CN116504543A - Symmetrical flexible supercapacitor and preparation method thereof - Google Patents
Symmetrical flexible supercapacitor and preparation method thereof Download PDFInfo
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- 238000009987 spinning Methods 0.000 claims abstract description 91
- 239000012528 membrane Substances 0.000 claims abstract description 31
- 238000004806 packaging method and process Methods 0.000 claims abstract description 27
- 238000007664 blowing Methods 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
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- 238000000034 method Methods 0.000 claims description 20
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 9
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- 238000005538 encapsulation Methods 0.000 claims description 8
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- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 229920001601 polyetherimide Polymers 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 229920000875 Dissolving pulp Polymers 0.000 claims description 2
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- 239000003990 capacitor Substances 0.000 abstract description 23
- 239000000243 solution Substances 0.000 description 62
- 239000002121 nanofiber Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 9
- 230000002572 peristaltic effect Effects 0.000 description 8
- 238000010041 electrostatic spinning Methods 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
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- 229910001220 stainless steel Inorganic materials 0.000 description 6
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- 239000007772 electrode material Substances 0.000 description 5
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Semiconductor Integrated Circuits (AREA)
Abstract
The invention relates to a symmetrical flexible super capacitor and a preparation method thereof, and belongs to the technical field of capacitors. The preparation method comprises the following steps of S1, respectively preparing a membrane layer spinning solution, an electrode layer spinning solution and a packaging layer spinning solution; s2, respectively spraying the spinning solution of the diaphragm layer, the spinning solution of the electrode layer and the spinning solution of the packaging layer through a solution blowing spinning technology, and sequentially forming a first packaging layer, a first electrode layer, the diaphragm layer, a second electrode layer and a second packaging layer on a receiving device to obtain the symmetrical flexible supercapacitor. According to the preparation method, three nozzles are adopted for intermittent spinning, and the symmetrical flexible super capacitor with high energy density, good mechanical property and cycle stability is prepared on the receiving device at one time, so that the assembly is not needed, and the manufacturing process is greatly simplified.
Description
Technical Field
The invention belongs to the technical field of capacitors, and particularly relates to a symmetrical flexible supercapacitor and a preparation method thereof.
Background
The development of the Internet of things promotes technical innovation in the textile and clothing industry, intelligent wearable equipment is inoculated, a traditional energy storage device is stiff and not soft enough, and development requirements of the flexibility of the wearable equipment are difficult to meet. The flexible super capacitor is a novel electrochemical energy storage device between the traditional capacitor and the battery, has the advantages of high energy density, good thermal stability, short charge and discharge time, long cycle life and the like, and has potential application value in the aspect of wearable energy storage. The nanofiber membrane has the characteristics of ideal capacitance, large specific surface area, softness and the like, and has great advantages in a flexible supercapacitor. At present, one of the most common methods for preparing nanofiber membranes is electrostatic spinning, but the problems of high energy consumption, high risk coefficient and the like exist.
Patent CN113808854a discloses a flexible supercapacitor, which is obtained by binding and attaching a microcrystalline fiber composite current collecting gel film with an aluminum film surface to a positive and negative electrode gel film, and then compacting the attached gel film on a protective film through a dry film laminator. However, in the preparation process, the positive electrode and the negative electrode and the packaging film are assembled by an adhesive and a film pressing machine, so that the operation is complex and the adhesive pollutes the environment.
Patent CN106229159a discloses a flexible supercapacitor and a preparation method of the flexible supercapacitor, wherein a dielectric material is prepared by soaking a diaphragm in a gel electrolyte of an ionic liquid and then adsorbing the gel electrolyte. However, the preparation process is complex, and the diaphragm has poor circulation stability, which is unfavorable for the stable and durable operation of the flexible super capacitor.
Patent CN111180218A discloses a flexible electrode material, a preparation method thereof and a flexible supercapacitor, which are prepared by obtaining a copolyamide/nylon 6 composite nanofiber membrane through electrostatic spinning, then performing hot-pressing treatment to obtain a reinforced composite nanofiber membrane, and finally performing in-situ polymerization growth on the reinforced composite nanofiber to obtain the flexible electrode material. The composite nanofiber membrane with high specific surface area is used as a flexible substrate, and the flexible electrode material is prepared by adopting an in-situ polymerization method, so that the flexible electrode material has good mechanical strength and electrical conductivity, but the preparation process is complex, and the high-voltage electricity used for electrostatic spinning has a certain danger.
