WO2024039349A1 - Mellitic acid doped polypyrrole coated carbon felt electrode and the preparation method thereof - Google Patents
Mellitic acid doped polypyrrole coated carbon felt electrode and the preparation method thereof Download PDFInfo
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- WO2024039349A1 WO2024039349A1 PCT/TR2023/050820 TR2023050820W WO2024039349A1 WO 2024039349 A1 WO2024039349 A1 WO 2024039349A1 TR 2023050820 W TR2023050820 W TR 2023050820W WO 2024039349 A1 WO2024039349 A1 WO 2024039349A1
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- supercapacitors
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- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims description 10
- 238000000034 method Methods 0.000 claims abstract description 20
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 11
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 8
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000002957 persistent organic pollutant Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 abstract description 14
- 239000003792 electrolyte Substances 0.000 description 27
- 238000002484 cyclic voltammetry Methods 0.000 description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 8
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 8
- 239000002608 ionic liquid Substances 0.000 description 6
- 239000005486 organic electrolyte Substances 0.000 description 6
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 125000002843 carboxylic acid group Chemical group 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
Definitions
- the invention relates to a mellitic acid doped, polypyrrole coated environmentally friendly carbon felt electrode for use in supercapacitors and a method of preparing this electrode.
- the electrode that is the subject of the invention With the use of the electrode that is the subject of the invention in supercapacitors, the energy storage performance of the supercapacitor is increased, and supercapacitors that have a long cycle life, low cost, and high energy density and maintain their performance depending on use are obtained.
- Supercapacitors are promising energy storage systems due to their long chargedischarge life, low cost and high energy density. While the energy storage mechanisms of batteries occur only through redox events, the energy storage mechanisms of supercapacitors are realised by both redox and charge transfer of electrolyte ions to the electrode surface [1], Among the components of supercapacitor systems are electrolytes. In supercapacitor systems, aqueous electrolytes such as sodium chloride (NaCI), potassium chloride (KCI), sulphuric acid (H2SO4), phosphoric acid (H3PO4) and potassium hydroxide (KOH) are used. These aqueous electrolytes exhibit a wide range of electrochemical working potential.
- NaCI sodium chloride
- KCI potassium chloride
- H2SO4 sulphuric acid
- H3PO4 phosphoric acid
- KOH potassium hydroxide
- aqueous electrolytes since the production costs of the aforementioned aqueous electrolytes are low, these aqueous electrolytes are often preferred in the production of supercapacitors.
- the working potential range of aqueous electrolytes is limited to about 1.2 V due to the thermodynamic decomposition potential of water. Therefore, the operating potential range of supercapacitors working with aqueous electrolytes is a great disadvantage since it cannot meet the operating potential required in electronic devices [2],
- a mellitic acid doped, polypyrrole coated environmentally friendly carbon felt electrode for use in supercapacitors and a method of preparing this electrode is described.
- the energy storage performance of the supercapacitor is increased, and supercapacitors that have a long cycle life, low cost, and high energy density and maintain their performance depending on use are obtained.
- An aim of the invention is to improve the energy storage, cycle life, energy density and usage-related performance characteristics of supercapacitors at a low cost. Improving the performance properties of supercapacitors at a low cost is provided by a mellitic acid doped, polypyrrole coated carbon felt electrode, which is the subject of the invention, and the preparation method thereof.
- expensive materials such as metal/metal oxide, which are used in supercapacitor electrodes in the state of the art, are not used in a mellitic acid doped, polypyrrole coated carbon felt electrode that is the subject of the invention.
- the electrode system that is the subject of the invention comprises aqueous electrolytes, which is a cheap material, also eliminates the cost problem in supercapacitors.
- the process costs to be incurred are eliminated by means of the fact that the carbon felt electrode, which is the subject of the invention, is produced with an effortless process compared to those known in the state of the art.
- the use of the supercapacitor electrode that is the subject of the invention as an electrode material directly as a result of a single chemical treatment with the addition of carbon felt and the specified chemicals into the hydrothermal reactor provides a great advantage in terms of process cost.
- the supercapacitor electrode that is the subject of the invention provides high performance properties without being subjected to any other coating and production process.
- the supercapacitor performance is increased by 4.7 times with the effect of mellitic acid doped as an ion against the structure of conductive polymers in the electrodes that are the subject of the invention, which are obtained at low cost.
- the chemical and physical properties of polypyrrole are improved and the supercapacitor performance is increased by means of the carboxyl (-COOH) groups excessively present in the film formation of mellitic acid, which is a carboxylic acid used as a counter ion.
- mellitic acid which is a carboxylic acid used as a counter ion.
- the energy storage performance of supercapacitors is improved. Improving the energy storage performance in supercapacitors is provided by a mellitic acid doped, polypyrrole coated carbon felt electrode and by the preparation method thereof, which are the subject of the invention.
- a mellitic acid doped, polypyrrole coated carbon felt electrode and by the preparation method thereof, which are the subject of the invention.
