CN114551111B - Ink direct-writing 3D printing conductive polymer-based micro supercapacitor and preparation method thereof - Google Patents
Ink direct-writing 3D printing conductive polymer-based micro supercapacitor and preparation method thereof Download PDFInfo
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- CN114551111B CN114551111B CN202210048487.5A CN202210048487A CN114551111B CN 114551111 B CN114551111 B CN 114551111B CN 202210048487 A CN202210048487 A CN 202210048487A CN 114551111 B CN114551111 B CN 114551111B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/48—Conductive polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a conductive polymer-based micro supercapacitor for ink direct-writing 3D printing and a preparation method thereof, and belongs to the technical field of electrochemical energy storage. The micro supercapacitor comprises a substrate, a current collector, an interdigital electrode, a gel electrolyte and a packaging layer, wherein the electrode material is PEDOT (PEDOT)/PSS/MXene composite hydrogel. According to the invention, the PEDOT and the PSS are subjected to phase separation through the ethylene glycol to form a conductive PEDOT phase, so that the conductivity of the material is improved. Through the electrostatic interaction of MXene and PEDOT, PSS prevents aggregation and ensures that the printing ink has excellent printable performance; meanwhile, the loose and porous structure is beneficial to the transmission of electrolyte ions, and excellent electrochemical performance is obtained. The conductive polymer-based micro super capacitor has high area capacitance, rate capability, energy density, power density and excellent low-temperature resistance, and has great potential in the field of flexible energy storage.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage, and particularly relates to a conductive polymer-based micro supercapacitor for ink direct-writing 3D printing and a preparation method thereof.
Background
With the development of the internet of things, flexible wearable electronic devices have been widely applied to the fields of smart homes, medical treatment, entertainment and the like, and therefore, it is a current research focus to provide a compatible flexible energy storage device to advance the application of these electronic devices. Compared with a battery, the super capacitor has the advantages of high power density, high charge-discharge rate, long cycle life, high safety coefficient and the like, and is an energy storage device with great potential. However, due to their light weight and small size, their energy density is generally low, which may not be sufficient to meet the continuous and stable power supply requirements of electronic devices. In addition to the requisite electrochemical performance, higher demands are also placed on the flexibility and integratability of energy storage devices to meet the demands of flexible wearable electronic device applications.
The interdigital super capacitor is a novel micro super capacitor, and is different from the traditional sandwich super capacitor, the ion transmission of the interdigital super capacitor mainly occurs in the direction parallel to the distance between two fingers, and is not related to the thickness direction, so that the loading capacity of an electroactive substance can be increased by increasing the thickness of an electrode, the surface energy density of a device is increased, and the ion transmission capability of the device is not lost. In addition, the interdigital type super capacitor is easy to integrate and is resistant to certain bending, and the requirement of the conventional flexible wearable electronic equipment can be met. The preparation of interdigital supercapacitors by photolithography and laser etching has been studied at present, but they both involve some complex and expensive processes; in addition, there have been studies on the preparation of an interdigital supercapacitor by screen printing and inkjet printing, and although such printing processes simplify the preparation process, it is difficult to achieve a high loading amount of electrochemically active materials due to the limitation of printing materials, and thus, there is a need for a method capable of preparing a high-performance interdigital supercapacitor.
3D printing, especially the Direct Ink Writing (DIW) technology is widely applied to the printing preparation of the electrode structure due to the characteristics of wide precision range, strong material expansibility and the like. Unlike other preparation methods, the DIW technique does not require template-assisted preparation, is simple in process, and requires a material with a relatively high viscosity to ensure moldability, which requires a material with a relatively high concentration, so that a high loading of the electrochemical substance can be achieved. Furthermore, the DIW technology can also realize printing of a fine and complicated three-dimensional structure, and can easily realize integrated printing. Therefore, the DIW technology can be used for obtaining the interdigital super capacitor with high performance. The most important thing to do with DIW technology is to obtain printable ink first.
