CN113838680A - Wearable full-flexible solid electrochromic supercapacitor and manufacturing method thereof - Google Patents

Wearable full-flexible solid electrochromic supercapacitor and manufacturing method thereof Download PDF

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CN113838680A
CN113838680A CN202111093979.8A CN202111093979A CN113838680A CN 113838680 A CN113838680 A CN 113838680A CN 202111093979 A CN202111093979 A CN 202111093979A CN 113838680 A CN113838680 A CN 113838680A
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silver nanowire
electrode
conjugated polymer
solution
flexible
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魏葳
张宇曦
张苗
常晶晶
林珍华
苏杰
胡赵胜
张凡
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Xidian University
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    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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    • G02F1/15Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
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    • HELECTRICITY
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Abstract

The invention discloses a wearable full-flexible solid electrochromic super capacitor and a preparation method thereof, and mainly solves the problems that the super capacitor in the prior art is poor in flexibility and energy storage effect and is difficult to wear. The device comprises a lower current collector (1), a first active layer (2), a gel polymer electrolyte layer (3), a second active layer (4) and an upper current collector (5) from bottom to top, wherein the upper current collector and the lower current collector are both composed of a flexible substrate and a silver nanowire electrode, and the silver nanowire electrode is coated on the flexible substrate; the active layer adopts a conjugated polymer material to realize the electrochromic function, and a part of the conjugated polymer is embedded into the reticular pores of the silver nanowire electrode to form the silver nanowire-conjugated polymer composite 3D electrode. The invention improves the mechanical flexibility and electrochemical performance of the super capacitor, realizes full flexibility, wearability and electric quantity visualization, and can be used for providing energy for human body wearable electronic equipment.

Description

Wearable full-flexible solid electrochromic supercapacitor and manufacturing method thereof
Technical Field
The invention relates to the technical field of electronic components, in particular to a wearable full-flexible solid-state electrochromic supercapacitor which can be used for providing energy for human body wearable electronic equipment.
Background
The super capacitor SC has a long cycle life of 100000 times or more and 10000W kg or more-1The high power density of the battery, and the rapid charging and discharging within a few seconds, become one of the most promising energy storage devices. Under the action of an external electric field, the ECDs of the electrochromic device can reversibly change the optical performance and color of the device along with the injection and extraction of electrons or ions. Because of the similarity between the super capacitor and the electrochromic device in the process of electrode material, charge storage and transmission, a novel super capacitor, namely an electrochromic super capacitor ECSC, is produced because the super capacitor ECSC simultaneously has transparent conductive material and can be used for charging and dischargingThe super capacitor has double-layer capacity of optical modulation and energy storage, and can visually observe the energy storage state through the state of color, thereby bringing new interaction experience to the energy storage device.
Electrochromic supercapacitors can provide energy to wearable electronics for the human body, and the delicate muscular activity of human body movements makes wearable electronics not only consider the performance of the device operating in a bent deformation state, but may also need to produce no significant performance degradation at tensile strains in excess of 20%. The fully flexible electrochromic super capacitor with good stretchability must ensure good mechanical flexibility of all structures including the substrate, current collector, active layer, electrolyte, etc.
At present, there are a variety of novel conductive materials that can meet the requirements of current collectors on flexibility, such as: the flexible conductive material comprises silver nanowires, metal grids, carbon nanotubes, graphene films, conductive polymers and the like, wherein the silver nanowires and the transparent conductive films thereof are novel flexible transparent conductive materials which are hopeful to replace ITO in the fields of medium-size and large-size flexible devices due to the excellent photoelectric characteristics, good bending and stretching resistance mechanical properties and low-cost mass production preparation process routes. However, the silver nanowire conductive network structure is easy to displace in the flexible deformation process, so that the conductive capability is reduced; the super capacitor is easy to slip and crack between layers under bending deformation, and the poor mechanical flexibility limits the wide application of the super capacitor in the flexible field; meanwhile, the traditional super capacitor has poor electrochemical energy storage performance due to large interface resistance and long electrolyte ion diffusion path, and the improvement of charge and discharge capacity is influenced.