- electron transfer is facilitated when the electrode material synthesised in the mellitic acid environment comes into contact with the electrolyte, and thus, the possibility of reaching wide operating voltage and high current densities is provided to the supercapacitors when the electrodes of the invention are used in supercapacitors.
- the electrode that is the subject of the invention increases the supercapacitance performance of the supercapacitors in which they are used, that is, the energy storage performance.
- the electrode that is the subject of the invention is used in supercapacitors, more charge-discharge cycles are provided to the supercapacitor compared to batteries.
- Another aim of the invention is to ensure that supercapacitors have a long cycle life.
- the long cycle life of supercapacitors is ensured by a mellitic acid doped, polypyrrole coated carbon felt electrode, which is the subject of the invention, and by the preparation method thereof. Since the electrode that is the subject of the invention comprises mellitic acid in addition to polypyrrole, it increases the cycle life of the supercapacitors where it is used. For example, at the end of 1000 cycles, a polypyrrole-based electrode can only maintain 16.8% of its capacitance performance, while a mellitic acid-doped and polypyrrole-coated carbon felt electrode, which is the subject of the invention, can maintain its capacitance value at the rate of 89.5%.
- Another aim of the invention is to enable supercapacitors to exhibit high energy density.
- Providing high energy density to supercapacitors is ensured by a mellitic acid doped and polypyrrole coated carbon felt electrode and the preparation method thereof.
- mellitic acid is added to the polypyrrole structure as a counterion, and by this means, said electrode can operate in a wide potential range such as 3.2 V.
- the electrode, which is the subject of the invention is used in supercapacitors, which can operate in a wide potential range such as 3.2 V, a high energy density is ensured in supercapacitors.
- Another aim of the invention is to provide an environmentally friendly electrode for use in supercapacitors.
- Environmentally harmful materials such as metal/metal oxide used in supercapacitor electrodes in the state of the art are not used in a mellitic acid doped and polypyrrole coated carbon felt electrode, which is the subject of the invention.
- Figure 1 Comparative graph of the cyclic voltammograms of the polypyrrole-based electrodes comprising different carboxylic acid groups in the prior art and the cyclic voltammogram of the polypyrrole and mellitic acid doped electrode, which is the subject of the invention; a) polypyrrole, b) polypyrrole/mellitic acid, c) polypyrrole/pyromellitic acid, d) polypyrrole/phthalic acid
- FIG. 1 Comparative graph of the galvanostatic charge/discharge (GCD) curves of the prior art polypyrrole-based electrodes comprising different carboxylic acid groups and the galvanostatic charge/discharge (GCD) curves of the polypyrrole and mellitic acid doped electrode, which is the subject of the invention; e) polypyrrole/mellitic acid, f) polypyrrole/pyromellitic acid, g) polypyrrole/phthalic acid, h) polypyrrole
- FIG. 7 Comparative graph of the cycle numbers of the polypyrrole-based electrodes comprising different carboxylic acid groups in the prior art at a current density of 1 A/g and the cycle number of the polypyrrole and mellitic acid doped electrode, which is the subject of the invention; i) polypyrrole/mellitic acid, i) polypyrrole/pyromellitic acid, j) polypyrrole/phthalic acid, k) polypyrrole
- Figure 15 Graph showing the % capacitance performance and the EIS test in the graph depending on the number of cycles of the supercapacitor in which the electrode that is the subject of the invention is used.
- the invention relates to a mellitic acid doped, polypyrrole coated environmentally friendly carbon felt electrode for use in supercapacitors and a method of preparing this electrode.
- the electrode that is the subject of the invention With the use of the electrode that is the subject of the invention in supercapacitors, the energy storage performance of the supercapacitor is increased, and supercapacitors that have a long cycle life, low cost, and high energy density and maintain their performance depending on use are obtained.
- a mellitic acid doped and polypyrrole coated, environmentally friendly carbon felt electrode that is the subject of the invention for use in the supercapacitors comprises pyrrole monomer, mellitic acid and ferric chloride hexahydrate and the concentrations of said components in 20 mL volume are 0.001-0.5 mol/L pyrrole monomer, 0.005-0.1 mol/L mellitic acid and 0.001 -0.5 mol/L ferric chloride hexahydrate.
- the surface area of said carbon felt electrode is 4x5 cm 2 .
- a method of preparing a mellitic acid doped and polypyrrole coated, environmentally friendly carbon felt electrode that is the subject of the invention for use in the supercapacitors comprises the process steps of; i. washing the carbon felt electrode with acetone in an ultrasonic bath for 30 minutes and drying it for 4-48 hours at room temperature for the removal of organic pollutants on the surface. ii. immersing the electrodes in nitric acid (HNOs) at room temperature and waiting for 1 -100 hours to activate the electrode surface iii. washing the electrodes kept in nitric acid with deionized water until neutral pH is reached and then drying in an oven at 40-60°C for 12- 36 hours, iv.
- HNOs nitric acid
- the polymerisation mentioned in the process step v in the method is carried out with a hydrothermal reaction.
- a hydrothermal reaction By means of said hydrothermal reaction, an electrode with a rougher and larger surface area is obtained. Therefore, it is ensured that the electrode interacts more with the electrolyte ions and when the electrode of the invention is used in supercapacitors, the capacitance properties of the supercapacitors are improved.