The conductive polymer has high conductivity and theoretical specific capacitance, low cost and excellent mechanical flexibility, so the conductive polymer has great prospect as a super capacitor material. But the acting force among molecular chains is strong, the agglomeration is easy, and the ink is difficult to be dissolved in water and most organic solvents, so that the universal ink for 3D printing is difficult to be directly obtained. PSS is the only commercial water-soluble conducting polymer-based material, wherein negatively charged hydrophilic PSS chains are used as a dispersant and a dopant, and positively charged hydrophobic PEDOT chains are uniformly dispersed in water through electrostatic interaction, so that the reprocessing of PEDOT is realized. However, since a large number of nonconductive PSS chains wrap conductive PEDOT chains, which causes very poor conductivity of the PEDOT: PSS and hardly can be directly used as an electrode material of a supercapacitor, improving the conductivity of the PEDOT: PSS on the basis of not losing the printability of the PEDOT: PSS is a problem which needs to be solved at present.
Currently, research is carried out to improve the conductivity of PEDOT and PSS by adding an organic solvent into a system, wherein the organic solvent can destroy the electrostatic interaction between the PEDOT and the PSS, so that the PEDOT and the PSS are separated from each other, and the PEDOT is stacked to form a conductive phase due to the strong pi-pi conjugation, so that the conductivity of the material is improved. However, the accumulation of large amounts of PEDOT may clog the needle, losing printability and therefore generally requiring mechanical grinding of the material to reduce the particle size of the material involves a complicated process and wastes material leading to high costs. Furthermore, high concentrations of materials are not generally employed to reduce such agglomeration, making higher loading of electrochemical species difficult to achieve. Most importantly, the non-conductive PSS phase is still present in the system in large amounts, which severely degrades the electrochemical performance of the supercapacitor. Therefore, further achieving high electrochemical performance supercapacitors by ink-direct writing 3D printing technology without sacrificing PEDOT: PSS printability at all remains a great challenge.
Disclosure of Invention
[ problem ] to
Currently, the interdigital supercapacitor is prepared by adopting a direct ink writing 3D printing technology through PEDOT (polymer stabilized ethylene terephthalate) (PSS). Existing methods of increasing the conductivity of PEDOT: PSS suffer from some loss of printable performance and involve complicated processes and high costs, and most importantly, high performance supercapacitors cannot be obtained.
[ solution ]
In order to solve the problems in the prior art, the invention provides PEDOT/PSS composite ink with good printing performance, and further prepares a high-performance interdigital supercapacitor by using an ink direct-writing 3D printing technology. According to the invention, firstly, the PEDOT-PSS phase separation is carried out by using the ethylene glycol to form a conductive PEDOT phase, so that the conductivity of the material is improved. On the basis, a two-dimensional conductive material MXene is further used for ensuring the printability and high electrochemical performance of the material. The negatively charged MXene can prevent the large aggregation of PEDOT through electrostatic interaction, so that the printable performance of PEDOT: PSS is not lost, the viscosity of the system can be additionally reduced, and the total concentration of the system can be continuously increased, so that the high loading of electrochemical substances is realized. Most importantly, a more loose and porous structure can be formed by adding MXene, and the MXene has high conductivity, so that more conductive paths can be provided in a system, a conductive PEDOT phase is connected, the influence of a non-conductive PSS phase is reduced, and the transmission of electrolyte ions is facilitated, so that the interdigital supercapacitor with printing performance and high electrochemical performance can be finally obtained. In addition, although pure PEDOT: PSS has a certain printing performance, it is difficult to ensure high electrochemical performance, and printing of pure MXene requires a complicated process to disperse MXene to obtain an extremely high concentration, and it is difficult to ensure stability of printing performance. The printing ink with proper viscosity and rheological property is regulated and controlled by simple compounding of PEDOT, PSS and MXene, and the interdigital supercapacitor with excellent performance is prepared by the ink direct writing 3D printing technology.
The invention firstly provides a conductive polymer-based micro supercapacitor for ink direct-writing printing, which comprises a substrate, a current collector, an interdigital electrode, a gel electrolyte and an encapsulation layer, wherein the current collector is made of gold, silver, copper or nickel, the interdigital electrode is made of PEDOT (PSS/MXene) composite hydrogel, the gel electrolyte is a polyvinyl alcohol/sulfuric acid gel electrolyte, and the encapsulation layer is styrene-butadiene-styrene block copolymer (SBS) or Polydimethylsiloxane (PDMS).