Patent CN107369561a discloses a flexible electrode, a preparation method thereof and a flexible supercapacitor, CN112103090a discloses a self-supporting flexible supercapacitor and CN110211815A discloses a preparation method of a flexible symmetrical supercapacitor. However, the preparation process of the flexible super capacitor needs to be assembled, is complicated and complex, has low manufacturing efficiency and is not beneficial to mass production.
In addition, compared with electrostatic spinning, the solution blowing spinning uses high-speed air flow to replace high-voltage electricity as driving force, so that the danger of the process is reduced, the process is controllable, the diameter of the nanofiber is smaller, and the wearable equipment prepared from the nanofiber is lighter and thinner. Therefore, the novel flexible supercapacitor based on the solution blowing spinning technology has a great market prospect.
Disclosure of Invention
Therefore, the invention aims to solve the technical problems that the preparation process of the flexible supercapacitor in the prior art is complex, an adhesive is needed, assembly is needed and the like.
In order to solve the technical problems, the invention provides a symmetrical flexible supercapacitor and a preparation method thereof. The symmetrical flexible supercapacitor is simple and controllable in preparation process, free of self-assembly by an adhesive, light, thin, soft, high in energy density, good in cycling stability and mechanical property, and suitable for being combined on wearable equipment as an energy accumulator.
The first object of the invention is to provide a preparation method of a symmetrical flexible super capacitor, which takes a solution blowing spinning device as a generating device, comprises a solution blowing spinning machine and a receiving device, and comprises the following steps,
s1, sequentially dissolving silicon dioxide nano particles and polyetherimide-polyurethane composite in dimethylformamide, and uniformly mixing to obtain a membrane layer spinning solution; the polyetherimide-polyurethane compound is prepared from polyetherimide and polyurethane according to a mass ratio of 1-3:1, mixing to obtain the product;
sequentially dissolving indole monomer, p-toluenesulfonic acid, polyethylene oxide and carbon nano tubes in chloroform, and uniformly mixing to obtain electrode layer spinning solution;
dissolving cellulose acetate in a mixed solvent, and uniformly mixing to obtain a packaging layer spinning solution;
s2, spraying the membrane layer spinning solution, the electrode layer spinning solution and the packaging layer spinning solution in the step S1 respectively through a solution blowing spinning technology, and sequentially forming a first packaging layer, a first electrode layer, a membrane layer, a second electrode layer and a second packaging layer on a receiving device to obtain the symmetrical flexible supercapacitor.
In one embodiment of the present invention, in S1, the mass ratio of the silica nanoparticles and the polyetherimide-polyurethane composite in the membrane layer dope is 5-11:100.
In one embodiment of the present invention, in S1, the total mass fraction of the silica nanoparticles and the polyetherimide-polyurethane composite in the membrane layer dope is 5% -10%.
In one embodiment of the present invention, in S1, the mass ratio of indole monomer, p-toluene sulfonic acid, polyethylene oxide and carbon nanotubes in the electrode layer spinning solution is 4:4:1:1.
In one embodiment of the invention, in S1, the mass fraction of indole monomer in the electrode layer spinning solution is 1.8% -2.05%.
In one embodiment of the invention, in S1, the concentration of the encapsulating layer dope is 0.1g/mL-0.3g/mL.
In one embodiment of the present invention, in S1, the mixed solvent is obtained by mixing acetone and N, N-dimethylacetamide according to a volume ratio of 3:2.
In one embodiment of the invention, the polyetherimide-polyurethane (PEI-PU) compound adopted in the membrane layer spinning solution has good flame retardance, heat stability and wear resistance, so that the membrane has good heat stability, high chemical stability and good dimensional stability; while silica nanoparticles (SiO) 2 NPs) to a certain extent increases the pores of the membrane layerGap rate, uniformity, and circularity. The separator layer shows a uniform pore size distribution, high ionic conductivity and good electrochemical stability thanks to the high porosity, interpenetrating network structure and synergy of the silica nanoparticles, PEI-PU.
In one embodiment of the invention, the pure polybenzazole Pind used in the electrode layer spinning solution is one of conductive polymers, has the characteristics of good thermal stability, high redox activity, slow degradation rate and the like, but has lower capacitance when used as an electrode active material in a supercapacitor, and the addition of CNTs can improve the specific surface area and conductivity of Pind to a certain extent, so that the flexible supercapacitor is endowed with excellent conductivity, mechanical property and electrochemical stability.
In one embodiment of the invention, the Cellulose Acetate (CA) used in the encapsulating layer spinning solution has better skin-friendly property, mechanical property and air permeability.