- the maximum capacitance value, energy density and cycle life values of the electrode, which is the subject of the invention, indicated in Table 1 were obtained by using pyrrole monomer at a concentration of 0.2 mol/L and mellitic acid at a concentration of 0.02 mol/L in a 20 mL volume.
- the electrode that is the subject of the invention exhibits maximum performance values by using pyrrole monomer at a concentration of 0.2 mol/L and mellitic acid at a concentration of 0.02 mol/L in a 20 mL volume in the process step iv.
- the electrode that is the subject of the invention increases the supercapacitance performance of the supercapacitors in which they are used, that is, the energy storage performance.
- the electrode that is the subject of the invention is used in supercapacitors, more charge-discharge cycles are provided to the supercapacitor compared to batteries.
- the mellitic acid doped and polypyrrole coated, environmentally friendly carbon felt electrode comprising only the aqueous electrolyte system, which is the subject of the invention, has a higher value than the electrodes in the state of the art in terms of energy density (Wh kg 1 ) provided to the supercapacitors.
- the carbon felt electrode described in the invention comprises only an aqueous electrolyte system, thereby providing an electrode for use in supercapacitors at a low cost.
- cycle life In the invention, high cycle life is provided to the supercapacitor with the use of low cost electrodes.
- the mellitic acid doped and polypyrrole coated, environmentally friendly carbon felt electrode comprising only the aqueous electrolyte system, which is the subject of the invention, compared to the electrodes in the state of the art, provides a very high energy density (785.8 Wh kg -1 ) to the supercapacitors, and despite the minimum electrode cost, it can maintain the supercapacitor capacitance value of 83% at the end of 5000 cycles and can provide the maximum capacitance value of 687 F/g to the supercapacitor at a scanning speed of 5 mV s’ 1 .
- the supercapacitor performance is increased by 4.7 times with the effect of mellitic acid doped as an ion against the structure of conductive polymers in the electrodes that are the subject of the invention, which are obtained at low cost.
- a polypyrrole-based electrode can only maintain 16.8% of its capacitance performance, while a mellitic acid-doped and polypyrrole-coated carbon felt electrode, which is the subject of the invention, can maintain its capacitance value at the rate of 89.5%.
- the electrode, which is the subject of the invention is used in supercapacitors, which can operate in a wide potential range such as 3.2 V, a high energy density is ensured in supercapacitors.
- Environmentally harmful materials such as metal/metal oxide used in supercapacitor electrodes in the state of the art are not used in a mellitic acid doped and polypyrrole coated carbon felt electrode, which is the subject of the invention.
Abstract
The invention relates to a mellitic acid doped, polypyrrole coated environmentally friendly carbon felt electrode for use in supercapacitors and a method of preparing this electrode. With the use of the electrode that is the subject of the invention in supercapacitors, the energy storage performance of the supercapacitor is increased, and supercapacitors that have a long cycle life, low cost, and high energy density and maintain their performance depending on use are obtained.
Description
MELLITIC ACID DOPED POLYPYRROLE COATED CARBON FELT ELECTRODE AND THE PREPARATION METHOD THEREOF
Technical Field of the Invention
The invention relates to a mellitic acid doped, polypyrrole coated environmentally friendly carbon felt electrode for use in supercapacitors and a method of preparing this electrode. With the use of the electrode that is the subject of the invention in supercapacitors, the energy storage performance of the supercapacitor is increased, and supercapacitors that have a long cycle life, low cost, and high energy density and maintain their performance depending on use are obtained.
State of the Art
Supercapacitors are promising energy storage systems due to their long chargedischarge life, low cost and high energy density. While the energy storage mechanisms of batteries occur only through redox events, the energy storage mechanisms of supercapacitors are realised by both redox and charge transfer of electrolyte ions to the electrode surface [1], Among the components of supercapacitor systems are electrolytes. In supercapacitor systems, aqueous electrolytes such as sodium chloride (NaCI), potassium chloride (KCI), sulphuric acid (H2SO4), phosphoric acid (H3PO4) and potassium hydroxide (KOH) are used. These aqueous electrolytes exhibit a wide range of electrochemical working potential. In addition, since the production costs of the aforementioned aqueous electrolytes are low, these aqueous electrolytes are often preferred in the production of supercapacitors. However, the working potential range of aqueous electrolytes is limited to about 1.2 V due to the thermodynamic decomposition potential of water. Therefore, the operating potential range of supercapacitors working with aqueous electrolytes is a great disadvantage since it cannot meet the operating potential required in electronic devices [2],
Some improvements have been made to eliminate the potential gap problem, which is caused by the fact that the potential gap of supercapacitors working with aqueous electrolytes is limited to a maximum of 1.2 V. One of these improvements is the preference of organic electrolytes or ionic liquids over aqueous electrolytes in supercapacitors. These organic electrolytes and ionic liquids are among the most important materials that help to expand the working potential range of supercapacitors
[3], Although these materials, which are used as electrolytes in supercapacitors, play a major role in expanding the working potential range of supercapacitors, these materials cause some problems such as efficiency and cost.