In one embodiment of the present invention, the electrode material of the interdigital electrode is prepared by the following method: MXene is dissolved in a solvent, the solvent is uniformly dispersed, PEDOT: PSS is added, printable ink which is uniformly mixed is obtained through stirring, and then the ink is directly written on a load current collector in a 3D printing mode.
In one embodiment of the invention, the solvent is water or a water-glycol mixed solvent, wherein the volume ratio of water to glycol in the mixed solvent is 2:1-20, and the water-glycol mixed solvent is preferably selected from the following group.
In one embodiment of the invention, the dispersion is preferably ultrasonic dispersion.
In one embodiment of the invention, the PEDOT: PSS is obtained by freeze-drying commercial aqueous pH1000 solutions; the MXene is obtained by the following steps: adding the MAX phase ceramic material into a hydrochloric acid/lithium fluoride mixed solution, etching at 25-40 ℃ to obtain an MXene phase, then washing to neutrality, centrifuging after ultrasonic stripping, collecting supernatant to obtain MXene dispersion liquid, and freeze-drying to obtain MXene.
In one embodiment of the present invention, the MAX-phase ceramic material has a mass of 1 to 6g, the hydrochloric acid concentration in the hydrochloric acid/lithium fluoride mixed solution is 7 to 10mol/L, and the lithium fluoride has a mass of 1 to 6g.
In one embodiment of the invention, the mass ratio of PEDOT to PSS to MXene is 7:1 to 1:5, and the total concentration of PEDOT to PSS to MXene is 60 to 180mg mL -1 The ultrasonic time is 15-90 min after MXene is added, and the stirring time is 60-180 min after PEDOT and PSS are added.
In one embodiment of the invention, the PEDOT to PSS to MXene mass ratio is preferably 1:1.
The invention also provides a preparation method of the conductive polymer-based micro supercapacitor, which comprises the following specific preparation steps:
(1) Loading a current collector on a substrate in an ink direct-writing 3D printing mode, and drying to obtain an interdigital pattern;
(2) Dissolving MXene in water or a water-ethylene glycol mixed solvent, uniformly dispersing, then adding PEDOT (PEDOT-PSS), and stirring to obtain uniformly mixed printable ink;
(3) Loading the ink obtained in the step (2) on the interdigital current collector obtained in the step (1) in an ink direct-writing 3D printing mode to obtain a composite hydrogel-based interdigital electrode;
(4) Coating an electrolyte aqueous solution on the interdigital electrode obtained in the step (3), and drying and concentrating to obtain a gel electrolyte;
(5) And (4) coating the packaging liquid on the gel electrolyte obtained in the step (4), and drying to obtain the packaged conductive polymer-based micro supercapacitor.
In one embodiment of the present invention, in the step (1), the substrate is any one of polyethylene terephthalate (PET), polydimethylsiloxane (PDMS), polyimide (PI), and Polystyrene (PS); the current collector is made of gold, silver, copper or nickel; the drying is carried out for 0.5 to 2 hours at the temperature of between 40 and 100 ℃.
In one embodiment of the invention, the PEDOT: PSS in step (2) is obtained by freeze-drying commercial aqueous pH1000 solutions; the MXene is obtained by the following steps: adding the MAX phase ceramic material into a hydrochloric acid/lithium fluoride mixed solution, etching at 25-40 ℃ to obtain an MXene phase, then washing to neutrality, centrifuging after ultrasonic stripping, collecting supernatant to obtain MXene dispersion liquid, and freeze-drying to obtain MXene.
In one embodiment of the invention, the mass ratio of PEDOT to PSS to MXene in the step (2) is 7:1-1:5, and the total concentration of the PEDOT to PSS to MXene is 60-180 mg mL -1 The volume ratio of water to glycol in the mixed solvent is 2:1-20; the ultrasonic time is 15-90 min after MXene is added, and the stirring time is 60-180 min after PEDOT and PSS are added.
In one embodiment of the present invention, the 3D printing air pressure in the step (3) is 20 to 400kPa and a printing speed of 1 to 10mm s -1 The diameter of the needle head is 0.06-1.5 mm.