In one embodiment of the present invention, in S2, the process parameters of the solution blowing spinning technology are: the inner diameter of the nozzle is 2mm, the drafting wind pressure is 0.08-0.4 MPa, the extrusion speed is 1.2-30 mL/h, the receiving distance is 20-60 cm, and the rotating speed of the receiving device is 1000-2000 rpm.
In one embodiment of the present invention, in S2, the environmental parameters of the solution blown spinning technology are: the temperature was 23.+ -. 2 ℃ and the relative humidity was 45.+ -. 3 ℃.
A second object of the present invention is to provide a symmetrical flexible supercapacitor prepared by the method, wherein the thickness of the separator layer is 50 μm to 60 μm, and the average fiber diameter is 400nm to 500nm;
the thickness of the first electrode layer and the second electrode layer is independently 45-51 μm, and the average fiber diameter is 320-400 nm;
the thickness of the first encapsulation layer and the second encapsulation layer is independently 20 μm to 25 μm, and the average fiber diameter is 120nm to 165nm.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) According to the preparation method, a small amount of spinning solution residues exist in the previous layer of nanofiber membrane after the preparation, so that the nanofiber membrane can be directly adhered when the subsequent layer of nanofiber membrane is prepared, a dry film pressing machine is not required to press or any adhesive is used, and the operation is simple and convenient, and environment-friendly.
(2) The preparation method adopts a solution blowing spinning process, has simple and controllable preparation process, and benefits from the high porosity, interpenetrating network structure and synergistic effect of the silicon dioxide nano particles and PEI-PU, increases the porosity, uniformity and circularity of the diaphragm layer, is favorable for rapid transmission of ions, and ensures that the flexible super capacitor has excellent circulation stability, thermal stability and high energy density.
(3) Compared with electrostatic spinning, the preparation method adopts high-speed air flow to replace high-voltage electricity as driving force, reduces the risk of the process, has simple and controllable process, smaller diameter of the nano fiber, can be directly used as an electrode without hot-pressing treatment or using any adhesive, and further increases the specific surface area and conductivity of indole monomers by introducing the carbon nano tube, so that the flexible super capacitor based on the nano fiber electrode layer has excellent electrical property, quick charge and discharge and cycle stability.
(4) According to the preparation method, three nozzles are adopted for intermittent spinning, and the symmetrical flexible super capacitor with high energy density, good mechanical property and cycle stability is prepared on the receiving device at one time, so that the assembly is not needed, and the manufacturing process is greatly simplified.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which:
FIG. 1 is a schematic illustration of the preparation of a symmetrical flexible supercapacitor according to example 1 of the present invention;
fig. 2 is a schematic structural diagram of a symmetrical flexible supercapacitor according to embodiment 1 of the present invention;
reference numerals illustrate: 1-high pressure air source, 2-peristaltic pump, 3-receiving device, 4-sealed beaker, 51-upper side syringe, 52-left side syringe, 53-right side syringe, 6-stainless steel nozzle, 7-symmetrical flexible super capacitor, 8-packaging layer, 9-electrode layer, 10-diaphragm layer.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
In the present invention, unless otherwise indicated, the preparation of the symmetrical flexible supercapacitor is carried out by using the solution blowing spinning device as a generating device as shown in fig. 1, and comprises a solution blowing spinning machine and a receiving device. The solution blowing and spraying spinning machine is characterized in that spinning solution is respectively filled into sealed beakers 4, peristaltic pumps 2 squeeze hoses to pump the spinning solution to injectors (membrane layer spinning solution to an upper side injector 51, electrode layer spinning solution to a left side injector 52 and packaging layer spinning solution to a right side injector 53), stainless steel nozzles 6 are respectively arranged on the injectors, the stainless steel nozzles 6 are sprayed by high-speed hot air supplied by a high-pressure air source 1 while spinning, the spinning solution is sprayed onto a receiving device 3, and three stainless steel nozzles 6 are controlled by peristaltic pumps 2 to alternately spray and spin, are stacked layer by layer and are deposited to form symmetrical flexible super capacitors 7.
In the present invention, the preparation of the dope and the like are also included in the whole process for the preparation and post-treatment of the symmetrical flexible supercapacitor unless otherwise specified.
In the following examples and comparative examples, the experimental methods used are conventional methods, and materials, reagents and the like used, unless otherwise specified, are commercially available.