Since most of the organic electrolytes used in supercapacitors in the state of the art are affected by oxygen and humidity in the air, removing the impurities in the environment brings along time and cost problems. If ionic liquids are used in the electrolytes of supercapacitors, it causes an extra cost problem.
A prior art study by Jincy Parayangattil Jyothibasu, Ming-Zhu Chen, and Rong-Ho Lee provides information on the preparation of a self-contained supercapacitor electrode that exhibits a high field capacitance. While preparing said electrode, a polypyrrole/carbon nanotube-based material was used, and when the prepared electrode was used in supercapacitors, a cycle life of 79.03% and a capacitance value of 327.5 F g-1 were obtained.
When we classify the electrodes used in supercapacitors in the state of the art as aqueous electrolytes, organic electrolytes and ionic liquids, organic electrolytes and ionic liquids bring along time and cost problems. On the other hand, supercapacitors using aqueous electrolytes, which are low cost and have a wide range of electrochemical working potential, cannot meet the working potential required in electronic devices. As a result, it does not seem possible to come across any electrolyte configuration that solves the cost, efficiency, time and operating potential problems of supercapacitors in the state of the art. In addition, the electrodes in the state of the art and used in supercapacitors comprise costly and non-environmental materials such as metal or metal oxide.
Due to the reasons such as limitations and inadequacies of electrolyte structures in supercapacitors in the state of the art in terms of efficiency, time, cost and working potential, the time and cost problems of organic electrolytes used as electrodes in supercapacitors in the state of the art, the systems obtained from supercapacitors, in which ionic liquids are used as electrolytes, being able to only meet the needs of daily life and said systems not being suitable for mass production and failure to meet the required working potential in electronic devices in supercapacitors where aqueous electrolytes are used as electrodes, which are low cost and have a wide range of electrochemical working potential, it has been necessary to develop an
environmentally friendly electrode that increases the energy storage performance of supercapacitors, provides a long cycle life for the supercapacitors in which it is used, exhibits high energy density, maintains its performance depending on use, and provides a low cost supercapacitor.
Brief Description and Aims of the Invention
In the invention, a mellitic acid doped, polypyrrole coated environmentally friendly carbon felt electrode for use in supercapacitors and a method of preparing this electrode is described. With the use of the electrode that is the subject of the invention in supercapacitors, the energy storage performance of the supercapacitor is increased, and supercapacitors that have a long cycle life, low cost, and high energy density and maintain their performance depending on use are obtained.
An aim of the invention is to improve the energy storage, cycle life, energy density and usage-related performance characteristics of supercapacitors at a low cost. Improving the performance properties of supercapacitors at a low cost is provided by a mellitic acid doped, polypyrrole coated carbon felt electrode, which is the subject of the invention, and the preparation method thereof. First of all, it should be noted that expensive materials such as metal/metal oxide, which are used in supercapacitor electrodes in the state of the art, are not used in a mellitic acid doped, polypyrrole coated carbon felt electrode that is the subject of the invention. In addition to all these, the fact that the electrode system that is the subject of the invention comprises aqueous electrolytes, which is a cheap material, also eliminates the cost problem in supercapacitors. In addition, the process costs to be incurred are eliminated by means of the fact that the carbon felt electrode, which is the subject of the invention, is produced with an effortless process compared to those known in the state of the art. The use of the supercapacitor electrode that is the subject of the invention as an electrode material directly as a result of a single chemical treatment with the addition of carbon felt and the specified chemicals into the hydrothermal reactor provides a great advantage in terms of process cost. The supercapacitor electrode that is the subject of the invention provides high performance properties without being subjected to any other coating and production process. The supercapacitor performance is increased by 4.7 times with the effect of mellitic acid doped as an ion against the structure of conductive polymers
in the electrodes that are the subject of the invention, which are obtained at low cost. The chemical and physical properties of polypyrrole are improved and the supercapacitor performance is increased by means of the carboxyl (-COOH) groups excessively present in the film formation of mellitic acid, which is a carboxylic acid used as a counter ion. As a result, providing a high performance supercapacitor at low cost is achieved by using an environmentally friendly, mellitic acid doped, polypyrrole coated carbon felt electrode, which is the subject of the invention, in supercapacitors.
In addition, the energy storage performance of supercapacitors is improved. Improving the energy storage performance in supercapacitors is provided by a mellitic acid doped, polypyrrole coated carbon felt electrode and by the preparation method thereof, which are the subject of the invention. In the invention, electron transfer is facilitated when the electrode material synthesised in the mellitic acid environment comes into contact with the electrolyte, and thus, the possibility of reaching wide operating voltage and high current densities is provided to the supercapacitors when the electrodes of the invention are used in supercapacitors. As a result, the electrode that is the subject of the invention increases the supercapacitance performance of the supercapacitors in which they are used, that is, the energy storage performance. When the electrode that is the subject of the invention is used in supercapacitors, more charge-discharge cycles are provided to the supercapacitor compared to batteries.