Disclosure of Invention
The invention aims to provide a wearable full-flexible solid electrochromic supercapacitor and a manufacturing method thereof aiming at the defects in the prior art, so that the mechanical flexibility of the supercapacitor is enhanced, the electrochemical property of the supercapacitor is improved, and the wearable requirement is met.
The technical scheme of the invention is as follows: the silver nanowire and the flexible transparent electrode thereof are improved, and a three-dimensional composite electrode structure is designed, and the three-dimensional composite electrode structure is specifically realized as follows:
the wearable full-flexible solid electrochromic super capacitor comprises a lower current collector, a first active layer, a gel polymer electrolyte layer, a second active layer and an upper current collector from bottom to top, and is characterized in that:
the upper current collector and the lower current collector both consist of a flexible substrate and a silver nanowire electrode, and the silver nanowire electrode is coated on the flexible substrate;
the active layer is made of a conjugated polymer material to realize the electrochromic function, and a part of the conjugated polymer is embedded into the mesh-shaped porous of the silver nanowire electrode to form the silver nanowire-conjugated polymer composite 3D electrode.
Further, the flexible substrate is made of one of polydimethylsiloxane PDMS, polyethylene terephthalate, polyurethane acrylate, hydrogenated styrene-butadiene-styrene block copolymer and polyvinyl alcohol.
Further, the silver nanowire electrode is obtained by coating silver nanowire ink, the diameter of the silver nanowire is 10-100nm, the length of the silver nanowire is 10-100 mu m, and the silver nanowire electrode accounts for 5% -60% of the ink in mass percent.
Further, the solvent adopted by the conjugated polymer material is a chlorobenzene solution, and the material is any one of the following three materials:
poly [ (5,5,11, 11-tetrakis (4-hexylphenyl) indian thieno [1,2-b ] dithiophene [3,2-b ] thiophen-2, 8-yl) - (4, 7-bisthienylbenzo [1,2,5] thiadiazole-5, 5') ] PIDTT-TBT,
poly [ (5,5,11, 11-tetrakis (4-hexylphenyl) imidazothieno [1,2-b ] dithiophene [3,2-b ] thiophen-2, 8-yl) - (4, 7-bis (2, 3-dihydrothiophene [3,2-b ] [1,4] dioxin-5) -benzo [1,2,5] thiadiazole-7, 7') ] PIDTT-EBE,
poly [ (5,5,11, 11-tetrakis (4-hexylphenyl) indian thieno [1,2-b ] dithiophene [3,2-b ] thiophen-2, 8-yl) - (4, 7-bis (thiophene-2) -2- (2-hexyldecyl) -2H-benzo [1,2,3] triazole-5, 5' ] PIDTT-TBzT.
Further, the gel polymer electrolyte layer is a polymerThe electrolyte layer is formed by combining a carrier and a neutral ionic liquid, wherein the polymer carrier adopts one of polyvinyl alcohol (PVA), Polyacrylamide (PAM), polyethylene oxide (PEO), polyacrylic acid (PAA) and polymethyl methacrylate (PMMA), and the ionic liquid adopts neutral Li2SO4And KCl is electrolyte salt or ionic liquid of solute.
