HNO 3in solution, prepare electrolyte material, in test, observe the carbon and oxygen functional group on carbosphere surface and the Cu in acid solution 2+react, also find CuCl in electrolyte simultaneously 2concentration the chemical property of porous carbon microsphere is had a great impact.Research finds that CuCl has good reactivity for most carbon back compounds.Therefore, by fixing carbon-oxygen bond in the position on carbon ball surface with the CuCl in reducing electrolyte 2, can produce easily extra redox reaction CuCl layer.Chloride can be so that the bonding action between copper oxygen be more firm in addition.In the situation that do not add conductive agent and binding agent, in order to improve its conductivity, the present invention takes porous carbon microsphere directly is adsorbed on carbon fiber paper, at CuCl 2and HNO 3electrolyte in very high ion diffusion rate is arranged.
In the present invention, the functional group on porous carbon microsphere surface is determined by the x-ray photoelectron power spectrum, quantitative analysis is presented at the porous carbon microsphere surface two kinds of functional groups, they are respectively carbon and oxygen functional group and hydroxy functional group, wherein carbon and oxygen functional group is 22%, hydroxy functional group is 78%, draws in the 0.1g porous carbon microsphere and contains 10% oxygen through test analysis simultaneously.In test, we find that working as electrolyte is H 2sO 4during solution, its specific discharge capacity is 460F/g, and electrolyte is CuSO 4and HNO 3mixed electrolytic solution the time its specific discharge capacity be 420F/g, but when CuSO 4change CuCl into 2the time, even if the CuCl added 2amount seldom, still can observe very strong redox peak.This makes its specific discharge capacity be greatly improved, and reaches 4700F/g, and this is because following reaction has occurred for the surface functional group of porous carbon microsphere and electrolyte
Figure BDA0000391240460000031
This porous carbon microsphere electrode material specific discharge capacity is not add CuCl in electrolyte 210 times.Be 10 times to 50 times of some carbon-based materials of crossing of other bibliographical information, the specific discharge capacity (3072F/g) of the high molecular polymer based super capacitor material of also crossing than those bibliographical informations is also much higher simultaneously.Mean energy density by calculating it is 163Wh/kg, is 1.7 to 2.3 times of energy density of the carbon back super capacitor material crossed of previous bibliographical information.The electrode material prepared has very high electric transmission speed and ion mobility, therefore the Charge-transfer resistance of comparing it with carbon fiber paper only has 0.04 Ω, and carbon fiber has 1361 Ω, this shows that porous carbon microsphere directly loads on carbon fiber the very large effect of playing.
In addition, the factor that allows electronics and ion transfer accelerate is its equivalent series resistance very low (0.65 Ω), and the whole ohmage of this resistance and ultracapacitor is relevant, comprises the contact resistance of porous carbon microsphere.Also have, the electrochemical impedance graphs shows that its slope is large, this means the hole that enters into porous carbon microsphere that ion in electrolyte can be very fast.
And, the electrode material for super capacitor that the present invention prepares still has the specific discharge capacity of 1335F/g under the current density of 60A/g, and after 5000 circulations, its capability retention is 99.4%, as can be seen here, this electrode material has extraordinary cyclical stability.This is very firm owing to the bonding action between copper oxygen in the situation that has chloride to exist mainly, the surface tension effects simultaneously reduced between porous carbon microsphere and carbon fiber paper also make absorption between them very firmly.
The invention has the beneficial effects as follows: utilize the ullrasonic spraying cracking process, in conjunction with later stage heat treatment, obtained the porous carbon microsphere of surperficial carbon containing oxygen, hydroxy functional group, this microballoon has high specific area, reaches 910m 2/ g, average pore size is about 20nm, can well directly be adsorbed on carbon fiber paper.At acid CuCl 2electro-chemical test in electrolyte, show CuCl in acidic electrolysis bath 2concentration from 0.0001 to 1mol/L the time, its energy density (specific discharge capacity) can increase, at CuCl 2concentration while being 0.09mol/L, there is the superior quality specific capacity of 4700F/g.The present invention has the characteristics of raw material cheapness, the simple environmental protection of technique, material electrochemical performance excellence.On ultracapacitor, lithium battery or other electrochemical energy storing device, larger application prospect is arranged.