Another aim of the invention is to ensure that supercapacitors have a long cycle life. The long cycle life of supercapacitors is ensured by a mellitic acid doped, polypyrrole coated carbon felt electrode, which is the subject of the invention, and by the preparation method thereof. Since the electrode that is the subject of the invention comprises mellitic acid in addition to polypyrrole, it increases the cycle life of the supercapacitors where it is used. For example, at the end of 1000 cycles, a polypyrrole-based electrode can only maintain 16.8% of its capacitance performance, while a mellitic acid-doped and polypyrrole-coated carbon felt electrode, which is the subject of the invention, can maintain its capacitance value at the rate of 89.5%.
Another aim of the invention is to enable supercapacitors to exhibit high energy density. Providing high energy density to supercapacitors is ensured by a mellitic acid doped and polypyrrole coated carbon felt electrode and the preparation method thereof. In the electrode that is the subject of the invention, mellitic acid is added to the polypyrrole
structure as a counterion, and by this means, said electrode can operate in a wide potential range such as 3.2 V. When the electrode, which is the subject of the invention, is used in supercapacitors, which can operate in a wide potential range such as 3.2 V, a high energy density is ensured in supercapacitors.
With the invention, it is ensured that the performances of supercapacitors are preserved depending on the use. Preservation of the performance of supercapacitors depending on use is provided by a mellitic acid doped polypyrrole coated carbon felt electrode, which is the subject of the invention, and by the preparation method thereof. As a result of the use of a large anion such as mellitic acid in the electrode, which is the subject of the invention, said mellitic acid enters the skeleton structure of the polymer, allowing the swelling and shrinking behaviour to occur with smaller volumetric changes, and therefore, if the electrode of the invention is used in supercapacitors, the supercapacitor performance is increased depending on the use.
When the electrode that is the subject of the invention is used in supercapacitors, an average of 80% of the capacitance value is preserved even after 5000 cycles, depending on the use.
Another aim of the invention is to provide an environmentally friendly electrode for use in supercapacitors. Environmentally harmful materials such as metal/metal oxide used in supercapacitor electrodes in the state of the art are not used in a mellitic acid doped and polypyrrole coated carbon felt electrode, which is the subject of the invention.
Description of Drawings
Figure 1. Comparative graph of the cyclic voltammograms of the polypyrrole-based electrodes comprising different carboxylic acid groups in the prior art and the cyclic voltammogram of the polypyrrole and mellitic acid doped electrode, which is the subject of the invention; a) polypyrrole, b) polypyrrole/mellitic acid, c) polypyrrole/pyromellitic acid, d) polypyrrole/phthalic acid
Figure 2. Comparative graph of the galvanostatic charge/discharge (GCD) curves of the prior art polypyrrole-based electrodes comprising different carboxylic acid groups and the galvanostatic charge/discharge (GCD) curves of the polypyrrole and mellitic
acid doped electrode, which is the subject of the invention; e) polypyrrole/mellitic acid, f) polypyrrole/pyromellitic acid, g) polypyrrole/phthalic acid, h) polypyrrole
Figure 3. IR drop graph at 0.8 A/g current density of the electrode that is the subject of the invention
Figure 4. Cyclic voltammograms of the electrode that is the subject of the invention at different potential ranges
Figure 5. Cyclic voltammograms of the electrode that is the subject of the invention at different scanning speeds.
Figure 6. Galvanostatic charge/discharge (GCD) curves of the electrode that is the subject of the invention at different current densities
Figure 7. Comparative graph of the cycle numbers of the polypyrrole-based electrodes comprising different carboxylic acid groups in the prior art at a current density of 1 A/g and the cycle number of the polypyrrole and mellitic acid doped electrode, which is the subject of the invention; i) polypyrrole/mellitic acid, i) polypyrrole/pyromellitic acid, j) polypyrrole/phthalic acid, k) polypyrrole
Figure 8. Graph showing the specific capacitance values obtained from the cyclic voltammogram of the electrode that is the subject of the invention at different scanning rates
Figure 9. Graph showing the specific capacitance values obtained from the GCD curves of the electrode that is the subject of the invention
Figure 10. Cyclic voltammograms of the supercapacitor formed by the electrode of the invention at different potential ranges.
Figure 11. Cyclic voltammograms of the supercapacitor using the electrode that is the subject of the invention at different scanning rates.
Figure 12. The galvanostatic charge/discharge (GCD) curves of the supercapacitor using the electrode of the invention at different current density
Figure 13. The specific capacitance values obtained from the cyclic voltammograms of the supercapacitor in which the electrode of the invention is used
Figure 14. The specific capacitance values obtained from the galvanostatic charge/discharge (GCD) curves of the supercapacitor using the electrode of the invention
Figure 15. Graph showing the % capacitance performance and the EIS test in the graph depending on the number of cycles of the supercapacitor in which the electrode that is the subject of the invention is used.
