CN107221449B - A kind of electrode material of supercapacitor and preparation method thereof - Google Patents
A kind of electrode material of supercapacitor and preparation method thereof Download PDFInfo
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Abstract
The present invention provides electrode materials of a kind of supercapacitor and preparation method thereof, the electrode material includes the following raw material component: the carbon nanotube of 5-15%, the Platinum Nanoparticles of 4-8%, the silver chlorate of 25-40% and the conductive high polymer monomer of 45-60% based on mass percentage.The preparation method is that dispersing the carbon nanotube of formula ratio, Platinum Nanoparticles and silver chlorate in the aqueous solution of surfactant, then the conductive high polymer monomer and electrolyte of formula ratio are added into the dispersion liquid A, it will be in working electrode and the dispersion liquid being placed in electrode after mixing, in the working electrode and to applying voltage between electrode, carry out electrochemical polymerization, after the completion of polymerization, the electrode material is obtained on the working electrode.Electrode material provided by the invention electric conductivity with higher and specific capacity, help to improve the power and energy of supercapacitor.
Description
Technical field
The invention belongs to electrode material technical fields, and in particular to a kind of electrode material of supercapacitor and its preparation side
Method.
Background technique
Supercapacitor is due to the incomparable high power density of conventional batteries, long circulation life and pollution-free etc. special
Point promises to be this century novel green power supply.Electrode material is the most key part of supercapacitor, and is determined
The principal element of its performance, therefore developing the electrode material with excellent properties is class most crucial in supercapacitor research
Topic.
The common electrode material of supercapacitor have conductive polymer material (polypyrrole, polyaniline, polythiophene and they
Derivative etc.), carbon materials (active carbon, carbon nanotube, carbon fiber, graphene etc.) and metal oxide (ruthenium-oxide etc.).
The advantages of above-mentioned electrode material all has respective advantage and disadvantage when being used alone, and combination electrode material can integrate different materials,
It can be further improved its electrical property, to obtain extensive research.
CN 105111702A disclose it is a kind of based on high molecular material/graphene combination electrode material, in electrode modification
The high temperature degradation for utilizing high-molecular organic material in the process, Platinum Nanoparticles and graphene are combined closely and are adhered on the electrode, are mentioned
The high uniformity of electrode modification object, considerably increases the electric conductivity of carrier electrode.But actually due to the combination electrode material
High molecular material used itself is non-conductive, and graphene and Platinum Nanoparticles difficulties in dispersion, and additive amount cannot form it into completely
Conductive path, therefore the electric conductivity of the combination electrode material and specific capacity are unsatisfactory, through studying, in 5mA/cm2's
Specific capacity under current density is only 30-42F/g.In addition, the preparation method of the combination electrode material is complicated, need to protect in argon gas
It is warming up to 650 DEG C or more under shield, is unfavorable for industrial production.
Therefore, it is needed to be further increased for the electric conductivity and specific capacity of the electrode material of supercapacitor,
Preparation method is also required to be further improved.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of electrode material of supercapacitor and
Preparation method.Electrode material electric conductivity with higher and specific capacity, help to improve supercapacitor power and
Energy.
To achieve this purpose, the present invention adopts the following technical scheme:
On the one hand, the present invention provides a kind of electrode material of supercapacitor, based on mass percentage, comprising following former
Expect component:
Carbon nanotube 5-15%, Platinum Nanoparticles 4-8%, silver chlorate 25-40% and conductive high polymer monomer 45-60%.
In electrode material provided by the invention, the conduction that carbon nanotube is coated on conductive high polymer monomer formation completely is gathered
It closes in object, the characteristics of carbon nanotube high length-diameter ratio allows to connect the conducting polymer of large area, is formed complete
Conductive path, and carbon nanotube, Platinum Nanoparticles and silver chlorate have synergistic effect, by adjusting the dosage of three suitable
In range, to make electrode material provided by the invention electric conductivity with higher and specific capacity.
In the present invention, the mass percentage of carbon nanotube can be 5%, 6%, 7%, 8%, 9%, 10%, 11%,
12%, 13%, 14% or 15% etc..
The mass percentage of Platinum Nanoparticles can be 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5% or
8% etc..
