Self-charging supercapacitor cell

Abstract

The invention relates to a self-charging nanocomposite (SWCNT / PANI / MnO2) electrode that can generate and use its own energy without being connected to a power source and has a reduced carbon footprint, and supercapacitors containing this electrode. The invention relates to supercapacitors containing self-charging nanocomposite electrodes developed for use in military equipment and weapons, especially in the automotive industry, and in daily home electronics such as laptops, mobile phones, tablets, and portable media players.

Description

[0001] SELF-CHARGING SUPERCAPACITOR CELL

[0002] Field of the Invention

[0003] The present invention relates to a self-charging nanocomposite (SWCNT / PANI / MnO2) electrode that can generate and use its own energy without being connected to a power source and has a reduced carbon footprint, and supercapacitors containing this electrode.

[0004] The present invention relates to supercapacitors containing self-charging nanocomposite electrodes developed for use in military equipment and weapons, especially in the automotive industry, and in daily home electronics such as laptops, mobile phones, tablets, portable media players.

[0005] State of the Art

[0006] Supercapacitors are electrical energy storage devices capable of storing large amounts of electrical charge and are used in electronic devices such as laptops, cell phones, tablets, portable media players, digital camera flashlights, flashlights with LEDs that can be charged in a short time, PC cards, microcontrollers, memories such as RAM, SRAM, UPS, etc; defibrillators in the medical field; photovoltaic systems, wind turbines, hybrid and electric vehicles, door and evacuation latches of airplanes, engines of tanks and submarines, trams, vehicles such as cranes and forklifts, etc. in the field of energy and power generation. Supercapacitors can also be used in military equipment such as radar antennas, laser power supplies, military radio communications, avionics displays and devices, airbag deployment, GPS-guided missiles and projectiles. The main determinant of its use is the working performance of the supercapacitor. For example, while low power and voltage are needed for memories, high power and voltage are essential for electric vehicles. Medium / high power and high voltage are required for military applications, while medium / high power and medium voltage are required for automotive subsystems.

[0007] In the present art, supercapacitors are energy storage devices with higher power density than conventional batteries but lower energy density. This puts supercapacitors at a disadvantage compared to batteries due to their long cycle counts (>10,000). In the studies, energy density increases due to the redox reaction thanks to the compounds with metal oxide and conductivepolymer in pseudocapacitors. Composite supercapacitors are preferred due to their environmental friendliness and low cost. Compared to ruthenium and conductive polymers, manganese dioxide (MnC>2) contains the manganese element, which is more economical and abundant in nature as a redox-active material. It can also be easily recycled. It provides high energy density and stability in supercapacitor applications. Another material, polyaniline (PANI), has good chemical stability and electrical conductivity. The use of carbon nanotubes (CNTs) in supercapacitors provides good electrical conductivity and plays a role in the electrochemically stable structure of the electrode. There are studies with PANI / MnC>2 and MnC>2 / ANI / CNT (Yuksel and Unalan, 2015), (Liu et aL, 2016). In these studies, stable supercapacitors have been demonstrated at high cycle counts. However, since the surface area of the multi-walled carbon nanotube (MWCNT) used as a carbon nanotube is lower than that of the single-walled carbon nanotube (SWCNT), the supercapacitor capacitance is lower.

[0008] There are also studies in the art of supercapacitors that can self-charge to meet the energy needs of the supercapacitor (Xue et aL, 2014; Xue et aL, 2012; Xue et aL, 2013). In these studies, it is aimed to provide polarization under mechanical behavior by using a film that exhibits the piezoelectric effect as a separator. Thus, it is aimed to provide the electrons necessary for supercapacitor operation. In their study, Ramadoss et aL implemented a supercapacitor application with PVDF-ZnO piezoelectric film layer. The processes and zinc oxide content in the preparation of this film provide a disadvantage in terms of cost. In addition, the energy density as a result of the electrochemical test in practice is very low (455 mF / g at 0.04 A / g scan rate).

