CN112509820A - 3D printing self-repairing flexible supercapacitor taking ionic gel electrolyte as substrate - Google Patents
3D printing self-repairing flexible supercapacitor taking ionic gel electrolyte as substrate Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
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Abstract
The invention provides a 3D printing self-repairing flexible supercapacitor taking an ionic gel electrolyte as a substrate, which is obtained by taking a carbon nano tube as printing ink, taking a 1-butyl-3-methylimidazole trifluoromethanesulfonimide film (BMIMTFSI-P) as the ionic gel electrolyte and the substrate at the same time, taking the carbon nano tube as a positive electrode material and a negative electrode material at the same time and adopting an ink direct writing technology. The self-repairing flexible supercapacitor based on the ionic gel electrolyte prepared by the invention has the working voltage of 0-3V, can keep high energy density and power density in stable work, and has good rate performance and cycling stability.
Description
Technical Field
The invention relates to the technical field of 3D printing and electrochemical energy storage, in particular to a 3D printing self-repairing flexible supercapacitor taking an ionic gel electrolyte as a substrate.
Background
With the continuous development of energy storage electronic devices, higher requirements are put forward on the aspects of energy density, cycling stability, flexibility, safety and the like. Although the existing button-shaped or soft-package energy storage device has higher energy and power density, the further development of equipment in the field of flexible electronic devices is seriously hindered by a layer-by-layer assembled structure and components. Super capacitors have attracted extensive attention because of their advantages of fast charge and discharge performance, green safety, and excellent cycle stability. At present, the miniaturization and integration of the flexible energy storage electronic device are also a great development trend, so that the miniaturization structure of the flexible miniature super capacitor is favorable for the rapid transmission of conductive ions, can meet the advantages, and is expected to promote the development of wearable electronic devices. However, the current planar micro-supercapacitors usually need to rely on pre-designed substrates such as textiles and plastics, resulting in poor compatibility with other original components of wearable electronics. And the manufacturing procedures of preparing the micro-nano common ink-jet printing, laser writing, electrophoretic deposition, casting mold and the like are complicated, so that the preparation efficiency and the practicability are greatly reduced. Therefore, in order to achieve reliable and efficient fabrication of flexible micro-supercapacitors, it is crucial to develop inexpensive fabrication processes for the variable substrates. As a new technology, the 3D printing technology can directly print functional ink on a preset substrate and has no special requirements on the strength of the substrate and the like. The integrated wearable electronic device is expected to be efficiently prepared by utilizing an ink direct writing technology and constructing the micro super capacitor by taking a flexible material as a substrate.
An ionic gel electrolyte system using a polymer as a matrix has both good mechanical flexibility and electrochemical stability, and has recently received much attention from scientists. However, most ionic gel electrolytes may still suffer from performance degradation due to structural failure when subjected to external stress to produce large deformation such as bending or stretching. Inspired by self-repairing behaviors of natural organisms, the development of the ionic gel electrolyte with self-repairing performance provides a new idea for developing a flexible electronic device with stable structure and long service life.
Carbon atoms in carbon nanotubes in sp2The hybrid material is mainly hybrid, has good mechanical and electrical properties, has tensile strength of 50-200 Gpa generally, and can be used as printing ink for direct writing of 3D printing ink, and is the most common electrode material. The 3D printing technology, also known as additive manufacturing technology, has the advantages of rapid molding, simple operation, etc., and is increasingly applied to the preparation of micro energy storage devices as a new technology. The ink direct writing technology is a branch of 3D printing, and the requirement of the ink direct writing technology on printing ink is that the ink has the shear thinning characteristic, namely the ink can be smoothly extruded at a higher shear rate, the viscosity of the ink is increased at a lower shear rate, and the ink can be rapidly cured and molded after being extruded, so that a 3D printed structure cannot collapse, and the next layer can be continuously printed.
