CN114605674A

CN114605674A - High-specific-capacitance polyaniline composite flexible conductive hydrogel and preparation method thereof

Info

Publication number: CN114605674A
Application number: CN202210424853.2A
Authority: CN
Inventors: 李晓; 赵海兰; 张卫英; 陈兰兰; 逄述博
Original assignee: Fuzhou University
Current assignee: Fuzhou University
Priority date: 2022-04-22
Filing date: 2022-04-22
Publication date: 2022-06-10
Anticipated expiration: 2042-04-22
Also published as: CN114605674B

Abstract

The invention discloses a high-specific-capacitance polyaniline composite flexible conductive hydrogel and a preparation method thereof, belonging to the field of flexible energy storage materials. The method comprises the steps of uniformly dispersing polyaniline dispersion liquid in a polyvinyl alcohol solution by virtue of the dispersibility of graphene oxide, forming substrate hybrid hydrogel with a primary conductive network by utilizing the interaction force of the polyaniline dispersion liquid and the polyvinyl alcohol and the crosslinking action of the polyvinyl alcohol and glutaraldehyde, and then adsorbing and inducing benzene on the substrate hybrid hydrogelAnd (3) performing amine self-assembly, and then adding ammonium persulfate to initiate aniline to polymerize in situ under the induction action of the primary conductive network to form a polyaniline secondary conductive network, thereby obtaining the composite flexible conductive hydrogel with the two-stage conductive network. The hydrogel obtained by the invention has a multi-stage microporous structure, and the specific capacitance of the hydrogel is up to 989 F.g^‑1The conductive film has excellent conductivity, electrochemical performance and tensile property, and can be widely applied to manufacturing of wearable electronic equipment such as flexible super capacitors.

Description

High-specific-capacitance polyaniline composite flexible conductive hydrogel and preparation method thereof

Technical Field

The invention belongs to the field of flexible energy storage materials, relates to conductive polymer hydrogel, and particularly relates to polyaniline composite flexible conductive hydrogel with high specific capacitance and a preparation method thereof.

Background

With the development of science and technology, the demand of flexible wearable electronic devices is rapidly increasing, wherein high-performance flexible supercapacitors have become a research hotspot. The electrode material is the key for determining the electrochemical performance of the supercapacitor, and the commonly used electrode materials mainly comprise carbon materials, metal oxides, conductive polymers and the like. Among conductive polymers, Polyaniline (PANI) is the first choice of electrode materials of super capacitors due to the advantages of easily available raw materials, simple synthesis, high chemical stability, high theoretical specific capacitance and the like. However, PANI as a rigid polymer has poor flexibility, and as ions are embedded and de-embedded in repeated doping and de-doping processes of PANI, the volume of PANI is continuously expanded and contracted, so that the capacitance of PANI is attenuated, and the cyclic use of PANI in a flexible supercapacitor is seriously influenced. Therefore, a polymer hydrogel or other materials with flexibility can be combined with polyaniline to form a composite conductive material with flexibility or multiple networks.

The three-dimensional water system network structure of the hydrogel is beneficial to the transmission of ions in electrolyte, and the Graphene Oxide (GO) is rich in various oxygen-containing functional groups, has the function of dispersing polyaniline, and is easy to compound with other materials. However, the hydrogel framework itself is not conductive, so that most of the composite conductive hydrogels have poor electrochemical performance. When the multiple networks are prepared, the arrangement of the networks is random and disordered, so that a good and through conductive network cannot be constructed, and the charge transmission efficiency cannot be ensured. Therefore, a stable conductive channel is constructed, the charge transmission efficiency is effectively improved, and the circulation stability of the material is ensured, so that the method is the key for preparing the high-electrochemical-property flexible conductive hydrogel electrode material.

Disclosure of Invention

The invention aims to provide a simple and effective secondary induction assembly in-situ polymerization method for preparing polyaniline composite flexible conductive hydrogel with high specific capacitance, aiming at the defects of the prior art, wherein the obtained hydrogel has excellent conductive performance, electrochemical performance and excellent tensile performance.

In order to realize the purpose, the invention adopts the following technical scheme:

a polyaniline composite flexible conductive hydrogel with high specific capacitance is characterized in that Polyaniline (PANI) dispersion liquid is uniformly dispersed in a polyvinyl alcohol (PVA) solution by virtue of the dispersibility of Graphene Oxide (GO), a substrate hybrid hydrogel with a primary conductive network is formed by utilizing the interaction force among the Polyaniline (PANI) dispersion liquid and a PVA (polyvinyl alcohol) solution and the crosslinking action between the PVA and glutaraldehyde, then aniline is adsorbed on the substrate hybrid hydrogel and induced to self-assemble, and then under the induction action of the primary conductive network, ammonium persulfate is added to initiate aniline in-situ polymerization to form a polyaniline secondary conductive network, so that the composite flexible conductive hydrogel with the two-stage conductive network is obtained.