Figure 16. FTIR spectrum of a prior art polypyrrole coated carbon felt electrode
Figure 17. FTIR spectrum of the electrode that is the subject of the invention
Figure 18. Graph showing thermal gravimetric analysis (TGA) of a prior art polypyrrole coated carbon felt electrode
Figure 19. Graphic showing the thermal gravimetric analysis (TGA) of the electrode that is the subject of the invention
Figure 20. SEM image of a prior art polypyrrole coated carbon felt electrode
Figure 21. SEM image of the electrode that is the subject of the invention
Figure 22. Graph showing the pore size distribution analysis of the electrode that is the subject of the invention
Figure 23. Graph showing the adsorption/desorption isotherm of the electrode that is the subject of the invention
Figure 24. Graph showing the multi-point BET surface area analysis of the electrode that is the subject of the invention
Detailed Description of the Invention
The invention relates to a mellitic acid doped, polypyrrole coated environmentally friendly carbon felt electrode for use in supercapacitors and a method of preparing this electrode. With the use of the electrode that is the subject of the invention in supercapacitors, the energy storage performance of the supercapacitor is increased, and supercapacitors that have a long cycle life, low cost, and high energy density and maintain their performance depending on use are obtained.
A mellitic acid doped and polypyrrole coated, environmentally friendly carbon felt electrode that is the subject of the invention for use in the supercapacitors comprises pyrrole monomer, mellitic acid and ferric chloride hexahydrate and the concentrations of said components in 20 mL volume are 0.001-0.5 mol/L pyrrole monomer, 0.005-0.1 mol/L mellitic acid and 0.001 -0.5 mol/L ferric chloride hexahydrate. As the volume of 20 mL changes, the values of the components forming the electrode that is the subject of the invention also change at the same rate. The surface area of said carbon felt electrode is 4x5 cm2.
A method of preparing a mellitic acid doped and polypyrrole coated, environmentally friendly carbon felt electrode that is the subject of the invention for use in the supercapacitors comprises the process steps of; i. washing the carbon felt electrode with acetone in an ultrasonic bath for 30 minutes and drying it for 4-48 hours at room temperature for the removal of organic pollutants on the surface. ii. immersing the electrodes in nitric acid (HNOs) at room temperature and waiting for 1 -100 hours to activate the electrode surface iii. washing the electrodes kept in nitric acid with deionized water until neutral pH is reached and then drying in an oven at 40-60°C for 12- 36 hours, iv. adding pyrrole monomer with a concentration of 0.001 -0.5 mol/L, mellitic acid with a concentration of 0.005-0.1 mol/L, and ferric chloride hexahydrate with a concentration of 0.001 -0.5 mol/L to a 50:50 ethanokwater mixture solution in a 20 mL volume and stirring at room temperature for 30-120 minutes, v. keeping the prepared solution and the carbon felt electrode with a surface area of 4x5 cm2 in an autoclave at 60-180°C for 3-12 hours and carrying out the polymerisation with a hydrothermal reaction, and vi. washing the composite electrodes obtained after the synthesis in 50:50 ethanokwater mixture solution and drying at 40-90°C for 6-24 hours.
The polymerisation mentioned in the process step v in the method is carried out with a hydrothermal reaction. By means of said hydrothermal reaction, an electrode with a rougher and larger surface area is obtained. Therefore, it is ensured that the electrode interacts more with the electrolyte ions and when the electrode of the invention is used in supercapacitors, the capacitance properties of the supercapacitors are improved. In addition to all these, as stated in the method above, in an embodiment of the invention, in the process step iv, the maximum capacitance value, energy density and cycle life values of the electrode, which is the subject of the invention, indicated in Table 1 were obtained by using pyrrole monomer at a concentration of 0.2 mol/L and mellitic acid at a concentration of 0.02 mol/L in a 20 mL volume. In other words, in an embodiment of the invention, the electrode that is the subject of the invention exhibits maximum performance values by using pyrrole monomer at a concentration of 0.2 mol/L and mellitic acid at a concentration of 0.02 mol/L in a 20 mL volume in the process step iv.
In the examination of the performance of the electrode, which is the subject of the invention, in supercapacitors, cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS) methods were used. In the system where 1 .0 M H2SO4 solution is used as the electrolyte, the supercapacitor potential gap of the electrode was optimised by using the cyclic voltammetry method (CV). After determining the potential range with capacitive properties, the same optimisation was also examined using the galvanostatic charge-discharge method (GCD). Finally, electrochemical impedance spectroscopy (EIS) measurements were performed. In addition, the cycle life offered by the electrode material and how much of the capacitance value can be preserved have been examined. Then, a supercapacitor cell was formed using a graphite sheet electrode and 1.0 M H2SO4-AMPS electrolyte. Likewise, the characterisation of the supercapacitor was made using electrochemical methods and said characterisations (spectroscopic, morphological and thermal characterisations) are shown in the figures.