Disclosure of Invention
The invention overcomes the defects in the prior art, the existing plane type micro super capacitor is usually supported on a pre-designed substrate, and the substrate has poor compatibility with other original parts of wearable electronic equipment; and the manufacturing procedures of preparing micro-super common ink-jet printing, laser writing, electrophoretic deposition, casting mold and the like are complicated, the preparation efficiency and the practicability are greatly reduced, and the 3D printing self-repairing flexible supercapacitor taking the ionic gel electrolyte as the substrate is provided, in particular to the flexible supercapacitor taking the carbon nano tube as the printing ink and based on Li+The BMIMTFSI-P film with-O metal coordination and complexation and double-network physical crosslinking based on hydrogen bonding is simultaneously used as an ion gel electrolyte and a substrate, and a flexible super capacitor is printed by an ink direct writing technology and has good electrochemical performance and self-repairing performance.
The purpose of the invention is realized by the following technical scheme.
A3D printing self-repairing flexible supercapacitor taking an ionic gel electrolyte as a substrate takes carbon nano tubes as printing ink, takes an ionic liquid gel electrolyte (BMIMTFSI-P) based on 1-butyl-3-methylimidazolium tetrafluoroborate as the ionic gel electrolyte and the substrate at the same time, takes the carbon nano tubes as a positive electrode material and a negative electrode material at the same time, obtains the self-repairing flexible supercapacitor through an ink direct writing technology, and is carried out according to the following steps:
preparing the carbon nano tube printing ink:
placing carbon nanotube powder in deionized water, performing ultrasonic treatment for 6-12h to obtain a carbon nanotube solution with the mass fraction of 10%, centrifuging the prepared carbon nanotube solution, and taking supernatant to obtain carbon nanotube printing ink;
preparation of 1-butyl-3-methylimidazolium tetrafluoroborate-based ionic liquid gel electrolyte (BMIMTFSI-P):
and 3, mixing the ethanol solution of the polyethylene oxide (PEO) prepared in the step 1 and the reaction mixed solution I prepared in the step 2 in equal amount, pouring the mixture into a tetrafluoro mold, and drying the mixture in vacuum to obtain the ionic liquid gel electrolyte (BMIMTFSI-P) based on the 1-butyl-3-methylimidazolium tetrafluoroborate.
Preparing the carbon nano tube printing ink: the rotation speed of the centrifugation is 6000-10000 r/min, and the centrifugation time is 4-10 min.
In step 2, the volume ratio of the ethanol solution of polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO) to 1-butyl-3-methylimidazolium bistrifluoromethylsulfimide salt (BMIMTFSI) was (1-3): (7-9).
In the step 3, the vacuum drying temperature is 40-60 ℃, and the vacuum drying time is 20-30 h.
The invention has the beneficial effects that: the self-repairing flexible supercapacitor based on the ionic gel electrolyte prepared by the invention has the working voltage of 0-3V, can keep high energy density and power density in stable work, and has good rate performance and cycling stability.
Drawings
Fig. 1 is a scanning electron microscope image of a self-repairing flexible supercapacitor based on an ionic gel electrolyte prepared in example 1 of the present invention, wherein, (a) is a cross section, (b) is a carbon nanotube outside the cross section, (c) is a carbon nanotube at an interface, and (d) is a cross section of the ionic gel electrolyte;
FIG. 2 is a graph of the relationship between modulus and shear stress of a 3D ink printing material prepared in example 1 of the present invention;
FIG. 3 is a cyclic voltammogram of an ionic gel electrolyte BMIMTFSI-P based supercapacitor made in example 1 of the present invention at different scan rates;
FIG. 4 is a charge-discharge diagram for different current densities using an ionic gel electrolyte based BMIMTFSI-P supercapacitor of the present invention;
FIG. 5 is a schematic diagram of the cutting self-healing of a self-healing flexible supercapacitor based on ionic gel electrolyte prepared using the present invention;
FIG. 6 is an infrared spectrum of an ionic liquid gel electrolyte based on 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMTFSI-P) prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1:
(1) weighing a proper amount of carbon nanotube powder, putting the carbon nanotube powder into a beaker filled with deionized water, and carrying out ultrasonic treatment for 12 hours to prepare a carbon nanotube solution with the mass fraction of 10%;
(2) and centrifuging the prepared solution, wherein the rotation speed of the centrifugation is 8000 revolutions per minute, and the centrifugation time is 8 minutes. And taking the supernatant to obtain the electrode ink for 3D printing. The rheological characteristics of the 3D printing ink can be obtained by rheological tests (see fig. 2).
