CN114940809A - Intrinsically stretchable conductive polymer hydrogel and preparation method and application thereof - Google Patents
Intrinsically stretchable conductive polymer hydrogel and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an intrinsically stretchable conductive polymer hydrogel as well as a preparation method and application thereof, wherein the conductive polymer hydrogel comprises a conductive polymer and double additives, and the double additives are a conductive reinforcing agent and a plasticizer; the invention also provides a preparation method of the intrinsically stretchable conductive polymer hydrogel, which comprises the following steps: (1) adding a conductive reinforcing agent and a plasticizer into a PEDOT (PSS) solution, and stirring at room temperature to obtain a PEDOT (PSS) mixed solution; (2) and injecting the PEDOT and PSS mixed solution into a mold, and heating to induce physical crosslinking to prepare the intrinsic stretchable conductive polymer hydrogel. The conductive polymer hydrogel prepared by the method has ultrahigh conductivity, excellent mechanical stretchability, high resilience, low Young modulus, high swelling performance and printability.
Description
Technical Field
The invention belongs to the field of energy storage materials and devices, and particularly relates to an intrinsically stretchable conductive polymer hydrogel, a preparation method thereof and a flexible supercapacitor.
Background
The flexible energy storage device is an important component of flexible electronics, and the research on the flexible Super Capacitor (SCs) energy storage device with high energy density and excellent mechanical property has great significance for the development of the flexible electronics.
Most flexible supercapacitors to date have been manufactured by loading electrode materials onto flexible substrates, which, while giving mechanical flexibility to the device, also reduces specific capacitance and energy density, while adding additional cost and integration inconvenience, because these substrates are generally not electrochemically active and occupy a large volume and mass in flexible SCs. Furthermore, misalignment between the electrode material and the substrate inevitably occurs due to mismatch of their young's moduli, severely limiting the deformability of these SCs.
The conductive polymer hydrogel generally has a unique porous layered structure, can realize the characteristics of electrical and mechanical property regulation and control and the like through molecular design and structure regulation, and has great prospect in the aspects of serving as high-performance electrodes and electrolytes of flexible electrochemical super capacitors.
However, the current conducting polymer hydrogel is generally prepared by using a conducting polymer as a filler and an insulating polymer matrix as a skeleton. These insulating polymer matrices bring about a reliable stretchability while severely reducing the electrical conductivity and electrochemical activity.
Therefore, it is a great challenge to develop an electrode material having both high conductivity and mechanical ductility.
Disclosure of Invention
In order to make up for the defects of the prior art and obtain an electrode material with high conductivity and mechanical ductility, the invention provides an intrinsically stretchable conductive polymer hydrogel as well as a preparation method and application thereof.
The technical scheme is as follows:
in a first aspect, the present invention provides an intrinsically stretchable conductive polymer hydrogel, the raw materials comprising a conductive polymer and a dual additive, the dual additive being a conductivity enhancer and a plasticizer;
preferably, the conductive polymer is one or more of polythiophene, polypyrrole, polyacetylene, polybenzazole or polyaniline.
Preferably, the conductivity enhancer is one or more of dimethyl sulfoxide (DMSO), Ethylene Glycol (EG), Dimethylformamide (DMF), ethylene glycol monomethyl ether, butanol, octanol, and octyl acetate.
Preferably, the plasticizer is one or more of polyoxyethylene alkyl ether, polyethylene glycol p-isooctyl phenyl ether, fatty alcohol polyoxyethylene ether (AEO), fatty acid glycol ester, sucrose fatty acid ester, pentaerythritol fatty acid ester, amine oxide and Alkyl Polyglycoside (APG).
The dual additive and the conductive polymer form physical crosslinking through heating induction, and the intrinsically stretchable conductive polymer hydrogel is prepared. The conducting polymer hydrogel prepared by physical crosslinking has ultrahigh conductivity, excellent mechanical stretchability, high resilience, low Young modulus, high swelling performance and printability.
In a second aspect, the present invention provides a method of preparing an intrinsically stretchable, electrically conductive polymer hydrogel according to the first aspect, comprising the steps of:
(1) adding a conductive reinforcing agent and a plasticizer into a conductive polymer, and stirring at room temperature to obtain a conductive polymer mixed solution;
(2) and (2) injecting the conductive polymer mixed solution obtained in the step (1) into a mould, and heating to induce physical crosslinking to obtain the intrinsic stretchable conductive polymer hydrogel.
Preferably, the mass ratio of the conductive reinforcing agent to the conductive polymer in the step (1) is 1-15%, and the mass ratio of the plasticizer to the conductive polymer is 1-30%.
Preferably, the temperature for heating to induce physical crosslinking in the step (2) is 25-130 ℃, and the heating time is 1-24 h.