The method for preparing the wearable full-flexible solid electrochromic supercapacitor provides the following two technical schemes:
the first technical scheme is as follows:
a preparation method of a wearable full-flexible solid electrochromic supercapacitor is characterized by comprising the following steps:
1) preparing a silver nanowire-conjugated polymer composite transparent electrode:
1a) coating the silver nanowire solution on a glass substrate to form a silver nanowire electrode, and heating and drying the silver nanowire electrode;
1b) mixing the PDMS precursor or other precursors with a curing agent in a mass ratio of 5:1-20:1, fully stirring, pouring the mixture on a glass plate with a silver nanowire electrode, standing the mixture in an air environment for 0.1-0.2h to naturally level PDMS, and then putting the mixture into an oven for heating and curing;
1c) stripping the cured PDMS film from the glass plate with the silver nanowire electrode to realize electrode transfer;
1d) soaking the stripped electrode in 5-25% NaCl solution to realize the low-temperature welding treatment at the silver nanowire lap joint, and washing the modified flexible silver nanowire transparent electrode in deionized water;
1e) preparing a conjugated polymer solution, coating the conjugated polymer solution on the surface of a silver nanowire electrode to form a conjugated polymer active layer with an electrochromic function, and heating and drying at the temperature of 50-70 ℃ for 10-20min to obtain a silver nanowire-conjugated polymer composite transparent electrode;
1f) repeating 1a) -1e), and manufacturing another same composite transparent electrode;
2) combining a polymer carrier with neutral ionic liquid to prepare a flexible gel-state electrolyte layer;
3) assembling the super capacitor:
and (2) pressing the two composite electrodes manufactured in the step (1) on two sides of the electrolyte layer manufactured in the step (2), wherein the pressure applied during pressing is 20-60Pa, and the surface of the composite electrode coated with the conjugated polymer solution is in contact with the electrolyte layer to form a symmetrical sandwich structure, so that the preparation of the wearable full-flexible solid electrochromic supercapacitor is completed.
The second technical scheme is as follows:
a preparation method of a wearable full-flexible solid electrochromic supercapacitor is characterized by comprising the following steps:
A) preparing a silver nanowire-conjugated polymer composite transparent electrode:
A1) coating the silver nanowire solution on a film-shaped flexible substrate to form a silver nanowire electrode, and heating and drying the silver nanowire electrode;
A2) soaking the electrode in 5-25% NaCl solution to realize the low temperature welding treatment at the silver nanowire lap joint, and washing the modified flexible silver nanowire transparent electrode in deionized water;
A3) preparing a conjugated polymer solution, coating the conjugated polymer solution on the surface of a silver nanowire electrode to form a conjugated polymer active layer with an electrochromic function, and heating and drying at the temperature of 50-70 ℃ for 10-20min to obtain a silver nanowire-conjugated polymer composite transparent electrode;
A4) repeat a1) -A3) to make another identical composite transparent electrode;
B) combining a polymer carrier with neutral ionic liquid to prepare a flexible gel-state electrolyte layer;
C) assembling the super capacitor:
and pressing the two composite electrodes manufactured in the step A) on two sides of the electrolyte layer manufactured in the step B), wherein the applied pressure is 20-60Pa, and the surface of the composite electrode coated with the conjugated polymer solution is in contact with the electrolyte layer to form a symmetrical sandwich structure, so that the preparation of the wearable full-flexible solid electrochromic super capacitor is completed.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the gel-state electrolyte layer and the conjugated polymer are used as the active layer, so that each layer of the super capacitor has intrinsic stretchability, and the requirement of stretching deformation can be better met; meanwhile, the conjugated polymer is used as an active layer material of the supercapacitor, so that the purpose of electric quantity visualization can be achieved, the conjugated electronic structure of the material can be changed by electrochemically doping the material, band gap change is generated, and the energy storage characteristic of the supercapacitor is improved.
2. According to the invention, the conjugated polymer active material is partially embedded into the porous electrode of the silver nanowire to form the silver nanowire-conjugated polymer composite 3D electrode, the composite electrode has richer electron transmission channels with lower resistivity, the speed of repeatedly capturing and releasing ions in the charging and discharging processes is increased, and the electrochemical performance of the device is further improved; in addition, the embedded structure of the composite electrode and the welding treatment of the silver nanowires reduce the possibility of the falling-off of the active layer and the substrate of the supercapacitor in the deformation process, and improve the stretchability and the mechanical flexibility of the supercapacitor.
3. The whole structure is all solid, and strong acid and strong alkali substances do not exist, so that the leakage of harmful substances cannot be generated in the deformation process, the circulation stability is good, and the flexible wearable electronic product can be bent, twisted or even stretched at will, so that the flexible wearable electronic product is particularly suitable for application in the future.