(3) A carbon nanotube slurry was used as a printing ink, and the printing ink was filled in a syringe having a capacity of 1mL, and a plastic head having a diameter of 410 μm was disposed.
(4) And (3) performing a 3D printing process by adopting a multi-axis positioning system (Prussa i3 and Ramps 1.4), and controlling the extrusion amount of a screw and a nozzle by using a G-code, wherein the moving speed of the nozzle in the printing process is 5 mm/s.
(5) The prepared BMIMTFSI-P film is used as an ionic gel electrolyte and a substrate at the same time, wherein polyethylene oxide (PEO) is dissolved in ethanol to obtain an ethanol solution of the polyethylene oxide (PEO), and the number average molecular weight of the polyethylene oxide (PEO) is 6000000; dissolving polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO) in ethanol to prepare an ethanol solution of polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO), dropwise adding 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt (BMIMTFSI) (ionic liquid) into the ethanol solution (polymer) of polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO), wherein the mass percent of polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO) in the ethanol solution of polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO) is 20 wt% and the mass percent of 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt (BMIMTFSI) is 20 wt% according to the volume ratio of the polymer to the ionic liquid of 2:8 Adding lithium bistrifluoromethanesulfonimide LiTFSI into the mixed solution to obtain a reaction mixed solution I, wherein the average molecular weight of polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO) is 5800; mixing the ethanol solution of polyethylene oxide (PEO) prepared in the step 1 and the reaction mixed solution I prepared in the step 2 in equal amount, pouring the mixture into a tetrafluoro mold, performing vacuum drying at 50 ℃ for 24h to obtain an ionic liquid gel electrolyte (BMIMTFSI-P) based on 1-butyl-3-methylimidazolium tetrafluoroborate, performing 3D printing on a BMIMTFSI-P film by adopting the carbon nanotube ink obtained in the step (2) to prepare a micro supercapacitor, and obtaining a topography of the 3D printed supercapacitor by adopting a cold field Scanning Electron Microscope (SEM), wherein the topography is shown in figure 1.
(6) And (4) putting the micro super capacitor obtained in the step (5) into a vacuum oven, and drying for 24 hours at the temperature of 40 ℃. The self-healing ionic gel electrolyte-based symmetrical supercapacitor is obtained, and has high safety and high voltage window.
As shown in fig. 2, the ink used for 3D printing is 10% carbon nanotube slurry, and rheological tests show that the ink has shear-thinning property, and meanwhile, the relationship between the storage modulus and shear modulus and the shear rate can also be obtained, and the carbon nanotube ink has printability. The method comprises the steps of directly printing the miniature super capacitor on the self-repairable ionic gel electrolyte to enable electrode materials to be in close contact with the electrolyte, cutting the miniature super capacitor based on the ionic gel electrolyte through a physical process to enable the miniature super capacitor to be broken, butting broken surfaces and slightly applying pressure to the miniature super capacitor, repairing the wound surface of the miniature super capacitor only through a self-healing process of a few seconds, wherein the healed miniature super capacitor still has excellent electrochemical performance, and the capacity retention rate of the healed miniature super capacitor is up to 98% of that of the original state.
As shown in FIG. 3, by using BMIMTFSI-P as the electrolyte, the voltage window of the supercapacitor can be as high as 3V, and the stability of the cyclic voltammetry curve is good along with the increase of the sweep rate, so that the self-repairing flexible supercapacitor has good ion conductivity, and therefore the device shows excellent capacitance performance. The specific capacity of the self-repairing micro super capacitor is calculated according to the cyclic voltammetry curve, so that the self-repairing micro super capacitor can be obtained at 5mV s-1The specific capacitance at the scanning rate reaches 71mF cm-2And at 100mV s-1The capacity retention rate reaches 59.2% at the scanning speed, and good rate performance is shown. The charging and discharging curves of the super capacitor under different current densities can be obtained, the voltage drop is increased along with the increase of the current density, but the overall voltage drop is kept in a lower range, which shows that the self-repairing flexible super capacitor has good reversible cycle performance, and when the current density is 0.5mA cm-2The specific capacity of the miniature super capacitor is up to about 65.5mF cm-2And increased to 5mA cm in current density-2When the capacity is 38.3mF cm-2And the capacity retention rate reaches 58%, so that the high-speed charge-discharge performance and the rate capability are better.