The accompanying drawing explanation
Fig. 1 is that in embodiment 1, porous carbon microsphere directly is adsorbed on the process on carbon fiber paper;
Fig. 2 is that the porous carbon microsphere of embodiment 1 is adsorbed on the SEM figure on carbon fiber paper;
Fig. 3 is BET collection of illustrative plates and the XPS collection of illustrative plates of the porous carbon microsphere for preparing in embodiment 1;
Fig. 4 is that the porous carbon microsphere of embodiment 1 is at CuCl 2aC impedance figure in acidic electrolysis bath;
Fig. 5 is the cyclic voltammetry curve figure in embodiment 1 and embodiment 2, and embedding figure is that the porous carbon microsphere electrode material is at H 2sO 4electrolyte and HNO 3and 0.12mol/LCuSO 4cyclic voltammetry curve figure in electrolyte;
Fig. 6 is the cycle performance figure of porous carbon microsphere ultracapacitor in embodiment 1.
Embodiment
In order to understand better the present invention, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
Preparation method based on function of surface functional group porous carbon microsphere electrode material ultracapacitor, it comprises the steps:
1) by 1.5molLiOH and 1.5molCl 2cH-COOH is dissolved in the 100ml deionized water, and magnetic agitation, to without bulky grain, forms Cl 2the CH-COOLi presoma, by the Cl obtained 2the CH-COOLi presoma forms micro-drop by the ullrasonic spraying cracking, and micro-drop of gained carries out pyrolysis under 800 ℃ at nitrogen atmosphere, collects and obtains black powder;
2) with ethanol and the centrifugation of deionized water difference, wash three times;
3) the dry porous carbon microsphere that obtains in 12 hours under 80 ℃;
4) carbon fiber paper is cut into to 2*3cm 2be immersed in the 5ml ethanolic solution that contains the 0.1g porous carbon microsphere 30 seconds, then take out, under high-pressure sodium lamp dry 1 minute, triplicate, to guarantee that on carbon fiber paper, load has appropriate porous carbon microsphere;
5) with deionized water, rinsed, under 80 ℃, drying is 3 hours, obtains the porous carbon microsphere electrode material based on function of surface functional group;
6) by CuCl 2join HNO 3in solution, CuCl wherein 2concentration be 0.09mol/L, obtain the electrolyte material of porous carbon microsphere ultracapacitor;
7) assemble ultracapacitor with three-electrode method, wherein, using the electrode material of step 5) gained as work electrode, platinum electrode is as to electrode, and calomel electrode is as reference electrode, usings the electrolyte of step 6) gained as the electrolyte material of ultracapacitor.
As shown in Figure 1, through step 4, make porous carbon microsphere directly be adsorbed on carbon fiber paper.
As shown in Figure 2, carbosphere directly is adsorbed on the scanning electron microscope (SEM) photograph on carbon fiber paper, and from figure, we can find out the size (700～800nm) of carbosphere, and some apertures are arranged on the carbosphere surface.
Fig. 3 a in Fig. 3 is the nitrogen adsorption figure of porous carbon microsphere, and the embedding figure of the inside demonstrates the pore-size distribution of porous carbon microsphere, and this microballoon has high specific area, reaches 910m 2/ g, average pore size is about 20nm.Fig. 3 b is the wide in range scanning energy of the x-ray photoelectron of porous carbon microsphere spectrogram (0-1100ev).Fig. 3 c is the energy spectrogram of x-ray photoelectron for oxygen-containing functional group, in conjunction with x-ray photoelectron power spectrum software analysis, show that wherein carbon and oxygen functional group content is 78%, and the hydroxyl-functional mass contg is 22%, and carbon content is 87%, and oxygen content is 10%, and hydrogen content is 3%.
Fig. 4 be porous carbon microsphere electrode material ultracapacitor at 50mHz-10KHz, (0.01V, 0.2V, the 0.32V) ac impedance spectroscopy under different test voltages.What embedding figure showed is at about 362Hz, the ac impedance spectroscopy of (0.01V, 0.2V, 0.32V) under different test voltages.