The mass percentage of silver chlorate can be 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%,
33%, 34%, 35%, 36%, 37%, 38%, 39% or 40% etc..
The mass percentage of conductive high polymer monomer can be 45%, 46%, 47%, 48%, 49%, 50%, 51%,
52%, 53%, 54%, 55%, 56%, 57%, 58%, 59% or 60% etc..
Preferably, the draw ratio of the carbon nanotube be 100-200:1, such as can be 100:1,110:1,120:1,
130:1,140:1,150:1,160:1,170:1,180:1,190:1 or 200:1 etc..
Preferably, the partial size of the Platinum Nanoparticles be 50-500nm, such as can be 50nm, 100nm, 150nm, 200nm,
250nm, 300nm, 350nm, 400nm, 450nm or 500nm etc..
Preferably, the partial size of the silver chlorate be 50-200nm, such as can be 50nm, 60nm, 80nm, 100nm,
120nm, 140nm, 150nm, 160nm, 180nm or 200nm etc..
Preferably, the conductive high polymer monomer is in pyrroles, aniline, thiophene, methylpyrrole or ethene dioxythiophene
One kind or at least two combination；Such as can be the combination of pyrroles and aniline, combination, pyrroles and the methyl of pyrroles and thiophene
The combination of pyrroles, the combination of aniline and thiophene, the combination of aniline and ethene dioxythiophene or methylpyrrole or ethene dioxythiophene
Combination etc..
On the other hand, the present invention provides a kind of preparation method of above-mentioned electrode material, includes the following steps:
(1) it disperses the carbon nanotube of formula ratio, Platinum Nanoparticles and silver chlorate in the aqueous solution of surfactant, is divided
Dispersion liquid A；
(2) conductive high polymer monomer and electrolyte of formula ratio are added in Xiang Suoshu dispersion liquid A, obtains dispersion liquid after mixing
B；
(3) it is placed in the dispersion liquid B by working electrode and to electrode, applies in the working electrode and between electrode
Voltage carries out electrochemical polymerization, after the completion of polymerization, the electrode material is obtained on the working electrode.
Preferably, the surfactant is lauryl sodium sulfate, dodecyl sodium sulfate, tetraethyl ammonium or the tetrabutyl
Ammonium.
Preferably, in the dispersion liquid A, the gross mass percentage composition of carbon nanotube, Platinum Nanoparticles and silver chlorate is 0.05-
0.2%, such as can be 0.05%, 0.08%, 0.1%, 0.12%, 0.15%, 0.18% or 0.2% etc..
Preferably, the electrolyte in sodium chloride, sodium nitrate, sodium sulphate, potassium chloride, potassium nitrate or potassium sulfate one
Kind or at least two combination, such as can be the combination of sodium chloride and potassium chloride, the combination of sodium nitrate and sodium sulphate, sodium sulphate
The combination etc. of combination or potassium nitrate and potassium sulfate with potassium chloride.
Preferably, in the dispersion liquid B, the concentration of electrolyte is 0.1-0.3mol/L, for example, can be 0.1mol/L,
0.15mol/L, 0.2mol/L, 0.25mol/L or 0.3mol/L etc..
Preferably, it disperse and mix described in step (2) to be carried out under ultrasonic vibration described in step (1).
Preferably, in step (3), the working electrode and the current density between electrode are 0.1-10mA/
cm2, such as can be 0.1mA/cm2、0.5mA/cm2、1mA/cm2、2mA/cm2、3mA/cm2、4mA/cm2、5mA/cm2、6mA/
cm2、7mA/cm2、8mA/cm2、9mA/cm2Or 10mA/cm2Deng.
Preferably, the time of polymerization described in step (3) be 15-30min, such as can be 15min, 16min, 17min,
18min, 19min, 20min, 21min, 22min, 23min, 24min, 25min, 26min, 27min, 28min, 29min or
30min etc..