SiO 2 NPs are available from Aba Ding Huaxue Co., ltd., specification (particle diameter: 7nm-40nm, specific surface area: 120 m) 2 /g); PEI is purchased from Changzhou Deyi New Material technology Co., ltd; PU was purchased from basf limited; DMF, DMAC, available from german chemical company, guangzhou; indole monomer (purity 99%), ammonium persulfate, p-TSA were all purchased from Shanghai national medicine control stock chemical reagent Co., ltd; PEO was purchased from GuangzhouMarket Rich trade Co., ltd., specification: molecular weight 50 ten thousand; CNTs are purchased from Shanghai Kaifeng industries, inc.; chloroform was purchased from Shanghai Lingfeng chemical reagent Co., ltd., specification: content of>99.5%; CA. Acetone was purchased from Nanjing chemical Co.
Example 1
Referring to fig. 1, the symmetrical flexible supercapacitor and the preparation method thereof of the invention specifically comprise the following steps:
s1, preparation of spinning solution
S11, membrane layer spinning solution: siO is made of 2 NPs (silica nanoparticles) are dissolved in an organic solvent DMF (dimethylformamide), and uniformly dispersed by ultrasound, and then a certain amount of PEI-PU (polyetherimide-polyurethane) composite solution (SiO 2 The mass ratio of NPs to PEI-PU compound is 8:100) is added into SiO 2 Mechanically stirring for 12 hours to obtain a membrane layer spinning solution; wherein the mass ratio of PEI to PU in the PEI-PU compound is 1:1, and SiO in the spinning solution of the diaphragm layer 2 The total mass fraction of NPs and PEI-PU is 7%.
S12, electrode layer spinning solution: pund (indole monomer) was reacted with p-TSA (p-toluene sulfonic acid) at 1:1, mixing to prepare a Pind (polybenzazole mixed solution), then immediately adding PEO (polyethylene oxide), magnetically stirring for 12 hours, uniformly dispersing by ultrasonic treatment, finally adding CNTs (carbon nanotubes), magnetically stirring for 12 hours in chloroform, and uniformly dispersing by ultrasonic to obtain an electrode layer spinning solution; wherein the mass fraction of Pund in the electrode layer spinning solution is 1.95%, and the mass ratio of Pund, p-TSA, PEO and CNTs is 4:4:1:1.
S13, packaging layer spinning solution: 2.5g of CA (cellulose acetate) was dissolved in a mixture of acetone and DMAC (N, N-dimethylacetamide) (3:2 by volume of acetone to DMAC), and the mixture was stirred at room temperature for 24h until complete dissolution, giving an encapsulating layer dope with a concentration of 0.2 g/mL.
S2, preparation of symmetrical flexible super capacitor
S21, injecting 10mL of membrane layer spinning solution into an upper sealing beaker, 10mL of electrode layer spinning solution into a left sealing beaker and 10mL of packaging layer spinning solution into a right sealing beaker, pumping the spinning solution into injectors by a peristaltic pump through extruding a hose, wherein the injectors are respectively positioned on the upper side, the left side and the right side of a receiving device, and stainless steel nozzles with the inner diameter of 2mm are arranged on the injectors.
S22, starting solution blowing spinning, namely spraying nanofibers to a receiving device with the rotating speed of 1500rpm while spraying the filaments by a stainless steel nozzle under the conditions that the drafting wind pressure is 0.1MPa, the extrusion speed is 20mL/h, the receiving distance is 40cm, the environment temperature is 23 ℃ and the environment relative humidity is 45 ℃, and depositing to form a nanofiber membrane layer.
S23, running a peristaltic pump connected with the packaging layer spinning solution, spinning by a nozzle, forming a packaging layer (a first packaging layer) on the receiving device after 2 hours, stopping conveying by the peristaltic pump, and suspending spinning; then a peristaltic pump connected with the electrode layer spinning solution is operated, a nozzle is used for spinning, part of the spinning solution can remain on the packaging layer to enable the packaging layer to have certain viscosity, the electrode layer can be directly overlapped on the packaging layer (the first electrode layer), and the spinning is stopped after 3 hours; then a peristaltic pump connected with the membrane spinning solution is operated, a nozzle is used for spinning, a membrane layer is formed on a receiving device after 2.5 hours, the peristaltic pump stops conveying, and spinning is stopped; sequentially spraying and superposing a first packaging layer, a first electrode layer, a diaphragm layer, a second electrode layer and a second packaging layer in sequence, manufacturing 5 nanofiber membrane layers at one time, and drying in a dryer to obtain the symmetrical flexible supercapacitor shown in figure 2, wherein the symmetrical flexible supercapacitor comprises a diaphragm layer 10, electrode layers 9 arranged on two sides of the diaphragm layer 10 and packaging layers 8 arranged on the outer sides of the electrode layers 9; wherein the thickness of the encapsulation layers is about 20 mu m, and the average fiber diameter is about 145nm; the thickness of the electrode layers is about 45 mu m, and the average fiber diameter is about 360nm; the thickness of the separator layer was about 50 μm and the average fiber diameter was about 450nm.