[0009] The utility model application numbered CN215265952, found in the literature research, is related to a self-charging supercapacitor. The mentioned supercapacitor comprises a first flexible substrate, a first electrode, a ZnO piezoelectric nanogenerator, a second electrode, a second flexible substrate, and a solid electrolyte. In addition, the capacitance to be achieved with the ZnO piezoelectric film is stated as 43.07 mF / cm2in the relevant application. However, the application does not mention the use of aligned PVDF-TrFE film with a stronger piezoelectric effect and the use of this film to obtain a supercapacitor with increased capacitance and mechanical strength.

[0010] As a result, due to the abovementioned disadvantages and the insufficiency of the current solutions regarding the subject matter, a development is required in the relevant technical field.Purpose of the Invention

[0011] The invention relates to a self-charging supercapacitor cell to eliminate the above-mentioned disadvantages and bring new advantages to the relevant technical field.

[0012] The main purpose of the invention is to develop a supercapacitor that can generate and use its own energy without being dependent on a power source in application areas requiring power, such as the automotive industry, military equipment and weapons, daily home electronics, etc. The invention aims to provide a device that exhibits a very high capacitance (1202 mF / cm2at a current density of 2 mA / cm2) compared to existing products and studies.

[0013] The purpose of the invention is to demonstrate the self-charging efficiency by exhibiting a piezoelectric effect with an aligned electrospun PVDF-TrFE film, as well as to increase the specific capacitance in addition to the mechanical strength of the supercapacitor.

[0014] One purpose of the invention is to contribute to the capacitance and electrochemical stability of the supercapacitor by using purified single-walled carbon nanotubes.

[0015] Another purpose of the invention is to reduce the carbon footprint with a device that can generate and use its own energy without being connected to a power source.

[0016] Another purpose of the invention is to provide a product with more economical and faster production.

[0017] In order to achieve the above-described purposes, the invention is a self-charging supercapacitor cell comprising PVA / H2SO4 gel electrolyte, aligned PVDF-TrFE film separator and at least two SWCNT / PANI / MnO2 electrodes.

[0018] In order to achieve the above-mentioned purposes, the invention is a method of producing a self-charging supercapacitor cell, comprising the process steps of;

[0019] i. Purifying single-walled carbon nanotubes (SWCNTs) and functionalizing with carboxylic acid groups,

[0020] ii. Obtaining SWCNT / PANI material by polymerizing aniline monomer in SWCNT, iii. Obtaining SWCNT / PANI / MnO2 nano composite by combining SWCNT / PANI material with potassium permanganate,iv. Preparing slurry using active material (MnO2 / PANI / SWCNT) with binder and conductive additives, and obtaining the electrode by coating the prepared material on the current collector,

[0021] v. Obtaining a separator by forming a uniformly aligned PVDF-TrFE piezoelectric film by electrospinning

[0022] vi. Preparing PVA / H2SO4 gel electrolyte,

[0023] vii. Immersing SWCNT / PANI / MnO2 electrodes and aligned PVDF-TrFE Piezoelectric film separator into PVA / H2SO4 gel electrolyte,

[0024] viii. Lamination of SWCNT / PANI / MnO2 electrode, PVA / H2SO4 gel electrolyte, aligned PVDF-TrFE film separator, and SWCNT / PANI / MnO2 electrode

[0025] The structural and characteristic features of the invention will be understood clearly by the following figures and the detailed description made with reference to these figures, and therefore, the evaluation shall be made by taking these figures and the detailed description into consideration.

[0026] Brief Description of Figures

[0027] Figure 1, Galvanostatic charge-discharge test of supercapacitor with a) randomly aligned E-PVDF-TrFE film (dashed line) and b) uniformly aligned E-PVDF-TrFE film (continuous line).

[0028] Figure 2, Electrochemical impedance spectroscopy (EIS) of supercapacitor with a) uniformly aligned E-PVDF-TrFE film (round pattern) and b) randomly aligned E-PVDF-TrFE film (square pattern)

[0029] Figure 3, Cyclic voltammetry (CV) test of self-charging supercapacitor with a) random electrospun PVDF-TrFE film (dashed line) and b) uniformly aligned electrospun PVDF-TrFE film (continuous line)

[0030] Figure 4, Representative illustration of a self-charging supercapacitor cell

[0031] Figure 5, SEM image at 15,000x magnification, showing the morphology of aligned electrospun PVDF-TrFE fibers

[0032] Figure 6, a) The morphological structure of randomly aligned electrospun PVDF-TrFE film fibers at 5Kx magnification B) The morphological structure of uniformly aligned electrospun PVDF-TrFE film fibers at 5Kx magnification is given.