In a third aspect, the conductive polymer mixed solution prepared in step (1) may be used as an ink for screen printing or 3D printing techniques.
In a fourth aspect, the use of the intrinsically stretchable conductive polymer hydrogel provided in the first aspect or prepared in the second aspect in a self-supporting all-hydrogel supercapacitor.
Has the advantages that:
in contrast to current conducting polymer hydrogels, which are typically prepared by mixing a conducting polymer with an insulating polymer matrix, this inevitably compromises their electrical and mechanical properties and limits their wide applicability. The invention develops a synergistic regulation strategy, and a conductive polymer hydrogel with ultrahigh conductivity and excellent mechanical stretchability is realized by inducing and forming an interconnected nanofiber network structure through a double additive and a conductive polymer under the condition of not using an insulating polymer matrix. Through the adjustment of components and microstructure, the obtained conductive hydrogel simultaneously shows ultrahigh conductivity, excellent mechanical stretchability, high resilience, low Young's modulus, high swelling property and excellent printability, and shows wide applicability. Meanwhile, the prepared intrinsic stretchable conductive polymer hydrogel is used as an electrode to prepare a substrate-free high-elasticity full-gel Supercapacitor (SCs), and the SCs have the characteristics of simple structure, simple and convenient assembly process, high specific capacitance, strong energy storage capacity, good cycle stability, random deformation and the like.
Drawings
FIG. 1 is a schematic structural diagram of a substrate-free elastic full-gel supercapacitor prepared by using the intrinsically stretchable conductive polymer hydrogel prepared by the invention as an electrode;
FIG. 2 is a plot of the maximum stress strain of the PEDOT PSS hydrogel prepared in example 1;
FIG. 3 is a stress-strain curve of the PEDOT PSS hydrogels prepared in examples 1 and 2;
FIG. 4 TEM images of PEDOT PSS films with different additives obtained in example 3;
FIG. 5 is a pattern of 3D printing of the PEDOT/PSS mixed solution b as an ink in example 4;
FIG. 6 is a plot of cyclic voltammetry curves at different scan rates for the substrate-free elastic full-gel supercapacitor made in example 5;
FIG. 7 is a constant current charge and discharge curve for the baseless elastic all-gel supercapacitor made in example 5 at different current densities;
fig. 8 is a cyclic voltammogram of the substrate-free elastic full-gel supercapacitor in example 6 in the original, bent and kinked states, respectively.
Detailed Description
The following merely illustrates the principles of the invention. Therefore, although not explicitly described or illustrated in the present specification, those skilled in the art may embody the principles of the invention and invent various apparatuses included in the concept and scope of the invention. Further, it is to be understood that all terms and embodiments of the appended claims are principally intended expressly to be only for understanding the concept of the invention, and are not to be construed as limiting the embodiments and aspects specifically enumerated herein.
The following examples illustrate the invention in more detail:
example 1:
(1) to 4.5g of PEDOT: PSS (Heraeus PH 1000) was added 0.27g of dimethyl sulfoxide (DMSO) to obtain a solution b;
(2) adding 0.675g of Triton X-100 (the mass ratio of the conductive polymer to the PEDOT: PSS is 15%) into the solution b, stirring for 1h at room temperature, and uniformly mixing to obtain a PEDOT: PSS solution c;
(3) and (3) dropwise casting the PEDOT/PSS mixed solution c obtained in the step (2) on a polytetrafluoroethylene mold, placing the polytetrafluoroethylene mold in a 40 ℃ forced air drying oven for 12h, and then annealing the polytetrafluoroethylene mold at 130 ℃ for 30min to obtain the intrinsic stretchable conductive polymer hydrogel.
The conductive polymer hydrogel with dimensions of 3mm × 1cm was placed in a tensile mode (1 mm. min.) on a universal test system ((INSTRON 3343) -1 ) The stress-strain curve was measured, and the maximum tensile rate was about 55%, as shown in FIG. 2.
Example 2:
the preparation process was the same as in example 1 except that the Triton X-100 mass in step (1) was replaced with 0.225g (5% by mass to the conductive polymer PEDOT: PSS), 0.45g (10% by mass to the conductive polymer PEDOT: PSS), and 0.9 g (20% by mass to the conductive polymer PEDOT: PSS), respectively.
Conducting polymer hydrogels with different Triton X-100 mass ratios with dimensions of 3mm × 1cm were taken in tensile mode (1 mm. min.) on a universal test system ((INSTRON 3343) -1 ) The following stress-strain curves are tested, and the results are shown in fig. 3, and it can be known that plasticizer Triton X-100 with different mass ratios has an influence on the mechanical properties of the conductive polymer hydrogel: with the increase in the plasticizer, the stretching of the produced conductive polymer hydrogel shows an upward tendency.