Fig. 5 is that the porous carbon microsphere electrode material is in acidic electrolysis bath and 0.09mol/L copper chloride acidic electrolysis bath, sweep speed for the cyclic voltammetric collection of illustrative plates under 5mv/s, as can be seen from the figure, the specific discharge capacity of porous carbon microsphere electrode material in sulfuric acid electrolyte is 460F/g, capacity in 0.09mol/L copper chloride and 1mol/L nitric acid electrolyte is 4700F/g, top-right embedding figure is that the porous carbon microsphere electrode material is in the lmol/L sulfuric acid electrolyte, sweep speed for the cyclic voltammetric collection of illustrative plates of 5mv/s, as can be seen from the figure, the capacity of porous carbon microsphere electrode material in this electrolyte is mass ratio 460F/g, bottom-right embedding figure is that the porous carbon microsphere electrode material is at 0.12mol/L CuSO 4+ 1mol/L H 2sO 4in mixed electrolytic solution, sweeping speed is the cyclic voltammetry curve collection of illustrative plates of 5mv/s, and as can be seen from the figure, the specific discharge capacity of porous carbon microsphere electrode material in this electrolyte is 420F/g.
Fig. 6 is that the porous carbon microsphere electrode material ultracapacitor in embodiment 1 is the circulation collection of illustrative plates under 60A/g in current density, from figure, we can find out that its first specific discharge capacity is 1335F/g under the 60A/g current density, after 5000 circulations, its capability retention is 99.4%, and it has extraordinary cyclical stability as can be seen here.Embedding figure is its last five cyclic curve figure.
Embodiment 2:
Preparation method based on function of surface functional group porous carbon microsphere electrode material ultracapacitor, it comprises the steps:
1) by 1.5molLiOH and 1.5molCl 2cH-COOH is dissolved in the 100ml deionized water, and magnetic agitation, to without bulky grain, forms Cl 2the CH-COOLi presoma, by the Cl obtained 2the CH-COOLi presoma forms micro-drop by the ullrasonic spraying cracking, and micro-drop of gained carries out pyrolysis under 800 ℃ at nitrogen atmosphere, collects and obtains black powder;
2) with ethanol and the centrifugation of deionized water difference, wash three times;
3) the dry porous carbon microsphere that obtains in 12 hours under 80 ℃;
4) carbon fiber paper is cut into to 2*3cm 2be immersed in the 5ml ethanolic solution that contains the 0.1g porous carbon microsphere 30 seconds, then take out, under high-pressure sodium lamp dry 1 minute, triplicate, to guarantee that on carbon fiber paper, load has appropriate porous carbon microsphere;
5) with deionized water, rinsed, under 80 ℃, drying is 3 hours, obtains the porous carbon microsphere electrode material based on function of surface functional group;
6) by CuCl 2join HNO 3in solution, CuCl wherein 2concentration be 0.06mol/L, obtain the electrolyte material of porous carbon microsphere ultracapacitor;
7) assemble ultracapacitor with three-electrode method, wherein, using the electrode material of step 5) gained as work electrode, platinum electrode is as to electrode, and calomel electrode is as reference electrode, usings the electrolyte of step 6) gained as the electrolyte material of ultracapacitor.
Fig. 5 is that the porous carbon microsphere electrode material is in acidic electrolysis bath and 0.06mol/L copper chloride acidic electrolysis bath, sweep speed for the cyclic voltammetric collection of illustrative plates under 5mv/s, as can be seen from the figure, the specific discharge capacity of porous carbon microsphere electrode material in sulfuric acid electrolyte is 460F/g, specific discharge capacity in 0.06mol/L copper chloride and 1mol/L nitric acid electrolyte is 3072F/g, top-right embedding figure is that the porous carbon microsphere electrode material is in the lmol/L sulfuric acid electrolyte, sweep speed for the cyclic voltammetric collection of illustrative plates of 5mv/s, as can be seen from the figure, the capacity of porous carbon microsphere electrode material in this electrolyte is mass ratio 460F/g, bottom-right embedding figure is that the porous carbon microsphere electrode material is at 0.12mol/L CuSO 4+ 1mol/L H 2sO 4in mixed electrolytic solution, sweeping speed is the cyclic voltammetry curve collection of illustrative plates of 5mv/s, and as can be seen from the figure, the specific discharge capacity of porous carbon microsphere electrode material in this electrolyte is 420F/g.