[0033] Reference Numbers

[0034] 10. MnC>2 / PANI / SWCNT nanocomposite electrode

[0035] 20. PVA / H2SO4 gel electrolyte30. Uniformly aligned electrospun PVDF-TrFE piezoelectric film

[0036] 40. MnO2 / PANI / SWCNT nanocomposite electrode

[0037] Detailed Description of the Invention

[0038] In this detailed description, the subject of the invention is described by means of examples only for clarifying the subject matter, such that no limiting effect is created.

[0039] The invention relates to a self-charging supercapacitor cell that can generate and use its own energy without being connected to a power source and has a reduced carbon footprint. The supercapacitor consists of PVA / H2SO4 gel electrolyte, aligned PVDF-TrFE film separator, and SWCNT / PANI / MnO2 electrode.

[0040] Manganese dioxide is a low-cost, low-toxicity, high theoretical capacitance (1370 F / g), and environmentally friendly material. In addition, it has an easy preparation process.

[0041] Polyaniline is a conductive polymer with high conductivity and a good capacitance effect. Pseudocapacitors play a role in fast redox reactions. When used for supercapacitors, PAN I as active material stores charge through redox reaction as PANI transitions between various oxidation states.

[0042] Single-walled carbon nanotubes (SWCNTs) have outstanding mechanical and electrical properties. SWCNTs have excellent electrical properties, with carrier mobility of ~ 10.000 cm2 V-1 s-1 , room temperature conductivity exceeding 5 x 105S m-1 , and the ability to carry electric current density of ~ 4 x 109A cm-2. The large capacitances available from SWCNTs are due to their high accessible surface area, where most of the charge is stored in the electric double layer (EDL). However, electrochemically active functionalities at the ends of the tubes also lead to a pseudocapacitive charge storage mechanism. Further addition of redox-active functional groups leads to increased specific capacitance.

[0043] When PVDF-TrFE film is compared to PVDF film, the beta phase that should exhibit piezoelectric effect is active at room temperature. This facilitates the use of the piezoelectric property of the PVDF-TrFE film. In addition, it protects the supercapacitor cell from short circuits by acting as a separator between the two electrodes.

[0044] PVA / H2SO4 gel electrolyte was observed to have the best ionic conductivity among the liquid electrolytes used in supercapacitors, sulfuric acid. However, since sulfuric acid can have a corrosive effect on the electrode and its liquid state poses a safety risk in the cell, it is appropriate to use it by making a gel with PVA.The invention is a method for producing a self-charging supercapacitor cell, comprising the process steps of;

[0045] i. Purifying single-walled carbon nanotubes (SWCNTs) and functionalizing with carboxylic acid groups,

[0046] ii. Obtaining SWCNT / PANI material by polymerizing aniline monomer in SWCNT,

[0047] iii. Obtaining SWCNT / PANI / MnO2 nano composite by combining SWCNT / PANI material with potassium permanganate,

[0048] iv. Preparing slurry using active material (MnO2 / PANI / SWCNT) with binder and conductive additives, and obtaining the electrode by coating the prepared material on the current collector,

[0049] v. Obtaining a separator by forming a uniformly aligned PVDF-TrFE piezoelectric film by electrospinning

[0050] vi. Preparing PVA / H2SO4 gel electrolyte,

[0051] vii. Immersing SWCNT / PANI / MnO2 electrodes and aligned PVDF-TrFE Piezoelectric film separator into PVA / H2SO4 gel electrolyte,

[0052] viii. lamination consisting of SWCNT / PANI / MnO2 electrode, PVA / H2SO4 gel electrolyte, aligned PVDF-TrFE film separator, and SWCNT / PANI / MnO2 electrode

[0053] In process step i) of the inventive method comprises purification of SWCNT by keeping it in an ultrasonic bath in nitric acid solution, washing, phase separation by centrifugation, and filtering and drying of the subphase remaining in the phase separation.