In one embodiment of the present invention, in step (3), the printed interdigital electrode structure has a finger width of 0.1 to 6mm, a finger length of 0.5 to 12mm, a finger pitch of 0.1 to 6mm, and a finger height of 0.05 to 6mm.
In one embodiment of the present invention, the electrolyte in step (4) is a polyvinyl alcohol/sulfuric acid aqueous solution, wherein the polyvinyl alcohol content is 3-20 wt%, and the sulfuric acid content is 0.1-4 mol L -1 The preparation method comprises the following specific steps: adding polyvinyl alcohol into the prepared sulfuric acid solution, and dissolving for 0.5-3 h at 65-90 ℃; the drying is carried out for 10-40 min at the temperature of 40-80 ℃.
In one embodiment of the present invention, the encapsulation liquid in step (5) is a toluene solution of SBS or a commercial PDMS encapsulation liquid, wherein the SBS content is 5 to 30wt%, and the specific preparation steps are as follows: adding SBS into toluene, dissolving at 50-80 deg.c for 3-8 hr; the drying is carried out for 10-240 min at the temperature of 25-80 ℃.
The invention also provides electronic equipment comprising the conductive polymer-based micro supercapacitor.
The invention also provides application of the conductive polymer-based micro supercapacitor in the fields of smart home, medical treatment and entertainment.
The invention has the beneficial effects that:
(1) The ink direct-writing 3D printing technology adopted by the invention does not need template auxiliary preparation, has simple process and low cost, and can realize high loading capacity of electrochemical substances.
(2) The invention has ingenious experimental design, and high-performance printable ink is obtained by compounding PEDOT, PSS and MXene in water or a water-glycol mixed solvent. Particularly, a water-ethylene glycol mixed solvent is used, and the ethylene glycol enables phase separation of PEDOT and PSS to form a conductive PEDOT phase, so that the conductivity of the material is improved. On the basis, the negatively charged MXene can prevent the PEDOT from gathering in a large amount through electrostatic interaction, so that the printable performance of the material is ensured; and a loose and porous structure can be formed, more conductive paths are provided in a system, the transmission of electrolyte ions is facilitated, and the high electrochemical performance of the material is ensured.
(3) The interdigital super capacitor prepared by adopting the ink direct-writing 3D printing technology obtains excellent electrochemical performance due to the synergistic effect of electrode materials and the unique electrode structure of the interdigital electrode, has high area capacitance, multiplying power performance, energy density and power density, additionally obtains excellent low-temperature resistance, has wider application places, and has huge application potential in the field of flexible energy storage.
Drawings
Fig. 1 is an optical photograph of the interdigital supercapacitor prepared in example 1.
FIG. 2 is a rheological property test of the inks prepared in example 1, comparative example 1 and comparative example 2.
Fig. 3 is an SEM image of interdigitated electrodes prepared from different component inks. Wherein (a) is the interdigitated electrode provided in comparative example 2; (b) the interdigitated electrodes provided for example 3; (c) the interdigitated electrode provided for example 2; and (d) is the interdigital electrode provided in example 1.
Fig. 4 is a test of electrochemical performance of the interdigital supercapacitors prepared in example 1, example 2 and example 3.
Fig. 5 shows electrochemical performance tests of the interdigital supercapacitors prepared in example 1, example 4 and example 5.
Fig. 6 is a test of electrochemical performance of the interdigital supercapacitors prepared in example 1, example 6 and example 7.
Fig. 7 shows the electrochemical performance test of the interdigital supercapacitor prepared in example 1 at different temperatures.