As shown in FIG. 4, the current density tested was 2mA cm-2The flexible supercapacitor still keeps the shape of a charge-discharge curve which is similar to a triangle after a plurality of cutting-self-healing processes, and shows excellent reversible cycle performance.
After cutting as shown in fig. 5, the capacity retention rate of the self-healing flexible supercapacitor subjected to the self-healing repair process reaches 98% of the original state, and the self-healing flexible supercapacitor shows excellent cutting-self-healing performance and rapid charge and discharge performance.
Example 2:
(1) weighing a proper amount of carbon nanotube powder, putting the carbon nanotube powder into a beaker filled with deionized water, and carrying out ultrasonic treatment for 6 hours to prepare a carbon nanotube solution with the mass fraction of 10%;
(2) and centrifuging the prepared solution, wherein the rotation speed of the centrifugation is 6000 r/min, and the centrifugation time is 10 min. And taking the supernatant to obtain the electrode ink for 3D printing.
(3) A carbon nanotube slurry was used as a printing ink, and the printing ink was filled in a syringe having a capacity of 1mL, and a plastic head having a diameter of 270 μm was disposed.
(4) And (3) performing a 3D printing process by adopting a multi-axis positioning system (Prussa i3 and Ramps 1.4), and controlling the extrusion amount of a screw and a nozzle by using a G-code, wherein the moving speed of the nozzle in the printing process is 8 mm/s.
(5) The prepared BMIMTFSI-P film is used as an ionic gel electrolyte and a substrate at the same time, wherein polyethylene oxide (PEO) is dissolved in ethanol to obtain an ethanol solution of the polyethylene oxide (PEO), and the number average molecular weight of the polyethylene oxide (PEO) is 6000000; dissolving polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO) in ethanol to prepare an ethanol solution of polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO), dropwise adding 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt (BMIMTFSI) (ionic liquid) into the ethanol solution (polymer) of polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO), wherein the mass percent of polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO) in the ethanol solution of polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO) is 18 wt% and the mass percent of 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt (BMIMTFSI) is 18 wt% according to the volume ratio of the polymer to the ionic liquid of 3:7 The number of the reaction solution is 95%, and then adding lithium bistrifluoromethanesulfonimide LiTFSI into the mixed solution to obtain a reaction mixed solution I, wherein the average molecular weight of polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO) is 5800; equivalently mixing the ethanol solution of polyethylene oxide (PEO) prepared in the step 1 with the reaction mixed solution I prepared in the step 2, pouring the mixture into a tetrafluoro mold, performing vacuum drying at the vacuum drying temperature of 60 ℃ for 20 hours to obtain 1-butyl-3-methylimidazolium tetrafluoroborate-based ionic liquid gel electrolyte (BMIMTFSI-P), and performing 3D printing on the BMIMTFSI-P film by adopting the nanotube ink obtained in the step (2) to prepare the miniature supercapacitor
(6) And (5) putting the micro super capacitor obtained in the step (5) into a vacuum oven, and drying for 18h at 55 ℃ to obtain the self-healing ion gel electrolyte-based symmetrical super capacitor.
Example 3:
(1) weighing a proper amount of carbon nanotube powder, putting the carbon nanotube powder into a beaker filled with deionized water, and carrying out ultrasonic treatment for 8 hours to prepare a carbon nanotube solution with the mass fraction of 10%;
(2) and centrifuging the prepared solution, wherein the rotation speed of the centrifugation is 10000 r/min, and the centrifugation time is 4 min. And taking the supernatant to obtain the electrode ink for 3D printing.
(3) A carbon nanotube slurry was used as a printing ink, and the printing ink was filled in a syringe having a capacity of 1mL, and a plastic head having a diameter of 310 μm was disposed.