[0054] In process step ii) of the inventive method comprises sonicating SWCNT in distilled water, adding aniline to this mixture and mixing, adding ammonium persulfate and HCI to the solution, and performing polymerization by mixing, finally centrifuging the mixture and obtaining SWCNT / PANI material by washing and drying the residue.

[0055] In process step iii) of the inventive method comprises sonicating SWCNT / PANI in distilled water, adding MnSO4 to this mixture and reducing it by stirring in a magnetic stirrer, adding ammonium persulfate to the solution and stirring, transferring the mixture to a hydrothermal reactor and keeping it at 1400 for 12 hours, filte ring the solution and repeated washing with distilled water and ethanol and then drying to obtain SWCNT / PANI / MnO2 nanocomposite.In process step iv) of the inventive method, a slurry is prepared using a ratio of 8:1 :1 or 7:2:1 of active material: binder: conductive carbon formulation.

[0056] In process step iv) of the inventive method comprises the preparation of the active material (MnO2 / PANI / SWCNT) slurry by the following steps.

[0057] - Dissolving PVDF (Binder) in N-methyl-pyrrolidone(NMP) by keeping it on a magnetic stirrer.

[0058] - Adding conductive carbon into the dissolved PVDF and mixing it in a magnetic stirrer at 300 rpm,

[0059] - Mixing the suspension in an ultrasonic mixer

[0060] - Adding the active material into this suspension and dispersing it in an ultrasonic mixer - Finally, mixing the mixture in a magnetic stirrer to prepare the active material (MnO2 / PANI / SWCNT) slurry

[0061] The process step iv) of the inventive method comprises coating the MnO2 / PANI / SWCNT active material on aluminum foil and then drying it in a vacuum oven at 70X3 for 4 hours.

[0062] The process step v) of the inventive method comprises dissolving PVDF-TrFE in a solution containing Acetone: DMF, preferably at a ratio of 3:1 , and then forming an aligned PVDF-TrFE Piezoelectric film by electrospinning.

[0063] The process step vi) of the inventive method comprises, mixing Polyvinyl alcohol (PVA) into pure water to obtain the PVA solution and adding Sulfuric acid (H2SO4) to the PVA solution under stirring (preferably 500 rpm) and cooling to obtain the PVA / H2SO4 gel electrolyte.

[0064] An application of the method, which is the subject of the invention, is as follows;

[0065] 1. STEP: Purification and functionalization of single-walled carbon nanotubes (SWCNTs) Purification Step

[0066] - 100 g of SWCNT is weighed and kept in an ultrasonic bath for 2-4 hours, preferably 4 hours, in a 3-6 M nitric acid solution.

[0067] - After the ultrasonic bath, the solution is washed and the pH is reduced to between 5-7, preferably pH=6.

[0068] - After the washing process, phase separation occurs by centrifugation, and the upper phase (SWCNT that does not react with nitric acid) is discarded.

[0069] - It is then passed through a 0.22 micron membrane filter and left to dry for 8 hours atSWCNT Functionalization

[0070] This process is applied to add the -COOH structure to the SWCNT structure.

[0071] - 100 g of SWCNT powder obtained in the purification step is left to react for 4 hours at 800 using a reflux condenser in a 3:1 ratio Sulfur ic acid / Nitric acid solution.

[0072] - The pH is adjusted to 6 by washing.

[0073] - After washing, the sample is left to dry at 600 for 12 hours.

[0074] 2 STEP: Obtaining SWCNT / PANI material by polymerizing polyaniline (PANI) in SWCNT - 30-50 mg preferably 30 mg SWCNT was sonicated for 30-45 minutes preferably 30 minutes in 50-75 ml preferably 50 ml distilled water.

[0075] - 3 ml of aniline was added to this mixture and stirred at room temperature.

[0076] - 7.2 g of ammonium persulfate (APS) and 1 M HCI were added to this solution.