Detailed Description
The present invention is further described below with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
The embodiment comprises the following steps:
(1) Adding 4g of lithium fluoride into 80mL of 9M hydrochloric acid, dissolving for 30min, then adding 4g of MAX-phase ceramic material into the mixed solution, etching for 24h at 35 ℃ to obtain MXene phase, then washing to neutrality, ultrasonically stripping for 15min, then centrifuging for 30min, collecting supernatant to obtain MXene dispersion liquid, and finally freeze-drying the MXene dispersion liquid and a commercial PH1000 aqueous solution to obtain freeze-dried MXene and PEDOT, namely PSS;
(2) Stirring and mixing 2.4mL of water and 0.6mL of ethylene glycol to obtain 3mL of mixed solvent (the volume ratio is 4:1), weighing 0.18g of MXene, adding the MXene into the mixed solvent, carrying out ultrasonic treatment for 60min to uniformly disperse, weighing 0.18g of PEDOT: PSS, adding the PEDOT: PSS into the mixed solution, stirring for 120min and uniformly mixing to obtain the total concentration of 120mg mL -1 The printable ink of (PEDOT: PSS and MXene mass ratio 1:1);
(3) Selecting a PET substrate, loading commercial silver paste on the substrate in an ink direct-writing 3D printing mode, drying in a drying oven at 60 ℃ for 120min to obtain an interdigital current collector pattern, then loading the printable ink obtained in the step (2) on an interdigital current collector in an ink direct-writing 3D printing mode to obtain a composite hydrogel-based interdigital electrode, wherein the printing specific parameters are set as: the specification of the needle head is 0.21mm, the printing air pressure is 84kPa, and the printing speed is 4mm s -1 ；
(4) 3g of polyvinyl alcohol are added to 30mL of 1M H 2 SO 4 Stirring and dissolving the solution for 120min at 85 ℃ to obtain a polyvinyl alcohol/sulfuric acid aqueous solution electrolyte, then coating the aqueous solution electrolyte on the interdigital electrode, drying the interdigital electrode for 30min in a drying oven at 60 ℃, and concentrating to obtain a gel electrolyte;
(5) Adding 4.5g of SBS into 25.5g of toluene, stirring and dissolving for 6h at 65 ℃ to obtain a packaging liquid, then coating the packaging liquid on a gel electrolyte, and drying for 30min at room temperature to obtain a packaged conductive polymer matrix micro supercapacitor which is marked as EPPM-1.
Example 2
The mass ratio of PEDOT to PSS to MXene in example 1 was changed to 3:1 (keeping the total concentration constant), the rest was the same as in example 1, and the finally obtained micro-supercapacitor was designated as EPPM-2.
Example 3
The mass ratio of PEDOT to PSS to MXene in example 1 was changed to 5:1 (keeping the total concentration constant), the rest was the same as in example 1, and the finally obtained micro-supercapacitor was designated as EPPM-3.
Example 4
The total mass concentration of PEDOT, PSS and MXene in example 1 was changed to 80mg mL -1 (keeping the mass ratio of the two constant), the rest is the same as that of the example 1, and the finally obtained miniature super capacitor is marked as EPPM-4.
Example 5
The total mass concentration of PEDOT, PSS and MXene in example 1 was changed to 160mg mL -1 (keeping the mass ratio of the two constant), the rest is the same as that of the example 1, and the finally obtained miniature super capacitor is marked as EPPM-5.
Example 6
The volume ratio of water and ethylene glycol of the mixed solvent in example 1 was changed to 2:1 (the total volume was kept constant), and the rest was the same as in example 1, and the finally obtained micro-supercapacitor was designated as EPPM-6.
Example 7
The mixed solvent of 3mL in example 1 was changed to water of 3mL, and the rest was the same as example 1, and the finally obtained micro-supercapacitor was designated as EPPM-7.
Comparative example 1
The comparative example comprises the following steps:
(1) Adding 4g of lithium fluoride into 80mL of 9M hydrochloric acid, dissolving for 30min, then adding 4g of MAX-phase ceramic material into the mixed solution, etching for 24h at 35 ℃ to obtain an MXene phase, then washing to neutrality, ultrasonically stripping for 15min, then centrifuging for 30min, collecting supernatant to obtain MXene dispersion liquid, and finally freeze-drying the MXene dispersion liquid to obtain freeze-dried MXene;
(2) Stirring and mixing 2.4mL of water and 0.6mL of ethylene glycol to obtain 3mL of mixed solvent (the volume ratio is 4:1), weighing 0.36g of MXene, adding into the mixed solvent, and performing ultrasonic treatment for 60min to uniformly disperse to obtain the total concentration of 120mg mL -1 The MXene ink of (1) was designated as MXene.