Drawings
FIG. 1 is a block diagram of an ultracapacitor of the present invention;
FIG. 2 is a flow chart of the present invention for fabricating the capacitor of FIG. 1;
FIG. 3 is an electron microscope image of a silver nanowire transparent electrode that is chemically welded to produce a lap joint junction in a capacitor made according to the present invention.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
Referring to fig. 1, the wearable fully flexible solid electrochromic supercapacitor of the present example comprises a lower current collector 1, a first active layer 2, a gel polymer electrolyte layer 3, a second active layer 4 and an upper current collector 5, forming a symmetrical sandwich structure, wherein:
the lower current collector 1 and the upper current collector 5 are silver nanowire-conjugated polymer composite 3D electrodes formed by coating a conjugated polymer solution on silver nanowire electrodes and embedding the silver nanowire electrodes and the conjugated polymer into each other, and are respectively positioned at the lower part of the first active layer 2 and the upper part of the second active layer 4 and positioned at the uppermost layer and the lowermost layer of the capacitor. The diameter of the silver nanowire electrode is 10-100nm, the length of the silver nanowire electrode is 10-100 mu m, the silver nanowire electrode accounts for 5-60% of the ink by mass, and a substrate used by the electrode adopts one of polydimethylsiloxane PDMS and polyethylene glycol terephthalate;
the first active layer 2 and the second active layer 4 are respectively arranged above the lower current collector 1 and below the upper current collector 5, and are formed by coating conjugated polymer materials to realize the electrochromic function, and a part of the conjugated polymer is embedded into the reticular pores of the silver nanowire electrode, and the conjugated polymer is formed by mixing chlorobenzene solution and one of the following three materials:
poly [ (5,5,11, 11-tetrakis (4-hexylphenyl) indian thieno [1,2-b ] dithiophene [3,2-b ] thiophen-2, 8-yl) - (4, 7-bisthienylbenzo [1,2,5] thiadiazole-5, 5') ] PIDTT-TBT,
poly [ (5,5,11, 11-tetrakis (4-hexylphenyl) imidazothieno [1,2-b ] dithiophene [3,2-b ] thiophen-2, 8-yl) - (4, 7-bis (2, 3-dihydrothiophene [3,2-b ] [1,4] dioxin-5) -benzo [1,2,5] thiadiazole-7, 7') ] PIDTT-EBE,
poly [ (5,5,11, 11-tetrakis (4-hexylphenyl) indian thieno [1,2-b ] dithiophene [3,2-b ] thiophen-2, 8-yl) - (4, 7-bis (thiophene-2) -2- (2-hexyldecyl) -2H-benzo [1,2,3] triazole-5, 5' ] PIDTT-TBzT.
The gel-state electrolyte layer is positioned between the first active layer 2 and the second active layer 4 and is formed by combining a polymer carrier and neutral ionic liquid, wherein the polymer carrier adopts one of polyvinyl alcohol (PVA), Polyacrylamide (PAM), polyethylene oxide (PEO), polyacrylic acid (PAA) and polymethyl methacrylate (PMMA), and the ionic liquidThe body adopts neutral Li2SO4And KCl is electrolyte salt or ionic liquid of solute.
Referring to fig. 2, three examples of two schemes for making a wearable fully flexible solid state electrochromic supercapacitor are given as follows:
example 1: preparing a wearable full-flexible solid electrochromic super capacitor with a PDMS substrate and a silver nanowire-PIDTT-TBzT composite transparent electrode.