[0077] - The mixture was stirred with a magnetic stirrer at 40 for 12 hours to allow polymerization to occur.

[0078] - Finally, the mixture is centrifuged, and the greenish residue formed is washed with water and ethanol.

[0079] - It is left to dry in a vacuum oven at 800 for 12 hours.

[0080] 3. STEP: Obtaining SWCNT / PANI / MnO2 nano composite by combining SWCNT / PANI material with potassium permanganate

[0081] - PANI / SWCNT is weighed as 270 mg and sonicated in 216 ml of water for 30 minutes. - Then, 1.4 g of manganese dioxide (MnO2) is added into this sonicated solution.

[0082] - This mixture is stirred at 600 on a magnetic sti rrer for 30 minutes and then reduced to room temperature.

[0083] - 1.85 g of APS is added to the solution at room temperature.

[0084] - This suspension is stirred for 2 hours at room temperature on a magnetic stirrer.

[0085] - This mixture is then transferred to the hydrothermal reactor and kept at 1400 for 12 hours.

[0086] - After the process, the solution is filtered. It is washed 3 times with pure water and 3 times with ethanol and left to dry at 600 for 12 h ours.

[0087] 4. STEP: Preparation of the active material (MnO2 / PANI / SWCNT) with binder and conductive additive slurry and coating the prepared active material on the current collector, preferably aluminum foil, to obtain the electrode.Preparation of active material (MnO2 / ANI / SWCNT) slurry

[0088] - Sludge is prepared using a formulation of 8:1:1. (Active material: Binder:

[0089] Conductive carbon)

[0090] 0.05 g of PVDF (Binder) is dissolved in 0.5 g of N-methyl-pyrrolidone (NMP) [an organic solvent used to prepare sludge in energy storage systems] by keeping it in a magnetic stirrer for 1 hour.

[0091] - Conductive carbon is added to the dissolved PVDF, and mixing is continued at 300 rpm in the magnetic stirrer.

[0092] - The suspension is transferred to the ultrasonic mixer and left for ultrasonic mixing at 50% power for 30 minutes.

[0093] - Finally, the active material is added to this suspension and dispersed in an ultrasonic mixer for 30 minutes.

[0094] Finally, the mixture is stirred for 2 hours with a magnetic stirrer at 200 rpm.

[0095] Coating the active material on aluminum foil

[0096] - The resulting sludge is coated on aluminum foil with the help of a steel knife.

[0097] - The coated foil is left to dry in a vacuum oven at 700 for 4 hours.

[0098] 5. STEP: Obtaining a separator by forming an aligned PVDF-TrFE piezoelectric film by electrospinning

[0099] 24% by weight of PVDF-TrFE is dissolved in Acetone: DMF at a ratio of 3:1. (1.92 g PVDF-TrFE is dissolved in 6 ml acetone: 2 ml DMF)

[0100] Dissolved PVDF-TrFE is transferred into a 10 ml syringe.

[0101] - The syringe is attached to the electrospinning device and the electrospinning process is completed. Electrospinning parameters are as follows:

[0102] Flow rate: 1.5 mL / s

[0103] Operating voltage: 18 kV

[0104] Operating distance: 18 cm

[0105] Drum collector speed: 1000 rpm

[0106] 6. STEP: Preparing PVA / H2SO4 gel electrolyte,

[0107] Preparing PVA / H2SO4 gel electrolyte

[0108] - 3 g PVA (Mw=10.000) is mixed in 30 ml of pure water at 900.

[0109] - After the PVA is completely dissolved, 3 g of H2SO4 is added to the PVA solution under 500 rpm stirring. The solution is then cooled to room temperature.7. STEP: Immersion of SWCNT / PANI / MnO2 electrodes and aligned PVDF-TrFE Piezoelectric film separator into PVA / H2SO4 gel electrolyte,

[0110] Before assembly, the electrodes and separator were immersed in the PVA / H2SO4 gel electrolyte for 5 minutes and then assembled individually and left at room temperature for 12 hours to evaporate the excess water in the electrolyte.