In the invention, electron transfer is facilitated when the electrode material synthesised in the mellitic acid environment comes into contact with the electrolyte, and thus, the possibility of reaching wide operating voltage and high current densities is provided to the supercapacitors when the electrodes of the invention are used in supercapacitors. As a result, the electrode that is the subject of the invention increases the supercapacitance performance of the supercapacitors in which they are used, that is, the energy storage performance. When the electrode that is the subject of the invention
is used in supercapacitors, more charge-discharge cycles are provided to the supercapacitor compared to batteries. By means of the six carboxyl (-COOH) groups contained in the mellitic acid used to obtain the electrode, which is the subject of the invention, high capacitance value is provided to the supercapacitors in which the
5 electrode is used. While phthalic acid used in supercapacitor electrodes in the prior art contains two carboxyl groups and pyromellitic acid contains four carboxyl groups, mellitic acid, which is one of the elements that forms the basis of the invention, contains six carboxyl groups. The effects of carboxyl numbers on supercapacitor performances are shown in Figure 1 , Figure 2 and Figure 7.
,o
Table 1. Comparison table of the performance of the electrode that is the subject of the invention and the electrodes in the state of the art
As can be seen from Table 1 and the graphics in Figure 1-24, the mellitic acid doped and polypyrrole coated, environmentally friendly carbon felt electrode comprising only the aqueous electrolyte system, which is the subject of the invention, has a higher value than the electrodes in the state of the art in terms of energy density (Wh kg 1) provided to the supercapacitors. The carbon felt electrode described in the invention comprises only an aqueous electrolyte system, thereby providing an electrode for use in supercapacitors at a low cost. The same is also true for cycle life. In the invention, high cycle life is provided to the supercapacitor with the use of low cost electrodes. In short, the mellitic acid doped and polypyrrole coated, environmentally friendly carbon felt electrode comprising only the aqueous electrolyte system, which is the subject of the invention, compared to the electrodes in the state of the art, provides a very high energy density (785.8 Wh kg-1) to the supercapacitors, and despite the minimum electrode cost, it can maintain the supercapacitor capacitance value of 83% at the end of 5000 cycles and can provide the maximum capacitance value of 687 F/g to the supercapacitor at a scanning speed of 5 mV s’1.
The supercapacitor performance is increased by 4.7 times with the effect of mellitic acid doped as an ion against the structure of conductive polymers in the electrodes that are the subject of the invention, which are obtained at low cost. At the end of 1000 cycles, a polypyrrole-based electrode can only maintain 16.8% of its capacitance performance, while a mellitic acid-doped and polypyrrole-coated carbon felt electrode, which is the subject of the invention, can maintain its capacitance value at the rate of 89.5%. When the electrode, which is the subject of the invention, is used in supercapacitors, which can operate in a wide potential range such as 3.2 V, a high
energy density is ensured in supercapacitors. Environmentally harmful materials such as metal/metal oxide used in supercapacitor electrodes in the state of the art are not used in a mellitic acid doped and polypyrrole coated carbon felt electrode, which is the subject of the invention.
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5-carboxylic acid) in different electrolytes and its symmetrical supercapacitor in HCIO4 aqueous electrolyte, Synth. Met. 203 (2015) 98-106. https://doi.Org/10.1016/j.synthmet.2O15.02.025. P. Khanra, T. Kuila, S.H. Bae, N.H. Kim, J.H. Lee, Electrochemically exfoliated graphene using 9-anthracene carboxylic acid for supercapacitor application, J. Mater. Chem. 22 (2012) 24403. https://doi.org/10.1039/c2jm34838a. M.D. Najafi, E. Kowsari, H.R. Naderi, A. Chinnappan, S. Ramakrishna, A. Ehsani, A. Shokravi, Functionalization of graphene oxide via chromium complexes coordinated on 5-aminopyridine-2-carboxylic acid as a symmetric
supercapacitor electrode materials in energy storage devices, Compos. Sci. Technol. 211 (2021 ) 108844. https://doi.Org/10.1016/j . com pscitech.2021 .108844. X. Ma, W. Zhou, D. Mo, J. Hou, J. Xu, Effect of substituent position on electrodeposition, morphology, and capacitance performance of polyindole bearing a carboxylic group, Electrochim. Acta. 176 (2015) 1302-1312. https://doi.Org/10.1016/j.electacta.2O15.07.148. T. Zhang, J. Lang, L. Liu, L. Liu, H. Li, Y. Gu, X. Yan, X. Ding, Effect of carboxylic acid groups on the supercapacitive performance of functional carbon frameworks derived from bacterial cellulose, Chinese Chem. Lett. 28 (2017) 2212-2218. https://doi.Org/https://doi.org/10.1016/j.cclet.2O17.08.013. N.C. Abeykoon, S.F. Mahmood, D.J. Yang, J.P. Ferraris, Electrospun poly(acrylonitrile- co -itaconic acid) as a porous carbon precursor for high performance supercapacitor: study of the porosity induced by in situ porogen activity of itaconic acid, Nanotechnology. 30 (2019) 435401. https://doi.Org/10.1088/1361 -6528/ab32c0. L. Yu, X. Wang, M. Cheng, H. Rong, Y. Song, Q. Liu, A Three-Dimensional Copper Coordination Polymer Constructed by 3-Methyl-1 H -pyrazole-4- carboxylic Acid with Higher Capacitance for Supercapacitors, Cryst. Growth Des. 18 (2018) 280-285. https://doi.org/10.1021/acs.cgd.7b01219. Q. Guo, X. Zhao, Z. Li, D. Wang, G. Nie, A novel solid-state electrochromic supercapacitor with high energy storage capacity and cycle stability based on poly(5-formylindole)/WO3 honeycombed porous nanocomposites, Chem. Eng. J. 384 (2020) 123370. https://doi.Org/10.1016/j.cej.2019.123370. S. Ghosh, X. An, R. Shah, D. Rawat, B. Dave, S. Kar, S. Talapatra, Effect of 1- pyrene carboxylic-acid functionalization of graphene on its capacitive energy storage, J. Phys. Chem. C. 116 (2012) 20688-20693. https://doi.Org/10.1021 /jp303339f.