Example 2
The invention relates to a symmetrical flexible supercapacitor and a preparation method thereof, which specifically comprise the following steps:
substantially the same as in example 1, the difference is that:
in S1, siO in the spinning solution of the diaphragm layer 2 Total mass fraction of NPs and PEI-PUThe number is 5%.
In S1, the mass ratio of PEI to PU in the PEI-PU compound is 1.5:1.
In S1, siO in the spinning solution of the diaphragm layer 2 The mass ratio of NPs to PEI-PU compound is 5:100.
In S1, the mass fraction of Pund in the electrode layer spinning solution is 1.8%.
In S1, the concentration of the spinning solution of the packaging layer is 0.15g/mL.
In S2, the technological parameters of the solution blowing spinning are as follows: the extrusion speed was 30mL/h at a draft wind pressure of 0.4MPa, a receiving distance of 35cm, an ambient temperature of 25℃and an ambient relative humidity of 47℃and a rotational speed of the receiving device of 1000rpm.
The thickness of the encapsulation layers of the obtained symmetrical flexible super capacitor is about 23 mu m, and the average fiber diameter is about 154nm; the thickness of the electrode layers is about 51 mu m, and the average fiber diameter is about 400nm; the thickness of the separator layer was about 56 μm and the average fiber diameter was about 410nm.
Example 3
The invention relates to a symmetrical flexible supercapacitor and a preparation method thereof, which specifically comprise the following steps:
substantially the same as in example 1, the difference is that:
in S1, siO in the spinning solution of the diaphragm layer 2 The total mass fraction of NPs and PEI-PU was 10%.
In S1, the mass ratio of PEI to PU in the PEI-PU compound is 2:1.
In S1, siO in the spinning solution of the diaphragm layer 2 The mass ratio of NPs to PEI-PU compound is 11:100.
In S1, the mass fraction of Pund in the electrode layer spinning solution is 2.0%.
In S1, the concentration of the spinning solution of the packaging layer is 0.26g/mL.
In S2, the technological parameters of the solution blowing spinning are as follows: the extrusion speed was 24mL/h at a draft wind pressure of 0.08MPa, a receiving distance of 50cm, an ambient temperature of 24℃and an ambient relative humidity of 46℃and a rotational speed of the receiving device of 1200rpm.
The thickness of the encapsulation layers of the obtained symmetrical flexible super capacitor is about 25 mu m, and the average fiber diameter is about 162nm; the thickness of the electrode layers is about 49 mu m, and the average fiber diameter is about 385nm; the thickness of the separator layer was about 60 μm and the average fiber diameter was about 500nm.
Comparative example 1
Substantially the same as in example 1, the difference is that:
in S2, the solution blowing spinning is changed into electrostatic spinning, and the technological parameters of the electrostatic spinning are as follows: the extrusion speed is 0.48mL/h, the receiving distance is 20cm, the electrostatic voltage is 18KV, the environment temperature is 25 ℃, the environment relative humidity is 43 ℃, the spinning solution is subjected to jet spinning in a strong electric field, and the spinning solution is pulled to a receiving device under the action of the electric field force, wherein the rotating speed of the receiving device is 50rpm.
Comparative example 2
Substantially the same as in example 1, the difference is that: CNTs are not added into the electrode layer spinning solution.
Comparative example 3
Substantially the same as in example 1, the difference is that: and no silica nano particles are added into the membrane layer spinning solution.