Compared with prior art, the invention has the following advantages:
In electrode material provided by the invention, the conduction that carbon nanotube is coated on conductive high polymer monomer formation completely is gathered
It closes in object, the characteristics of carbon nanotube high length-diameter ratio allows to connect the conducting polymer of large area, is formed complete
Conductive path, and carbon nanotube, Platinum Nanoparticles and silver chlorate have synergistic effect, by adjusting the dosage of three suitable
In range, to make electrode material provided by the invention electric conductivity with higher and specific capacity, volume resistivity 50-
200 Ω cm, in 5mA/cm2Current density under specific capacity be 240-300F/g.
Specific embodiment
Below by specific embodiment to further illustrate the technical scheme of the present invention.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
A kind of electrode material of supercapacitor includes the following raw material component: carbon nanotube based on mass percentage
5%, Platinum Nanoparticles 8%, silver chlorate 27% and pyrroles 60%；
Wherein, the draw ratio of carbon nanotube is 100:1, and the partial size of Platinum Nanoparticles is 50-100nm, and the partial size of silver chlorate is
100-120nm。
The preparation method of above-mentioned electrode material includes the following steps:
(1) it disperses the carbon nanotube of formula ratio, Platinum Nanoparticles and silver chlorate in the aqueous solution of lauryl sodium sulfate, makes
The gross mass percentage composition of carbon nanotube, Platinum Nanoparticles and silver chlorate is 0.05%, and ultrasonic vibration 5-30min obtains dispersion liquid A；
(2) pyrroles and the sodium sulphate of formula ratio are added into dispersion liquid A, makes the concentration 0.1mol/L of sodium sulphate, ultrasound
5-30min is shaken, dispersion liquid B is obtained；
(3) it is placed in dispersion liquid B by working electrode and to electrode, in working electrode and to voltage is applied between electrode, makes
Current density is 5mA/cm2, electrochemical polymerization is carried out, polymerization time 20min after the completion of polymerization, is obtained on the working electrode (s
Above-mentioned electrode material.
Embodiment 2
A kind of electrode material of supercapacitor includes the following raw material component: carbon nanotube based on mass percentage
15%, Platinum Nanoparticles 4%, silver chlorate 31% and aniline 50%；
Wherein, the draw ratio 100:1 of carbon nanotube, the partial size of Platinum Nanoparticles are 150-200nm, and the partial size of silver chlorate is 50-
80nm。
The preparation method of above-mentioned electrode material includes the following steps:
(1) it disperses the carbon nanotube of formula ratio, Platinum Nanoparticles and silver chlorate in the aqueous solution of dodecyl sodium sulfate, makes
The gross mass percentage composition of carbon nanotube, Platinum Nanoparticles and silver chlorate is 0.2%, and ultrasonic vibration 5-30min obtains dispersion liquid A；
(2) aniline and potassium sulfate of formula ratio are added into dispersion liquid A, makes the concentration 0.3mol/L of potassium sulfate, ultrasound
5-30min is shaken, dispersion liquid B is obtained；
(3) it is placed in dispersion liquid B by working electrode and to electrode, in working electrode and to voltage is applied between electrode, makes
Current density is 0.1mA/cm2, electrochemical polymerization is carried out, polymerization time 30min after the completion of polymerization, is obtained on the working electrode (s
To above-mentioned electrode material.
Embodiment 3
A kind of electrode material of supercapacitor includes the following raw material component: carbon nanotube based on mass percentage
10%, Platinum Nanoparticles 5%, silver chlorate 40% and thiophene 45%；
Wherein, the draw ratio of carbon nanotube is 150:1, and the partial size of Platinum Nanoparticles is 200-250nm, and the partial size of silver chlorate is
80-100nm。
The preparation method of above-mentioned electrode material includes the following steps:
(1) it disperses the carbon nanotube of formula ratio, Platinum Nanoparticles and silver chlorate in the aqueous solution of tetrabutylammonium, makes carbon nanometer
The gross mass percentage composition of pipe, Platinum Nanoparticles and silver chlorate is 0.1%, and ultrasonic vibration 5-30min obtains dispersion liquid A；
(2) thiophene and sodium chloride of formula ratio are added into dispersion liquid A, makes the concentration 0.2mol/L of sodium chloride, ultrasound
5-30min is shaken, dispersion liquid B is obtained；
(3) it is placed in dispersion liquid B by working electrode and to electrode, in working electrode and to voltage is applied between electrode, makes
Current density is 1mA/cm2, electrochemical polymerization is carried out, polymerization time 25min after the completion of polymerization, is obtained on the working electrode (s
Above-mentioned electrode material.