The method comprises the following steps: preparing a silver nanowire-PIDTT-TBzT composite transparent electrode with a PDMS substrate:
1.1) spin-coating 30 wt% of silver nanowire ink on a glass substrate to form a silver nanowire electrode, and heating and drying at 50 ℃ for 20 min;
1.2) mixing a precursor of polydimethylsiloxane PDMS and a curing agent in a mass ratio of 10:1, fully stirring, pouring the mixture on a glass plate of the 1.1), standing the mixture in an air environment for 0.1h to naturally level the PDMS, and then putting the mixture into an oven to be heated and cured for 5.5h at 70 ℃;
1.3) stripping the cured PDMS film from the glass plate with the silver nanowire electrode to realize electrode transfer;
1.4) soaking the stripped electrode in 10% NaCl solution for 80s to realize modification treatment of low-temperature welding at the silver nanowire lap joint, and washing the modified flexible silver nanowire transparent electrode in deionized water for 3 times, 7s each time; an electron microscope image of the lap joint generated by the silver nanowire electrode after chemical welding is shown in fig. 3;
1.5) dissolving the PIDTT-TBzT in chlorobenzene solution to form a mass fraction of 15mg mL-1The conjugated polymer solution is coated on the surface of the silver nanowire electrode in a spinning mode to form a conjugated polymer active layer with an electrochromic function, and then the conjugated polymer active layer is heated and dried for 10min at 70 ℃ to obtain a silver nanowire-PIDTT-TBzT composite transparent electrode;
1.6) repeating 1.1) -1.5) to prepare another same silver nanowire-PIDTT-TBzT composite transparent electrode.
Step two: manufacturing a flexible gel state electrolyte layer:
2.1) preparing 10 wt% polyvinyl alcohol PVA aqueous solution, and putting the aqueous solution in a drying oven at 90 ℃ for 24 hours to uniformly disperse the aqueous solution;
2.2) taking out 10g of PVA aqueous solution, adding 3.0g of 1-butyl-3-methylimidazolium chloride BMIMCl ionic liquid, and stirring at 50 ℃ to form a PVA-BMIMCl system;
2.3) 0.5g of Li2SO4Dissolving in 15g of deionized water to prepare Li2SO4Adding the solution into a PVA-BMIMCl system of 2.2), and stirring for 30min at 50 ℃;
2.4) transferring the obtained mixed solution into a culture dish, freezing the mixed solution in a cold trap of a freeze dryer for 60min, and then freeze-drying the frozen mixed solution for 24h to prepare the PVA-BMIMCl-Li2SO4A flexible gel state electrolyte layer.
Step three: assembling the super capacitor:
and pressing the two composite electrodes manufactured in the first step on two sides of the electrolyte layer manufactured in the second step, wherein the applied pressure is 40Pa, and the surface of the composite electrode coated with the conjugated polymer solution is in contact with the electrolyte layer to form a symmetrical sandwich structure, so that the wearable full-flexible solid electrochromic supercapacitor is prepared.
Example 2: and preparing the wearable full-flexible solid electrochromic super capacitor with the polyurethane acrylate substrate, namely the silver nanowire-PIDTT-EBE composite transparent electrode.
Step A: and preparing the silver nanowire-PIDTT-EBE composite transparent electrode.
A1) Coating 5 wt% of silver nanowire ink on a polyurethane acrylate substrate in a spinning mode to form a silver nanowire electrode, and heating and drying at the temperature of 60 ℃ for 14 min;
A2) soaking the electrode in a NaCl solution with the concentration of 20% for 60s to realize the modification treatment of the low-temperature welding at the lap joint of the silver nanowires, which is shown in figure 3; washing the modified flexible silver nanowire transparent electrode in deionized water for 2 times, wherein the time of each time is 15 s;
A3) dissolving PIDTT-EBE in chlorobenzene solution to form a mass fraction of 17mg mL-1And spin coating the conjugated polymer solution on the surface of the silver nanowire electrodeForming a conjugated polymer active layer with electrochromic function, and then heating and drying at the temperature of 60 ℃ for 20min to obtain a silver nanowire-PIDTT-EBE composite transparent electrode;
A4) repeat A1) -A3) to make another identical piece of silver nanowire-PIDTT-EBE composite transparent electrode.
And B: and manufacturing the flexible gel state electrolyte layer.