[0111] 8. STEP lamination of SWCNT / PANI / MnO2 electrode, PVA / H2SO4 gel electrolyte, aligned PVDF-TrFE film separator, and SWCNT / PANI / MnO2 electrode.

[0112] - The system consisting of electrodes prepared with MnO2 / PANI / SWCNT, separator made of PVDF-TrFE piezoelectric film and PVA / H2SO4 gel electrolyte is closed by lamination. An example supercapacitor device and its components are shown in Figure 4.

[0113] In the invention, the alignment of the fibers during electrospinning ensures that the dipoles are organized in a single direction, which increases the piezoelectric coefficient (d33). Thanks to this natural p-phase structure, it has a higher piezoelectric coefficient than PVDF and other polymers.

[0114] The invention provides a product with high mechanical strength, unlike inorganic materials such as ZnO, which is ideal for flexible electronics and wearable devices.

[0115] The invention provides a product suitable for easy and large-scale production using methods such as electrospinning.

[0116] In addition, the aligned fibers in the invention ensure that the applied mechanical stress is distributed evenly, thus allowing the material to carry more load without cracking or deformation. The regular structure of the fibers provides a material with increased flexibility and durability.

[0117] Fiber alignment allows electrical charges to move faster and more efficiently along the fiber. This increases the energy storage capacity of the material. Figure 1 shows the Galvanostatic charge-discharge test values of the supercapacitor with a) randomly aligned E-PVDF-T rFE film (dashed line) and b) uniformly aligned E-PVDF-TrFE film (continuous line), [(a.) With randomly aligned PVDF-TrFE film, SC: 571 mF / cm2 capacitance at 2 mA / cm2 current density, while (b) with uniformly aligned PVDF-TrFE film, SC: 1202 mF / cm2 capacitance at 2 mA / cm2 current density.] This test shows the voltage change with time and is also used to calculate capacitance. As can be seen, the supercapacitor constructed with randomly alignedpiezoelectric film shows approximately 150 seconds of charging and approximately 170 seconds of discharging. This offers a capacitance value of 429 mF / cm2. On the other hand, the supercapacitor formed with a uniformly aligned piezoelectric film exhibits a capacitance of 827 mF / cm2, showing a charge time of approximately 300 seconds and a discharge time of approximately 400 seconds.

[0118] Figure 2 shows the electrochemical impedance spectroscopy (EIS) data of the supercapacitor with a) uniformly aligned E-PVDF-TrFE film (round pattern) and b) randomly aligned E-PVDF-TrFE film (square pattern). This electrochemical impedance spectroscopy (EIS) provides information about the internal resistance of the supercapacitor cell. The supercapacitor cell constructed with an aligned piezoelectric film has a lower internal resistance compared to the randomly aligned piezoelectric film supercapacitor. This increases the capacitance and efficiency of the supercapacitor.

[0119] Figure 3 shows the Cyclic voltammetry (CV) test of a self-charging supercapacitor with a) random electrospun PVDF-TrFE film (dashed line) and b) uniformly aligned electrospun PVDF-TrFE film (continuous line). In this test, the cell's voltage versus current value is measured at a scanning speed of 100 mV / s. The area of the CV curve is directly related to the specific capacitance of the supercapacitor. The larger area indicates that the supercapacitor constructed with aligned PVDF-TrFE has a higher capacitance value. This increase can be explained by the fact that aligned fibers optimize piezoelectric response and ion transfer. In the aligned PVDF-TrFE curve (b), the current density (I) values are higher than the random PVDF-TrFE (a) in the entire potential range. This indicates that the aligned PVDF-TrFE film utilizes the piezoelectric properties and charge storage capacity more effectively.

[0120] Figure 5 shows the morphology of aligned electrospun PVDF-TrFE fibers in a 15.000x magnification SEM image. The fibers exhibit a highly uniform and smooth surface with minimal bead formation indicating optimized electrospinning parameters. Aligning the fibers improved the piezoelectric properties of the material by aligning their dipole moments in a preferred direction. The average fiber diameter appears consistent, reflecting precise control over polymer solution concentration, applied voltage, and flow rate during the electrospinning process.