Embodiment 4
A kind of electrode material of supercapacitor includes the following raw material component: carbon nanotube based on mass percentage
8%, Platinum Nanoparticles 6%, silver chlorate 36% and methylpyrrole 45%；
Wherein, the draw ratio of carbon nanotube is 160-180:1, and the partial size of Platinum Nanoparticles is 250-300nm, the partial size of silver chlorate
For 150-160nm.
The preparation method of above-mentioned electrode material includes the following steps:
(1) it disperses the carbon nanotube of formula ratio, Platinum Nanoparticles and silver chlorate in the aqueous solution of tetraethyl ammonium, makes carbon nanometer
The gross mass percentage composition of pipe, Platinum Nanoparticles and silver chlorate is 0.15%, and ultrasonic vibration 5-30min obtains dispersion liquid A；
(2) methylpyrrole and sodium nitrate of formula ratio are added into dispersion liquid A, makes the concentration 0.15mol/L of sodium nitrate,
Ultrasonic vibration 5-30min obtains dispersion liquid B；
(3) it is placed in dispersion liquid B by working electrode and to electrode, in working electrode and to voltage is applied between electrode, makes
Current density is 8mA/cm2, electrochemical polymerization is carried out, polymerization time 15min after the completion of polymerization, is obtained on the working electrode (s
Above-mentioned electrode material.
Embodiment 5
A kind of electrode material of supercapacitor includes the following raw material component: carbon nanotube based on mass percentage
7%, Platinum Nanoparticles 8%, silver chlorate 30% and ethene dioxythiophene 55%；
Wherein, the draw ratio of carbon nanotube is 100-120:1, and the partial size of Platinum Nanoparticles is 350-500nm, the partial size of silver chlorate
For 180-200nm.
The preparation method of above-mentioned electrode material includes the following steps:
(1) it disperses the carbon nanotube of formula ratio, Platinum Nanoparticles and silver chlorate in the aqueous solution of dodecyl sodium sulfate, makes
The gross mass percentage composition of carbon nanotube, Platinum Nanoparticles and silver chlorate is 0.2%, and ultrasonic vibration 5-30min obtains dispersion liquid A；
(2) ethene dioxythiophene and sodium sulphate of formula ratio are added into dispersion liquid A, makes the concentration of sodium sulphate
0.25mol/L, ultrasonic vibration 5-30min obtain dispersion liquid B；
(3) it is placed in dispersion liquid B by working electrode and to electrode, in working electrode and to voltage is applied between electrode, makes
Current density is 2mA/cm2, electrochemical polymerization is carried out, polymerization time 22min after the completion of polymerization, is obtained on the working electrode (s
Above-mentioned electrode material.
Comparative example 1
The difference from embodiment 1 is that the mass percentage of each raw material component is respectively as follows: carbon nanotube 0%, Platinum Nanoparticles
8%, silver chlorate 32% and pyrroles 60%.
Comparative example 2
The difference from embodiment 1 is that the mass percentage of each raw material component is respectively as follows: carbon nanotube 5%, Platinum Nanoparticles
0%, silver chlorate 35% and pyrroles 60%.
Comparative example 3
The difference from embodiment 1 is that the mass percentage of each raw material component is respectively as follows: carbon nanotube 20%, Platinum Nanoparticles
20%, silver chlorate 0% and pyrroles 60%.
Comparative example 4
The difference from embodiment 1 is that the mass percentage of each raw material component is respectively as follows: carbon nanotube 3%, Platinum Nanoparticles
10%, silver chlorate 20% and pyrroles 60%
Comparative example 5
The difference from embodiment 1 is that the mass percentage of each raw material component is respectively as follows: carbon nanotube 18%, Platinum Nanoparticles
2%, silver chlorate 20% and pyrroles 60%.
Comparative example 6
The difference from embodiment 1 is that the mass percentage of each raw material component is respectively as follows: carbon nanotube 4%, Platinum Nanoparticles
3%, silver chlorate 43% and pyrroles 60%.