B1) Preparing 10 wt% of polyvinyl alcohol PVA aqueous solution, and placing the aqueous solution in a 90 ℃ oven for 24 hours to uniformly disperse the aqueous solution;
B2) taking out 10g of PVA aqueous solution, adding 3.0g of 1-butyl-3-methylimidazolium chloride BMIMCl ionic liquid, and stirring at 50 ℃ to form PVA-BMIMCl liquid;
B3) 0.5g of Li2SO4Dissolving in 15g of deionized water to prepare Li2SO4Adding the solution into PVA-BMIMCl liquid B2), and stirring at 50 deg.C for 30 min;
B4) transferring the mixed solution obtained in B3) into a culture dish, putting the culture dish into a cold trap of a freeze dryer, freezing for 60min, and freeze-drying for 24h to prepare the PVA-BMIMCl-Li2SO4A flexible gel state electrolyte layer.
And C: and assembling the super capacitor.
And B, pressing the two composite electrodes manufactured in the step A on two sides of the electrolyte layer manufactured in the step B, wherein the pressure applied during pressing is 25Pa, and the surface of the composite electrode coated with the conjugated polymer solution is in contact with the electrolyte layer to form a symmetrical sandwich structure, so that the preparation of the wearable full-flexible solid electrochromic super capacitor is completed.
Example 3: and preparing the wearable full-flexible solid electrochromic super capacitor with the silver nanowire-PIDTT-TBT composite transparent electrode with the polyethylene glycol terephthalate as the substrate.
Step 1: and preparing the silver nanowire-PIDTT-TBT composite transparent electrode with the polyethylene glycol terephthalate substrate.
Firstly, 50 wt% of silver nanowire ink is coated on a polyethylene glycol terephthalate substrate in a spinning mode to form a silver nanowire electrode, and the silver nanowire electrode is heated and dried for 10min at the temperature of 70 ℃;
secondly, soaking the electrode for 90s by using a 5% NaCl solution, washing the modified flexible silver nanowire transparent electrode in deionized water for 5 times, wherein 5s is needed each time, so that the modification treatment of low-temperature welding at the silver nanowire lap joint is realized, and an electron microscope image of the lap joint generated by the silver nanowire electrode after chemical welding is shown in figure 3;
thirdly, dissolving the PIDTT-TBT in chlorobenzene solution to form 12mg mL of mass fraction-1The conjugated polymer solution is coated on the surface of the silver nanowire electrode in a spinning mode to form a conjugated polymer active layer with an electrochromic function, and then the conjugated polymer active layer is heated and dried for 10min at 65 ℃ to obtain a silver nanowire-PIDTT-TBT composite transparent electrode;
and fourthly, repeating the first step to the third step to manufacture another same silver nanowire-PIDTT-TBT composite transparent electrode.
Step 2: and manufacturing the flexible gel state electrolyte layer.
Firstly, preparing 10 wt% polyvinyl alcohol PVA aqueous solution, and placing the aqueous solution in a 90 ℃ oven for 24 hours to uniformly disperse the aqueous solution;
then, 10g of PVA aqueous solution is taken out, 3.0g of 1-butyl-3-methylimidazolium chloride BMIMCl ionic liquid is added, and the mixture is stirred at 50 ℃ to form PVA-BMIMCl solution;
next, 0.5g of Li was added2SO4Dissolving in 15g of deionized water to prepare Li2SO4Adding the solution into PVA-BMIMCl solution, and stirring at 50 ℃ for 30min to form a mixed solution;
then, the obtained mixed solution is transferred into a culture dish, and then is put into a cold trap of a freeze dryer to be frozen for 60min, and then is freeze-dried for 24h, so that the PVA-BMIMCl-Li is prepared2SO4A flexible gel state electrolyte layer.
And step 3: and assembling the super capacitor.
And (3) pressing the two composite electrodes manufactured in the step (1) on two sides of the electrolyte layer manufactured in the step (2) by using the pressure of 55Pa, and enabling the surface of the composite electrode coated with the conjugated polymer solution to be in contact with the electrolyte layer, so that the wearable full-flexible solid electrochromic super capacitor with the symmetrical sandwich structure is prepared.