Example 3:
PSS film structure characterization of PEDOT under different additives:
PSS solution a, the solution b in the step (1) in the example 1 and the solution c in the step (2) in the example 1 are dried and annealed to form a PEDOT/PSS film containing different additives; the films of PEDOT: PSS with different additives were subjected to structural characterization to obtain TEM images as shown in FIG. 4. The conductivity enhancer DMSO, when combined with the plasticizer Triton X-100, synergistically contributes to the conformational change of the PEDOT chain from a benzene structure to a quinone structure.
Example 4:
the PEDOT: PSS mixed solution b prepared in example 1 was printed as an ink on a flexible photographic paper substrate, and then heat-treated to obtain a PEDOT: PSS pattern, as shown in fig. 5.
Example 5:
adding 1g of PVA and 1g of phosphoric acid into 10mL of deionized water, and dissolving for 4h at 85 ℃ to obtain a gel electrolyte;
two pieces of the intrinsically stretchable conductive polymer hydrogel prepared in example 1, which are 1cm x 2cm, are respectively used as two electrodes of a capacitor, and the two electrodes are adhered by a gel electrolyte to prepare a substrate-free elastic full-gel supercapacitor, wherein the structure of the substrate-free elastic full-gel supercapacitor is shown in figure 1.
The electrochemical activity of the substrate-free elastic full-gel supercapacitor is characterized by Cyclic Voltammetry (CV) and constant current charging and discharging (GCD), and the results are shown in fig. 6 and fig. 7 respectively. As can be seen from FIG. 6, the scan speed is from 10mV · s -1 To 100 mV. s -1 The shape of the CV curve remains quasi-rectangular. The super capacitor prepared by the method has excellent electrochemical activity and stable performance. As can be seen from FIG. 7, the current density was from 0.5mA cm -2 To 5mA cm -2 The shape of the GCD curve is a standard isosceles triangle and is calculated to be 0.5mA cm -2 、1mA·cm -2 、1.5mA·cm -2 、2mA·cm -2 、5mA·cm -2 The area specific capacitance of (A) is 117.4mF · cm -2 、119.0mF·cm -2 、111.6mF·cm -2 、112mF·cm -2 、95mF·cm -2 。
Example 6:
the electrochemical activity of the substrate-free elastic full-gel supercapacitor prepared in example 5 in the original, bent and kinked states is characterized by Cyclic Voltammetry (CV), and as shown in fig. 8, the nearly coincident CV curves illustrate that the assembled device still has excellent electrochemical stability under deformation.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (9)
1. An intrinsically stretchable conductive polymer hydrogel characterized by: the raw materials comprise a conductive polymer and a double additive, wherein the double additive comprises a conductive reinforcing agent and a plasticizer.
2. An intrinsically stretchable conductive polymer hydrogel according to claim 1 in which: the conductive polymer is one or a mixture of more of polythiophene, polypyrrole, polyacetylene, polybenzazole or polyaniline.
3. An intrinsically stretchable conductive polymer hydrogel according to claim 1 in which: the conductive reinforcing agent is one or a mixture of more of dimethyl sulfoxide, ethylene glycol, dimethylformamide, ethylene glycol monomethyl ether, butanol, octanol and octyl acetate.
4. An intrinsically stretchable conductive polymer hydrogel of claim 1 in which: the plasticizer is one or a mixture of more of polyoxyethylene alkyl ether, polyethylene glycol p-isooctyl phenyl ether, fatty alcohol polyoxyethylene ether, fatty acid glycol ester, sucrose fatty acid ester, pentaerythritol fatty acid ester, amine oxide and alkyl polyglycoside.
5. A process for the preparation of an intrinsically stretchable conductive polymer hydrogel of claim 1 comprising the steps of:
(1) adding a conductive reinforcing agent and a plasticizer into a conductive polymer, and stirring at room temperature to obtain a conductive polymer mixed solution;
(2) and (2) injecting the conductive polymer mixed solution obtained in the step (1) into a mould, and heating to induce physical crosslinking to obtain the intrinsic stretchable conductive polymer hydrogel.
6. A method of making an intrinsically stretchable conductive polymer hydrogel of claim 5 in which: the mass ratio of the conductive reinforcing agent to the conductive polymer in the step (1) is 1-15%, and the mass ratio of the plasticizer to the conductive polymer is 1-30%.
7. A method of making an intrinsically stretchable conductive polymer hydrogel of claim 5 in which: in the step (2), the temperature for heating and inducing physical crosslinking is 25-130 ℃, and the heating time is 1-24 h.
8. The method of claim 5, wherein the conductive polymer mixture prepared in step (1) is used as an ink for screen printing or 3D printing.
9. Use of an intrinsically stretchable conductive polymer hydrogel of any one of claims 1 to 4 in a self-supporting all-hydrogel supercapacitor.
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