[0121] The aligned fibers in the invention create a uniform pore structure and enable electrolytes to reach the active sites more easily. This increases diffusion in the supercapacitor, providing higher energy density.In the invention, regular fiber alignment throughout the material ensures equal piezoelectric response at every point.

[0122] SEM Images are given in Figure 6. (A. morphological structure of randomly aligned electrospun PVDF-TrFE film fibers in 5Kx magnification B. The morphological structure of uniformly aligned electrospun PVDF-TrFE film fibers in 5Kx magnification is given). The alignment effect was supported by measurements made with the d33 meter. In the randomized film, the d33 piezoelectric coefficient was measured at 15 pC / N, while in the aligned film, this value increased to 28 pC / N. This difference is due to the fact that the molecular arrangement of the aligned film is more uniform, resulting in increased net piezoelectric efficiency. This provides significant advantages in terms of higher energy conversion efficiency, higher energy density, and cyclic stability in the supercapacitor cell.

Claims

CLAIMS1. A self-charging supercapacitor cell, characterized by comprising: PVA / H2SO4 gel electrolyte, aligned PVDF-TrFE film separator, and at least two SWCNT / PANI / MnO2 electrodes.

2. A method for producing a self-charging supercapacitor cell, characterized by comprising the process steps of;i. Purifying single-walled carbon nanotubes (SWCNTs) and functionalization with carboxylic acid groups,ii. Obtaining SWCNT / PANI material by polymerizing aniline monomer in SWCNT, iii. Obtaining SWCNT / PANI / MnO2 nano composite by combining SWCNT / PANI material with potassium permanganate,iv. Preparing slurry using active material (MnO2 / PANI / SWCNT) with binder and conductive additives, and obtaining an electrode by coating the prepared material on the current collector,v. Obtaining a separator by forming a uniformly aligned PVDF-TrFE piezoelectric film by electrospinningvi. Preparing PVA / H2SO4 gel electrolyte,vii. Immersing SWCNT / PANI / MnO2 electrodes and aligned PVDF-TrFE Piezoelectric film separator into PVA / H2SO4 gel electrolyte,viii. lamination of SWCNT / PANI / MnO2 electrode, PVA / H2SO4 gel electrolyte, aligned PVDF-TrFE film separator, and SWCNT / PANI / Mn2 electrode.

3. The method according to claim 2, characterized by comprising: in process step i) purification of SWCNT by keeping it in an ultrasonic bath in nitric acid solution, washing, phase separation by centrifugation, and filtering and drying of the subphase remaining in the phase separation.

4. The method according to claim 2, characterized in that, in the process step ii) the SWCNT / PANI material is obtained by the following steps;- Sonicating SWCNT in distilled water,- adding aniline to this mixture and mixing,- adding ammonium persulfate and HCI to the solution and mixing to carry out polymerization,- Finally, centrifuging the mixture and- washing and drying the resulting residue.

5. The method according to claim 2, characterized in that; In the process step iii), the SWCNT / PANI / MnO2 nano composite is obtained by the following steps;- Sonicating SWCNT / PANI in distilled water,- Reduction by adding MnSC to this mixture and mixing with a magnetic stirrer, - adding ammonium persulfate to the solution and mixing- transferring the mixture to the hydrothermal reactor and keeping it at 1400 for 12 hours- Filtering the solution and washing it repeatedly with pure water and ethanol, followed by drying.

6. The method according to claim 2, characterized in that, in the process step iv), slurry is prepared with the formulation of 8:1 :1 or 7:2:1 ratio Active material: Binder: Conductive carbon, respectively.

7. The method according to claim 2, characterized in that the process step v) comprises dissolving PVDF-TrFE in a solution containing Acetone: DM F, preferably at a ratio of 3:1, and then forming an aligned PVDF-TrFE Piezoelectric film by electrospinning.

8. The method according to claim 2, characterized by comprising the process step vi) Polyvinyl alcohol mixing into pure water to obtain the PVA solution and adding Sulfuric acid to the PVA solution under stirring and cooling to obtain the PVA / H2SO4 gel electrolyte.

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