The foregoing is illustrative of three specific embodiments of the present invention and is not to be construed as limiting thereof, as it will be apparent to those skilled in the art that various changes in form and detail may be made therein without departing from the principles and arrangements of the invention, for example: the flexible substrate can adopt one of hydrogenated styrene-butadiene-styrene block copolymer and polyvinyl alcohol besides polydimethylsiloxane PDMS, polyethylene terephthalate and polyurethane acrylate used in the embodiment; gel Polymer electrolyte layer except for PVA polymer carrier and Li used in examples2SO4In addition to the ionic liquid, the polymer carrier can also adopt one of polyacrylamide PAM, polyethylene oxide PEO, polyacrylic acid PAA and polymethyl methacrylate PMMA, and the ionic liquid can also adopt neutral Li2SO4And KCl is electrolyte salt or ionic liquid of solute. Such modifications and variations that are based on the inventive idea are nevertheless within the scope of the appended claims.

Claims (10)

1. The utility model provides a wearable full flexible solid state electrochromic ultracapacitor system, includes from bottom to top that collector fluid (1), first active layer (2), gel polymer electrolyte layer (3), second active layer (4) and last collector fluid (5), its characterized in that:
the upper current collector (1) and the lower current collector (5) are both composed of a flexible substrate and a silver nanowire electrode, and the silver nanowire electrode is coated on the flexible substrate;
the active layer is made of a conjugated polymer material to realize the electrochromic function, and a part of the conjugated polymer is embedded into the mesh-shaped porous of the silver nanowire electrode to form the silver nanowire-conjugated polymer composite 3D electrode.
2. The capacitor of claim 1, wherein the flexible substrate is one of Polydimethylsiloxane (PDMS), polyethylene terephthalate, polyurethane acrylate, hydrogenated styrene-butadiene-styrene block copolymer, and polyvinyl alcohol.
3. The capacitor of claim 1, wherein the silver nanowire electrode is coated with a silver nanowire ink, the silver nanowire has a diameter of 10-100nm and a length of 10-100 μm, and the silver nanowire accounts for 5-60% of the ink by mass.
4. The capacitor as claimed in claim 1, wherein the solvent used for the conjugated polymer material is chlorobenzene solution, and the material is any one of the following three materials:
poly [ (5,5,11, 11-tetrakis (4-hexylphenyl) indian thieno [1,2-b ] dithiophene [3,2-b ] thiophen-2, 8-yl) - (4, 7-bisthienylbenzo [1,2,5] thiadiazole-5, 5') ] PIDTT-TBT,
poly [ (5,5,11, 11-tetrakis (4-hexylphenyl) imidazothieno [1,2-b ] dithiophene [3,2-b ] thiophen-2, 8-yl) - (4, 7-bis (2, 3-dihydrothiophene [3,2-b ] [1,4] dioxin-5) -benzo [1,2,5] thiadiazole-7, 7') ] PIDTT-EBE,
poly [ (5,5,11, 11-tetrakis (4-hexylphenyl) indian thieno [1,2-b ] dithiophene [3,2-b ] thiophen-2, 8-yl) - (4, 7-bis (thiophene-2) -2- (2-hexyldecyl) -2H-benzo [1,2,3] triazole-5, 5' ] PIDTT-TBzT.
5. A capacitor according to claim 1, characterized in that the gel polymer electrolyte layer (3) is an electrolyte layer of a polymer carrier using one of polyvinyl alcohol PVA, polyacrylamide PAM, polyethylene oxide PEO, polyacrylic acid PAA and polymethyl methacrylate PMMA combined with a neutral ionic liquid using neutral Li2SO4And KCl is electrolyte salt or ionic liquid of solute.