Claims (5)

1. based on function of surface functional group porous carbon microsphere electrode material, it is following preparation method's products therefrom, includes following steps:
1) by 1.5molLiOH and 1.5molCl 2cH-COOH is dissolved in the 100ml deionized water, and magnetic agitation, to without bulky grain, forms Cl 2the CH-COOLi presoma, by the Cl obtained 2the CH-COOLi presoma forms micro-drop by the ullrasonic spraying cracking, and micro-drop of gained carries out pyrolysis under 800 ℃ at nitrogen atmosphere, collects and obtains black powder;
2) with ethanol and the centrifugation of deionized water difference, wash three times;
3) under 80 ℃, dry 6-12 hour obtains porous carbon microsphere;
4) carbon fiber paper is cut into to 2*3cm 2be immersed in the 5ml ethanolic solution that contains the 0.1g porous carbon microsphere 30 seconds, then take out, under high-pressure sodium lamp dry 1 minute, triplicate, to guarantee that on carbon fiber paper, load has appropriate porous carbon microsphere;
5) with deionized water, rinsed, under 80 ℃, drying is 3 hours, obtains the porous carbon microsphere electrode material based on function of surface functional group.
2. the preparation method based on function of surface functional group porous carbon microsphere electrode material claimed in claim 1 includes following steps:
1) by 1.5molLiOH and 1.5molCl 2cH-COOH is dissolved in the 100ml deionized water, and magnetic agitation, to without bulky grain, forms Cl 2the CH-COOLi presoma, by the Cl obtained 2the CH-COOLi presoma forms micro-drop by the ullrasonic spraying cracking, and micro-drop of gained carries out pyrolysis under 800 ℃ at nitrogen atmosphere, collects and obtains black powder;
2) with ethanol and the centrifugation of deionized water difference, wash three times;
3) under 80 ℃, dry 6-12 hour obtains porous carbon microsphere;
4) carbon fiber paper is cut into to 2*3cm 2be immersed in the 5ml ethanolic solution that contains the 0.1g porous carbon microsphere 30 seconds, then take out, under high-pressure sodium lamp dry 1 minute,, triplicate, to guarantee that on carbon fiber paper, load has appropriate porous carbon microsphere;
5) with deionized water, rinsed, under 80 ℃, drying is 3 hours, obtains the porous carbon microsphere electrode material based on function of surface functional group.
3. one kind includes the ultracapacitor based on function of surface functional group porous carbon microsphere electrode material claimed in claim 1.
4. the preparation method of the ultracapacitor based on function of surface functional group porous carbon microsphere electrode material claimed in claim 3 includes following steps:
1) by 1.5molLiOH and 1.5molCl 2cH-COOH is dissolved in the 100ml deionized water, and magnetic agitation, to without bulky grain, forms Cl 2the CH-COOLi presoma, by the Cl obtained 2the CH-COOLi presoma forms micro-drop by the ullrasonic spraying cracking, and micro-drop of gained carries out pyrolysis under 800 ℃ at nitrogen atmosphere, collects and obtains black powder;
2) with ethanol and the centrifugation of deionized water difference, wash three times;
3) under 80 ℃, dry 6-12 hour obtains porous carbon microsphere;
4) carbon fiber paper is cut into to 2*3cm 2be immersed in the 5ml ethanolic solution that contains the 0.1g porous carbon microsphere 30 seconds, then take out, under high-pressure sodium lamp dry 1 minute,, triplicate, to guarantee that on carbon fiber paper, load has appropriate porous carbon microsphere;
5) with deionized water, rinsed, under 80 ℃, drying is 3 hours, obtains the porous carbon microsphere electrode material based on function of surface functional group;
6) by CuCl 2join HNO 3in solution, CuCl wherein 2concentration change from 0.0001 to 1mol/L, obtain the electrolyte material of porous carbon microsphere ultracapacitor;
7) assemble ultracapacitor with three-electrode method, wherein, using the electrode material of step 5) gained as work electrode, platinum electrode is as to electrode, and calomel electrode is as reference electrode, usings the electrolyte of step 6) gained as the electrolyte material of ultracapacitor.
5. the preparation method of the ultracapacitor based on function of surface functional group porous carbon microsphere electrode material as claimed in claim 4, is characterized in that, CuCl in described electrolyte material 2concentration be 0.06～0.09mol/L.
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Publication number Priority date Publication date Assignee Title
US9914106B2 (en) 2015-01-23 2018-03-13 The Board Of Trustees Of The University Of Illinois Method of producing silicone microspheres
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