Test example 1
The capacitors prepared in examples 1-3 and comparative examples 1-3 above were subjected to average thickness measurements, energy density, power density, mechanical testing and cycle performance testing according to the following criteria:
energy density, power density test index: DL/T2081-2020, test procedure for super capacitor for Power storage
Mechanical performance test index: DL/T2080-2020 super capacitor for electric energy storage;
cycle performance test index: DL/T2081-2020, test procedure for super capacitor for Power storage; table 1 shows the relevant parameters of the final measured capacitor:
TABLE 1
| Sample preparation | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Average thickness/. Mu.m | 187 | 210 | 214 | 239 | 182 | 187 |
| Energy Density/(Wh/kg) | 17.14 | 17 | 16.88 | 15 | 8.84 | 10.65 |
| Power density/(W/kg) | 431 | 423 | 416 | 411 | 396 | 401 |
| Tensile Strength (MPa) | 10.86 | 10.98 | 11.36 | 13.76 | 12.40 | 19.15 |
| Capacitor retention after cycling (%) | 93％ | 86％ | 88％ | 80％ | 81％ | 65％ |
As can be seen from Table 1, the average thickness, energy density, power density, mechanical properties and cyclic properties of the symmetrical flexible supercapacitors prepared in examples 1-3 are all superior to those of the symmetrical flexible supercapacitors prepared in comparative examples 1-3, and the symmetrical flexible supercapacitors have better performance.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. A preparation method of a symmetrical flexible supercapacitor is characterized by taking a solution blowing spinning device as a generating device and comprising a solution blowing spinning machine and a receiving device, wherein the preparation method comprises the following steps,
s1, sequentially dissolving silicon dioxide nano particles and polyetherimide-polyurethane composite in dimethylformamide, and uniformly mixing to obtain a membrane layer spinning solution; the polyetherimide-polyurethane compound is prepared from polyetherimide and polyurethane according to a mass ratio of 1-3:1, mixing to obtain the product;
sequentially dissolving indole monomer, p-toluenesulfonic acid, polyethylene oxide and carbon nano tubes in chloroform, and uniformly mixing to obtain electrode layer spinning solution;
dissolving cellulose acetate in a mixed solvent, and uniformly mixing to obtain a packaging layer spinning solution;
s2, spraying the membrane layer spinning solution, the electrode layer spinning solution and the packaging layer spinning solution in the step S1 respectively through a solution blowing spinning technology, and sequentially forming a first packaging layer, a first electrode layer, a membrane layer, a second electrode layer and a second packaging layer on a receiving device to obtain the symmetrical flexible supercapacitor.
2. The method for manufacturing a symmetrical flexible supercapacitor according to claim 1, wherein in S1, the mass ratio of the silica nanoparticles to the polyetherimide-polyurethane composite in the membrane layer dope is 5-11:100.
3. The method for manufacturing a symmetrical flexible supercapacitor according to claim 1, wherein in S1, the total mass fraction of the silica nanoparticles and the polyetherimide-polyurethane composite in the membrane layer dope is 5% -10%.
4. The method for manufacturing the symmetrical flexible supercapacitor according to claim 1, wherein in S1, the mass ratio of indole monomer, p-toluene sulfonic acid, polyethylene oxide and carbon nanotubes in the electrode layer spinning solution is 4:4:1:1.
5. The method for manufacturing the symmetrical flexible supercapacitor according to claim 1, wherein in S1, the mass fraction of indole monomer in the electrode layer spinning solution is 1.8% -2.05%.
6. The method for manufacturing a symmetrical flexible supercapacitor according to claim 1, wherein in S1, the concentration of the dope of the encapsulation layer is 0.1g/mL to 0.3g/mL.
7. The method for manufacturing the symmetrical flexible supercapacitor according to claim 1, wherein in S1, the mixed solvent is obtained by mixing acetone and N, N-dimethylacetamide according to a volume ratio of 3:2.
8. The method for manufacturing a symmetrical flexible supercapacitor according to claim 1, wherein in S2, the technological parameters of the solution blowing spinning technique are: the inner diameter of the nozzle is 2mm, the drafting wind pressure is 0.08-0.4 MPa, the extrusion speed is 1.2-30 mL/h, the receiving distance is 20-60 cm, and the rotating speed of the receiving device is 1000-2000 rpm.
9. The method for manufacturing a symmetrical flexible supercapacitor according to claim 1, wherein in S2, the environmental parameters of the solution blown spinning technique are: the temperature was 23.+ -. 2 ℃ and the relative humidity was 45.+ -. 3 ℃.
10. A symmetrical flexible supercapacitor made by the method of any one of claims 1 to 9, wherein the separator layer has a thickness of 50 μm to 60 μm and an average fiber diameter of 400nm to 500nm;
the thickness of the first electrode layer and the second electrode layer is independently 45-51 μm, and the average fiber diameter is 320-400 nm;
the thickness of the first encapsulation layer and the second encapsulation layer is independently 20 μm to 25 μm, and the average fiber diameter is 120nm to 165nm.
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