6. A preparation method of a wearable full-flexible solid electrochromic supercapacitor is characterized by comprising the following steps:
1) preparing a silver nanowire-conjugated polymer composite transparent electrode:
1a) coating the silver nanowire solution on a glass substrate to form a silver nanowire electrode, and heating and drying the silver nanowire electrode;
1b) mixing the PDMS precursor and a curing agent according to the mass ratio of 5:1-20:1, fully stirring, pouring the mixture on a glass plate with a silver nanowire electrode, standing the mixture in an air environment for 0.1-0.2h to naturally level PDMS, and then putting the mixture into an oven for heating and curing;
1c) stripping the cured PDMS film from the glass plate with the silver nanowire electrode to realize electrode transfer;
1d) soaking the stripped electrode in 5-25% NaCl solution to realize the modification treatment of the low-temperature welding at the silver nanowire lap joint, and washing the modified flexible silver nanowire transparent electrode in deionized water;
1e) preparing a conjugated polymer solution, coating the conjugated polymer solution on the surface of a silver nanowire electrode to form a conjugated polymer active layer with an electrochromic function, and heating and drying at the temperature of 50-70 ℃ for 10-20min to obtain a silver nanowire-conjugated polymer composite transparent electrode;
1f) repeating 1a) -1e), and manufacturing another same composite transparent electrode;
2) combining a polymer carrier with neutral ionic liquid to prepare a flexible gel-state electrolyte layer;
3) assembling the super capacitor:
and (2) pressing the two composite electrodes manufactured in the step (1) on two sides of the electrolyte layer manufactured in the step (2), wherein the pressure applied during pressing is 20-60Pa, and the surface of the composite electrode coated with the conjugated polymer solution is in contact with the electrolyte layer to form a symmetrical sandwich structure, so that the preparation of the wearable full-flexible solid electrochromic supercapacitor is completed.
7. A preparation method of a wearable full-flexible solid electrochromic supercapacitor is characterized by comprising the following steps:
A) preparing a silver nanowire-conjugated polymer composite transparent electrode:
A1) coating the silver nanowire solution on a film-shaped flexible substrate to form a silver nanowire electrode, and heating and drying the silver nanowire electrode;
A2) soaking the electrode in 5-25% NaCl solution to realize the low temperature welding treatment at the silver nanowire lap joint, and washing the modified flexible silver nanowire transparent electrode in deionized water;
A3) preparing a conjugated polymer solution, coating the conjugated polymer solution on the surface of a silver nanowire electrode to form a conjugated polymer active layer with an electrochromic function, and heating and drying at the temperature of 50-70 ℃ for 10-20min to obtain a silver nanowire-conjugated polymer composite transparent electrode;
A4) repeat a1) -A3) to make another identical composite transparent electrode;
B) combining a polymer carrier with neutral ionic liquid to prepare a flexible gel-state electrolyte layer;
C) assembling the super capacitor:
and pressing the two composite electrodes manufactured in the step A) on two sides of the electrolyte layer manufactured in the step B), wherein the applied pressure is 20-60Pa, and the surface of the composite electrode coated with the conjugated polymer solution is in contact with the electrolyte layer to form a symmetrical sandwich structure, so that the preparation of the wearable full-flexible solid electrochromic super capacitor is completed.
8. The method of claim 6, further comprising:
the coating method in the step 1a) comprises the following steps: one of spin coating, spray coating, suction filtration transfer printing and blade coating, wherein the silver wire drying temperature is 50-70 ℃, and the time is 4-10 min.
The curing temperature of the oven in the step 1b) is 60-120 ℃, and the curing time is 1-6 h.
9. The method according to claim 6, wherein the soaking time of the NaCl solution in 1d) is 50-90 s; the number of times of washing the silver nanowire transparent electrode by deionized water is 1-5, and the washing time is 5-20s each time.
10. The method of claim 6, wherein the mass fraction of the conjugated polymer solution in 1e) is 10-20mg mL-1Solution of conjugated polymerThe conjugated polymer in the solution adopts one of PIDTT-TBT, PIDTT-EBE and PIDTT-TBzT, and the solvent is chlorobenzene solution.
CN202111093979.8A 2021-09-17 2021-09-17 Wearable full-flexible solid electrochromic supercapacitor and manufacturing method thereof Pending CN113838680A (en)

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