(4) And (3) performing a 3D printing process by adopting a multi-axis positioning system (Prussa i3 and Ramps 1.4), and controlling the extrusion amount of a screw and a nozzle by using a G-code, wherein the moving speed of the nozzle in the printing process is 6 mm/s.
(5) The prepared BMIMTFSI-P film is used as an ionic gel electrolyte and a substrate at the same time, wherein polyethylene oxide (PEO) is dissolved in ethanol to obtain an ethanol solution of the polyethylene oxide (PEO), and the number average molecular weight of the polyethylene oxide (PEO) is 6000000; dissolving polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO) in ethanol to prepare an ethanol solution of polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO), dropwise adding 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt (BMIMTFSI) (ionic liquid) into the ethanol solution (polymer) of polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO), wherein the mass percent of polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO) in the ethanol solution of polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO) is 25 wt% and the mass percent of 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt (BMIMTFSI) is 25 wt% according to the volume ratio of the polymer to the ionic liquid of 1:9 Adding bis (trifluoromethanesulfonyl) imide lithium salt LiTFSI into the mixed solution to obtain a reaction mixed solution I, wherein the average molecular weight of polyethylene oxide-polyphenyl ether-polyethylene oxide (PEO-PPO-PEO) is 5800; equivalently mixing the ethanol solution of polyethylene oxide (PEO) prepared in the step 1 with the reaction mixed solution I prepared in the step 2, pouring the mixture into a tetrafluoro mold, performing vacuum drying at 40 ℃ for 30 hours to obtain 1-butyl-3-methylimidazolium tetrafluoroborate-based ionic liquid gel electrolyte (BMIMTFSI-P), and performing 3D printing on the BMIMTFSI-P film by adopting the carbon nanotube ink obtained in the step (2) to prepare the micro supercapacitor
(6) And (4) putting the micro super capacitor obtained in the step (5) into a vacuum oven, and drying for 22h at the temperature of 60 ℃ to obtain the symmetrical super capacitor based on the self-healing ion gel electrolyte.
Example 4
(1) Weighing a proper amount of carbon nanotube powder, putting the carbon nanotube powder into a beaker filled with deionized water, and carrying out ultrasonic treatment for 8 hours to prepare a carbon nanotube solution with the mass fraction of 10%;
(2) and centrifuging the prepared solution, wherein the rotation speed of the centrifugation is 10000 r/min, and the centrifugation time is 4 min. And taking the supernatant to obtain the electrode ink for 3D printing.
(3) A carbon nanotube slurry was used as a printing ink, and the printing ink was filled in a syringe having a capacity of 1mL, and a plastic head having a diameter of 310 μm was disposed.
(4) And (3) performing a 3D printing process by adopting a multi-axis positioning system (Prussa i3 and Ramps 1.4), and controlling the extrusion amount of a screw and a nozzle by using a G-code, wherein the moving speed of the nozzle in the printing process is 6 mm/s.