The performance data for the electrode material that above-described embodiment 1-5 and comparative example 1-6 is provided is as shown in table 1 below.
Table 1
By the performance data of table 1 it is found that when not adding any of carbon nanotube, Platinum Nanoparticles and silver chlorate,
The volume resistivity that will lead to electrode material obtained is significantly raised, and specific capacity declines to a great extent；When carbon nanotube, Platinum Nanoparticles or chlorine
When the dosage of change silver goes beyond the scope, the electric conductivity and specific capacity for also resulting in electrode material obtained are reduced；Only work as carbon
When the dosage of nanotube, Platinum Nanoparticles or silver chlorate is in suitable range, three could preferably play synergistic effect, improve
The electric conductivity and specific capacity of electrode material.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (13)
1. a kind of electrode material of supercapacitor, which is characterized in that the electrode material is based on mass percentage, comprising such as
Lower raw material components:
Carbon nanotube 5-15%, Platinum Nanoparticles 4-8%, silver chlorate 25-40% and conductive high polymer monomer 45-60%.
2. electrode material according to claim 1, which is characterized in that the draw ratio of the carbon nanotube is 100-200:1.
3. electrode material according to claim 1 or 2, which is characterized in that the partial size of the Platinum Nanoparticles is 50-500nm.
4. electrode material according to claim 1, which is characterized in that the partial size of the silver chlorate is 50-200nm.
5. electrode material according to claim 1, which is characterized in that the conductive high polymer monomer be selected from pyrroles, aniline,
One of thiophene, methylpyrrole or ethene dioxythiophene or at least two combination.
6. the preparation method of electrode material according to claim 1-5, which is characterized in that the preparation method packet
Include following steps:
(1) it disperses the carbon nanotube of formula ratio, Platinum Nanoparticles and silver chlorate in the aqueous solution of surfactant, obtains dispersion liquid
A；
(2) conductive high polymer monomer and electrolyte of formula ratio are added in Xiang Suoshu dispersion liquid A, dispersion liquid B is obtained after mixing；
(3) it is placed in the dispersion liquid B by working electrode and to electrode, in the working electrode and to application electricity between electrode
Pressure carries out electrochemical polymerization, after the completion of polymerization, the electrode material is obtained on the working electrode.
7. preparation method according to claim 6, which is characterized in that the surfactant be lauryl sodium sulfate,
Dodecyl sodium sulfate, tetraethyl ammonium or tetrabutylammonium.
8. preparation method according to claim 6, which is characterized in that in the dispersion liquid A, carbon nanotube, Platinum Nanoparticles and
The gross mass percentage composition of silver chlorate is 0.05-0.2%.
9. preparation method according to claim 6, which is characterized in that the electrolyte is selected from sodium chloride, sodium nitrate, sulfuric acid
One of sodium, potassium chloride, potassium nitrate or potassium sulfate or at least two combination.
10. preparation method according to claim 6, which is characterized in that in the dispersion liquid B, the concentration of electrolyte is
0.1-0.3mol/L。
11. preparation method according to claim 6, which is characterized in that institute in dispersion described in step (1) and step (2)
Stating mixing is carried out under ultrasonic vibration.
12. preparation method according to claim 6, which is characterized in that in step (3), the working electrode and described right
Current density between electrode is 0.1-10mA/cm2。
13. preparation method according to claim 6, which is characterized in that the time of polymerization described in step (3) is 15-
30min。
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| KR100894481B1 (en) * | 2007-04-16 | 2009-04-22 | 한국과학기술연구원 | Electrode for supercapacitor having metal oxide deposited onto ultrafine carbon fiber and the fabrication method thereof |
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Effective date of registration: 20211130 Address after: Room 705-146, floor 7, No. 22, dongbeitang east section, Xigang Road, Xishan District, Wuxi City, Jiangsu Province, 214000 Patentee after: Wuxi Pinyuan intellectual property affairs Co.,Ltd. Address before: Room 111-1, building 6, Ruiyun, No. 99, Furong Zhongsan Road, Xishan Economic Development Zone, Wuxi City, Jiangsu Province Patentee before: Wuxi Pinyuan Intellectual Property Consulting Co., Ltd |
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