Claims
1. A carbon felt electrode for use in supercapacitors comprising pyrrole monomer, mellitic acid and ferric chloride hexahydrate, wherein the concentrations of said components in a volume of 20 mL are 0.001 -0.5 mol/L pyrrole monomer, 0.005- 0.1 mol/L mellitic acid and 0.001 -0.5 mol/L ferric chloride hexahydrate.
2. An electrode according to Claim 1 , wherein surface area of said carbon felt electrode is 4x5 cm2.
3. The preparation method of the mellitic acid doped, polypyrrole coated environmentally friendly carbon felt electrode for use in supercapacitors, comprising the process steps of: vii. washing the carbon felt electrode with acetone in an ultrasonic bath for 30 minutes and drying it for 4-48 hours at room temperature for the removal of organic pollutants on the surface. viii. immersing the electrodes in nitric acid (HNOs) at room temperature and waiting for 1 -100 hours to activate the electrode surface ix. washing the electrodes kept in nitric acid with deionized water until neutral pH is reached and then drying in an oven at 40-60°C for 12- 36 hours, x. adding pyrrole monomer with a concentration of 0.001 -0.5 mol/L, mellitic acid with a concentration of 0.005-0.1 mol/L, and ferric chloride hexahydrate with a concentration of 0.001 -0.5 mol/L to a 50:50 ethanokwater mixture solution in a 20 mL volume and stirring at room temperature for 30-120 minutes, xi. keeping the prepared solution and the carbon felt electrode with a surface area of 4x5 cm2 in an autoclave at 60-180°C for 3-12 hours and carrying out the polymerisation with a hydrothermal reaction, and xii. washing the composite electrodes obtained after the synthesis in 50:50 ethanokwater mixture solution and drying at 40-90°C for 6-24 hours.
4. A preparation method according to Claim 3, comprising, in process step iv., adding pyrrole monomer with a concentration of 0.001 -0.5 mol/L, mellitic acid with a concentration of 0.0050.02 mol/L, and ferric chloride hexahydrate with a
concentration of 0.001-0.5 mol/L to a 50:50 ethanokwater mixture solution in a 20 mL volume and stirring at room temperature for 30-120 minutes, A carbon felt electrode prepared by a method according to claim 3 for use in supercapacitors, comprising pyrrole monomer with a concentration of 0.001 -0.5 mol/L, mellitic acid with a concentration of 0.005-0.1 mol/L, and ferric chloride hexahydrate with a concentration of 0.001 -0.5 mol/L in a 20 mL volume and having a surface area of 4x5 cm2. A carbon felt electrode according to Claim 5, comprising 0.2 mol/L concentration of pyrrole monomer and 0.02 mol/L concentration of mellitic acid in a volume of 20 mL.
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| US4442185A (en) * | 1981-10-19 | 1984-04-10 | The United States Of America As Represented By The United States Department Of Energy | Photoelectrochemical cells for conversion of solar energy to electricity and methods of their manufacture |
| US20140017557A1 (en) * | 2012-07-16 | 2014-01-16 | Nthdegree Technologies Worldwide Inc. | Printable Composition for an Ionic Gel Separation Layer for Energy Storage Devices |
| US20190393394A1 (en) * | 2018-06-22 | 2019-12-26 | Board Of Regents, The University Of Texas System | Liquid-based thermoelectric device |
| US20210119100A1 (en) * | 2019-10-18 | 2021-04-22 | Kookmin University Industry Academy Cooperation Foundation | Organic thermoelectric material and thermoelectric generator including the same |
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| US4442185A (en) * | 1981-10-19 | 1984-04-10 | The United States Of America As Represented By The United States Department Of Energy | Photoelectrochemical cells for conversion of solar energy to electricity and methods of their manufacture |
| US20140017557A1 (en) * | 2012-07-16 | 2014-01-16 | Nthdegree Technologies Worldwide Inc. | Printable Composition for an Ionic Gel Separation Layer for Energy Storage Devices |
| US20190393394A1 (en) * | 2018-06-22 | 2019-12-26 | Board Of Regents, The University Of Texas System | Liquid-based thermoelectric device |
| US20210119100A1 (en) * | 2019-10-18 | 2021-04-22 | Kookmin University Industry Academy Cooperation Foundation | Organic thermoelectric material and thermoelectric generator including the same |
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