(5) The prepared BMIMTFSI-P film is used as an ionic gel electrolyte and a substrate at the same time, wherein polyethylene oxide (PEO) is dissolved in ethanol to obtain an ethanol solution of the polyethylene oxide (PEO), and the number average molecular weight of the polyethylene oxide (PEO) is 6000000; dissolving polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO) in ethanol to prepare an ethanol solution of polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO), dropwise adding 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt (BMIMTFSI) (ionic liquid) into the ethanol solution (polymer) of polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO), wherein the mass percent of polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO) in the ethanol solution of polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO) is 22 wt% and the mass percent of 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt (BMIMTFSI) is 4:10 according to the volume ratio of the polymer to the ionic liquid Adding bis (trifluoromethanesulfonyl) imide lithium salt LiTFSI into the mixed solution to obtain a reaction mixed solution I, wherein the average molecular weight of polyethylene oxide-polyphenyl ether-polyethylene oxide (PEO-PPO-PEO) is 5800; equivalently mixing the ethanol solution of polyethylene oxide (PEO) prepared in the step 1 with the reaction mixed solution I prepared in the step 2, pouring the mixture into a tetrafluoro mold, performing vacuum drying at 40 ℃ for 30 hours to obtain 1-butyl-3-methylimidazolium tetrafluoroborate-based ionic liquid gel electrolyte (BMIMTFSI-P), and performing 3D printing on the BMIMTFSI-P film by adopting the carbon nanotube ink obtained in the step (2) to prepare the micro supercapacitor
(6) And (4) putting the micro super capacitor obtained in the step (5) into a vacuum oven, and drying for 22h at the temperature of 60 ℃ to obtain the symmetrical super capacitor based on the self-healing ion gel electrolyte.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (8)
1. The utility model provides an use flexible ultracapacitor system of 3D printing self-repair of ionic gel electrolyte as basement which characterized in that: the method comprises the following steps of taking carbon nanotubes as printing ink, taking 1-butyl-3-methylimidazolium tetrafluoroborate-based ionic liquid gel electrolyte (BMIMTFSI-P) as the ionic gel electrolyte and a substrate, taking the carbon nanotubes as a positive electrode material and a negative electrode material, and obtaining the self-repairing flexible supercapacitor by an ink direct writing technology, wherein the method comprises the following steps:
preparing the carbon nano tube printing ink:
placing carbon nanotube powder in deionized water, performing ultrasonic treatment for 6-12h to obtain a carbon nanotube solution with the mass fraction of 10%, centrifuging the prepared carbon nanotube solution, and taking supernatant to obtain carbon nanotube printing ink;
preparation of 1-butyl-3-methylimidazolium tetrafluoroborate-based ionic liquid gel electrolyte (BMIMTFSI-P):
step 1, dissolving polyethylene oxide (PEO) in ethanol to obtain an ethanol solution of the polyethylene oxide (PEO), wherein the number average molecular weight of the polyethylene oxide (PEO) is 6000000;
step 2, dissolving polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO) in ethanol to prepare an ethanol solution of polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO), dropwise adding 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt (BMIMTFSI) into the ethanol solution of polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO), and adding lithium bistrifluoromethylsulfonyl imide salt LiTFSI into the mixed solution to obtain a reaction mixed solution I, wherein the average molecular weight of the polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO) is 5800, the ethanol solution of the polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO) and the 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl imide are added to obtain a reaction mixed solution I The volume ratio of the salt (BMIMTFSI) is (1-4): (7-10), the mass percent of the polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO) in the ethanol solution of the polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO) is 18-25 wt%, and the mass percent of the 1-butyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt (BMIMTFSI) is 95-98%;
and 3, mixing the ethanol solution of the polyethylene oxide (PEO) prepared in the step 1 and the reaction mixed solution I prepared in the step 2 in equal amount, pouring the mixture into a tetrafluoro mold, and drying the mixture in vacuum to obtain the ionic liquid gel electrolyte (BMIMTFSI-P) based on the 1-butyl-3-methylimidazolium tetrafluoroborate.
2. The ionic gel electrolyte based 3D printed self-repairing flexible supercapacitor according to claim 1, wherein the ionic gel electrolyte based 3D printed self-repairing flexible supercapacitor comprises: preparing the carbon nano tube printing ink: the rotation speed of the centrifugation is 6000-10000 r/min, and the centrifugation time is 4-10 min.
3. The ionic gel electrolyte based 3D printed self-repairing flexible supercapacitor according to claim 1, wherein the ionic gel electrolyte based 3D printed self-repairing flexible supercapacitor comprises: in step 2, the volume ratio of the ethanol solution of polyethylene oxide-polyphenylene oxide-polyethylene oxide (PEO-PPO-PEO) to 1-butyl-3-methylimidazolium bistrifluoromethylsulfimide salt (BMIMTFSI) was (1-3): (7-9).
4. The ionic gel electrolyte based 3D printed self-repairing flexible supercapacitor according to claim 1, wherein the ionic gel electrolyte based 3D printed self-repairing flexible supercapacitor comprises: in the step 3, the vacuum drying temperature is 40-60 ℃, and the vacuum drying time is 20-30 h.