Comparative example 2
Freeze-dried PED obtained by freeze-drying commercial aqueous pH1000 solutionPSS, 2.4mL of water and 0.6mL of ethylene glycol are stirred and mixed to obtain 3mL of mixed solvent (the volume ratio is 4:1), 0.36g of the PSS is weighed and added into the mixed solvent, and the mixture is stirred for 120min and mixed uniformly to obtain the total concentration of 120mg mL -1 The PEDOT: PSS inks are noted PEDOT: PSS.
As shown in fig. 1: the preparation method provided by the embodiment 1 of the invention can successfully prepare the interdigital supercapacitor, does not need template-assisted preparation, and has a simple process. As shown in the figure a, a layer of interdigital current collector is successfully printed; as shown in fig. b, 3 layers of interdigitated electrodes were successfully printed, and it can be seen that the composite ink has excellent formability, which is attributed to the improvement of rheological properties of the composite system by MXene; as shown in fig. c, a layer of gel electrolyte was successfully applied; as shown in fig. d, an encapsulation layer was successfully applied, thereby successfully preparing an encapsulated interdigital supercapacitor.
As shown in fig. 2: the ink prepared in the invention (example 1) has rheological property suitable for printing, pure MXene ink (comparative example 1) has very low modulus and almost no formability under the same concentration, pure PEDOT (PSS ink (comparative example 2) has high modulus, is difficult to extrude and is difficult to print, and is not suitable for printing from the rheological property of the two, and the composite ink (example 1) has suitable modulus due to strong interaction force between the two and has better printing property within a printable range.
As shown in fig. 3: the interdigital electrode prepared by the invention has a loose and porous structure. As shown in FIG. a (comparative example 2), pure PEDOT: PSS is prone to aggregation, forming a large sheet structure; as shown in FIG. b (example 3), a pore structure is formed after addition of MXene, since electrostatic interaction prevents aggregation of PEDOT: PSS, making the lamella smaller; as shown in fig. c (example 2), the pore structure continues to increase and the lamellae continue to decrease after increasing MXene content; it is shown by the graph d (example 1) that the highest MXene content has an extremely porous structure, providing more conductive paths and facilitating the transport of electrolyte ions.
As shown in fig. 4: interdigital super capacitor prepared by the inventionThe embodiment 1, the embodiment 2 and the embodiment 3) have excellent electrochemical performance, which exceeds most of the prior interdigital supercapacitors, and it can be seen that with the increase of the MXene content, the conductive paths in the electrodes are increased, the electrolyte ion transmission is enhanced, and therefore, the charging and discharging time of the supercapacitor is correspondingly increased, namely, the electrochemical performance is correspondingly increased, and the figure can calculate that when the MXene content is the highest, namely, the embodiment 1 has the maximum specific capacitance of 270mF cm -2 And an energy density of 23.96. Mu. Wh cm -2 。
As shown in fig. 5: the interdigital supercapacitors (example 1, example 4 and example 5) prepared by the method have excellent electrochemical performance, which exceeds most of the conventional interdigital supercapacitors, and it can be seen that the loading amount of electrochemical substances in the electrode is increased along with the increase of the total concentration, so that the charging and discharging time of the supercapacitor is correspondingly increased, namely the electrochemical performance is correspondingly increased.
As shown in fig. 6: the interdigital supercapacitors (example 1, example 6 and example 7) prepared by the method have excellent electrochemical performance, which exceeds most of the conventional interdigital supercapacitors, and it can be seen that after the ethylene glycol is added into the system (example 1), the ethylene glycol makes the PEDOT to PSS phase separated to form a conductive PEDOT phase, so that the conductivity of the material is improved, and therefore, the charging and discharging time of the supercapacitor is correspondingly increased, namely the electrochemical performance is correspondingly increased.