5. The 3D printing self-repairing flexible supercapacitor taking the ionic gel electrolyte as the substrate as claimed in any one of claims 1 to 4, wherein the ionic gel electrolyte is used for carrying out self-repairing on the substrate, and the ionic gel electrolyte is used for carrying out self-repairing on the substrate according to the following steps: the working voltage of the 3D printing self-repairing flexible supercapacitor taking the ionic gel electrolyte as the substrate is 0-3.0V (excluding 0).
6. The 3D printing self-repairing flexible supercapacitor taking the ionic gel electrolyte as the substrate as claimed in any one of claims 1 to 4, wherein the ionic gel electrolyte is used for carrying out self-repairing on the substrate, and the ionic gel electrolyte is used for carrying out self-repairing on the substrate according to the following steps: with the increase of the sweep rate, the stability of the cyclic voltammetry curve is good, namely the self-repairing flexible supercapacitor has good ion conduction capability and shows excellent capacitance performance.
7. The 3D printing self-repairing flexible supercapacitor taking the ionic gel electrolyte as the substrate as claimed in any one of claims 1 to 4, wherein the ionic gel electrolyte is used for carrying out self-repairing on the substrate, and the ionic gel electrolyte is used for carrying out self-repairing on the substrate according to the following steps: the self-repairing flexible super capacitor is arranged at 5mV s-1The specific capacitance at the scanning rate is 70-74mF cm-2And at 100mV s-1The capacity retention rate reaches 58-62% at the scanning speed, and good rate performance is shown.
8. The 3D printing self-repairing flexible supercapacitor taking the ionic gel electrolyte as the substrate as claimed in any one of claims 1 to 4, wherein the ionic gel electrolyte is used for carrying out self-repairing on the substrate, and the ionic gel electrolyte is used for carrying out self-repairing on the substrate according to the following steps: when the current density is 0.5-5mA cm-2In time, the specific capacity of the self-repairing flexible super capacitor is 38-66mF cm-2The capacity retention rate is 55-60%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113421778A (en) * | 2021-06-21 | 2021-09-21 | 青岛理工大学 | Flexible micro super capacitor and manufacturing method thereof |
| CN115394571A (en) * | 2022-08-03 | 2022-11-25 | 西北工业大学宁波研究院 | Integrated 3D printing flexible supercapacitor prepared through ionic crosslinking and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150061538A (en) * | 2013-11-25 | 2015-06-04 | 한국화학연구원 | Electrolyte membrane made of resin composition comprising polymer formed by branching of block copolymer comprising poly(propylene oxide) block and poly(ethylene oxide) block, and ionic electrolyte |
| CN110098067A (en) * | 2018-01-29 | 2019-08-06 | 天津大学 | It can ink direct write printing flexible electrode and its preparation method and application |
-
2019
- 2019-09-16 CN CN201910872475.2A patent/CN112509820B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150061538A (en) * | 2013-11-25 | 2015-06-04 | 한국화학연구원 | Electrolyte membrane made of resin composition comprising polymer formed by branching of block copolymer comprising poly(propylene oxide) block and poly(ethylene oxide) block, and ionic electrolyte |
| CN110098067A (en) * | 2018-01-29 | 2019-08-06 | 天津大学 | It can ink direct write printing flexible electrode and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| JAE HEE HAN: ""Electrode-Impregnable and Cross-Linkable Poly(ethylene oxide)−Poly(propylene oxide)−Poly(ethylene oxide) Triblock Polymer Electrolytes with High Ionic Conductivity and a Large Voltage Window for Flexible Solid-State Supercapacitors"", 《APPLIED MATERIALS & INTERFACES》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113421778A (en) * | 2021-06-21 | 2021-09-21 | 青岛理工大学 | Flexible micro super capacitor and manufacturing method thereof |
| CN115394571A (en) * | 2022-08-03 | 2022-11-25 | 西北工业大学宁波研究院 | Integrated 3D printing flexible supercapacitor prepared through ionic crosslinking and preparation method thereof |
| CN115394571B (en) * | 2022-08-03 | 2023-08-18 | 西北工业大学宁波研究院 | Integrated 3D printing flexible supercapacitor prepared through ionic crosslinking and preparation method thereof |
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