As shown in fig. 7: the interdigital supercapacitor prepared in the invention (example 1) has excellent low-temperature resistance, and the addition of ethylene glycol in the system can effectively lower the freezing point of the system, prevent the system from freezing, still can transmit ions at low temperature, and even at-40 ℃, the supercapacitor still has 186mF cm -2 The capacity retention rate is as high as 69%.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (9)
1. The conductive polymer-based micro supercapacitor is characterized by comprising a substrate, a current collector, an interdigital electrode, a gel electrolyte and an encapsulation layer, wherein the current collector is made of gold, silver, copper or nickel, the interdigital electrode is made of PEDOT (polyethylene glycol terephthalate)/MXene (polyethylene glycol/polyethylene glycol terephthalate) composite hydrogel, the gel electrolyte is a polyvinyl alcohol/sulfuric acid gel electrolyte, and the encapsulation layer is a styrene-butadiene-styrene block copolymer or polydimethylsiloxane; the electrode material PEDOT/PSS/MXene composite hydrogel is prepared by the following method: MXene is dissolved in water or a water-ethylene glycol mixed solvent, the mixture is uniformly dispersed, PEDOT: PSS is added, printable ink which is uniformly mixed is obtained through stirring, and then the ink is loaded on a current collector in a 3D printing mode.
2. The conductive polymer-based micro supercapacitor according to claim 1, wherein the volume ratio of water to ethylene glycol in the water-ethylene glycol mixed solvent is 2:1-20.
3. The conductive polymer-based micro supercapacitor according to claim 1 or 2, wherein the mass ratio of PEDOT to PSS to MXene is 7:1 to 1:5, and the total concentration of the PEDOT to PSS to MXene is 60mg mL to 180mg mL -1 。
4. A method for preparing a conducting polymer based micro supercapacitor according to any one of claims 1 to 3, characterised in that it comprises the following steps:
(1) Loading a current collector on a substrate in an ink direct-writing 3D printing mode, and drying to obtain an interdigital pattern;
(2) Dissolving MXene in water or a water-ethylene glycol mixed solvent, uniformly dispersing, then adding PEDOT (PEDOT-PSS), and stirring to obtain uniformly mixed printable ink;
(3) Loading the ink obtained in the step (2) on the interdigital current collector obtained in the step (1) in an ink direct-writing 3D printing mode to obtain a composite hydrogel-based interdigital electrode;
(4) Coating an electrolyte aqueous solution on the interdigital electrode obtained in the step (3), and drying and concentrating to obtain a gel electrolyte;
(5) And (4) coating the packaging liquid on the gel electrolyte obtained in the step (4), and drying to obtain the packaged conductive polymer-based micro supercapacitor.
5. The method according to claim 4, wherein the substrate in the step (1) is any one of polyethylene terephthalate, polydimethylsiloxane, polyimide, and polystyrene.
6. The production method according to claim 4 or 5, wherein the 3D printing air pressure in the step (3) is 20 to 400kPa, and the printing speed is 1 to 10mm s -1 The diameter of the needle head is 0.06-1.5 mm.
7. The method according to claim 4, wherein the electrolyte in the step (4) is an aqueous solution of polyvinyl alcohol/sulfuric acid, wherein the polyvinyl alcohol content is 3 to 20wt% and the sulfuric acid content is 0.1 to 4mol L -1 。
8. An electronic device comprising a conducting polymer-based micro supercapacitor according to any one of claims 1 to 3.
9. The application of the conducting polymer-based micro supercapacitor of any one of claims 1 to 3 in the fields of smart home, medical treatment and entertainment.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210048487.5A CN114551111B (en) | 2022-01-17 | 2022-01-17 | Ink direct-writing 3D printing conductive polymer-based micro supercapacitor and preparation method thereof |
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| CN116039075B (en) * | 2023-03-31 | 2023-06-20 | 四川大学 | Rapid liquid phase 3D printing method for preparing PEDOT (polyethylene glycol terephthalate)/PSS (polybutylene terephthalate) flexible wire |
| CN116589886A (en) * | 2023-06-01 | 2023-08-15 | 东北林业大学 | MXene/conductive cellulose/conductive polymer high-conductivity ink, preparation method thereof and application thereof in flexible micro supercapacitor |
| CN116741550B (en) * | 2023-08-14 | 2023-11-17 | 中国科学技术大学 | Flexible stretchable hydrogel interdigital electrode and micro-super capacitor based on same |
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| WO2020096366A1 (en) * | 2018-11-07 | 2020-05-14 | 성균관대학교산학협력단 | Mxene-conductive polymer composite material and supercapacitor comprising same |
| CN111223687A (en) * | 2020-01-13 | 2020-06-02 | 常州大学 | Preparation method of MXene/PANI-based high-capacity linear supercapacitor electrode |
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