The preparation method comprises the following steps:

(1) preparation of substrate hybrid hydrogel (PPG) with primary conductive network (with induction function)

Dispersing graphene oxide in water to form 3mg/ml graphene oxide dispersion liquid;

dissolving 1.2959-2.5918g of aniline hydrochloride and 0.2-0.6ml of 70wt% phytic acid solution in 20-40ml of deionized water, and marking as solution a; 2.282-4.564g of ammonium persulfate is dissolved in 5-20ml of deionized water and is marked as solution b; cooling the solution a and the solution b to 0-5 ℃, then quickly pouring the solution b into the solution a, uniformly stirring, sealing a film, and reacting for 8-15h at the temperature of 0-5 ℃ to obtain polyaniline dispersion liquid;

dissolving 1-6g of PVA in 10-30ml of deionized water to obtain a PVA solution; uniformly mixing 150-micron graphene oxide dispersion liquid with 200 mu m of ion-doped graphene oxide dispersion liquid with 60-80 mu l of polyaniline dispersion liquid, then adding 300-700 mu l of PVA solution into the dispersion liquid, stirring and mixing for 5min to ensure that the mixture is uniform, finally adding 200-300 mu l of 1vol% glutaraldehyde solution into the mixture, and crosslinking and curing for 1-10min to prepare the substrate hybrid hydrogel PPG;

(2) preparation of aniline self-assembly mixed system

Mixing 30ml of 0.01-0.05mol/l aniline hydrochloride solution and 0.2-0.6ml of 70wt% phytic acid solution, then soaking PPG in the mixed solution for 4-8h, adsorbing and inducing aniline to perform directional self-assembly to form a mixed system;

(3) preparation of high specific capacitance polyaniline composite flexible conductive hydrogel (PPG-P)

And (3) dissolving 0.1141-0.4564g of ammonium persulfate in 1-10ml of deionized water, then quickly pouring the solution into the aniline self-assembly mixed system obtained in the step (2), sealing the membrane, and reacting at the temperature of 0-5 ℃ for 10-15h to polymerize aniline in situ to obtain the hydrogel PPG-P with the two-stage conductive network.

According to the preparation method, firstly, the dispersion effect of Graphene Oxide (GO) is utilized, GO solution and polyaniline dispersion liquid are uniformly blended to obtain mixed solution, then PVA and glutaraldehyde are sequentially added for crosslinking and curing, and the substrate hybrid hydrogel PPG with a primary conductive network is prepared by utilizing the interaction force between every two molecules of PANI, PVA and GO and the crosslinking effect between PVA and glutaraldehyde, wherein GO mainly plays the role of a dispersant, so that PANI can be uniformly distributed in PVA; then, on the basis of the induction action of the primary conductive network, the PPG hydrogel adsorbs and induces self-assembly of aniline (strong interaction force exists between functional groups of various components contained on the primary conductive network and aniline, and the aniline can be induced to be directionally self-assembled on the primary conductive network); and then the polyaniline secondary conductive network can directionally grow on the primary conductive network framework by initiating the in-situ polymerization of aniline, and the two conductive networks are interwoven and run through to form a multi-stage microporous structure, so that the polyaniline composite flexible conductive hydrogel PPG-P with high specific capacitance is obtained. The two-stage conductive network in the polyaniline composite flexible conductive hydrogel provided by the invention not only provides a good transport channel for charge transfer, but also enhances the cycling stability of the material, so that the polyaniline composite flexible conductive hydrogel has excellent conductivity and electrochemical performance.

Compared with the prior art, the invention has the following advantages:

(1) the invention adopts a simple secondary induced assembly in-situ polymerization method to prepare the PPG-P conductive hydrogel with two stages of conductive networks (a primary conductive network and a polyaniline secondary conductive network). Wherein, the primary conductive network with special induction function is prepared by utilizing the interaction force between every two molecules of PANI, PVA and GO and the crosslinking action between PVA and glutaraldehyde; due to strong interaction force between functional groups of various components (such as PANI, GO and PVA) contained in the primary conductive network and aniline, the aniline can be induced to complete oriented self-assembly on the primary conductive network, and then the formed polyaniline secondary conductive network can be directionally grown on the primary conductive network by initiating in-situ polymerization of the aniline. And interweaving the two stages of conductive networks to finally obtain the polyaniline composite flexible conductive hydrogel PPG-P with high specific capacitance.

(2) Based on the special functionality of the first-level conductive network and the function of inducing the directional self-assembly of aniline, the distribution of the polyaniline second-level conductive network is not random any more, but is regularly distributed on the first-level conductive network framework, so that the formed two-level conductive network not only provides a good transport channel for charge transfer, improves the charge transfer efficiency and the utilization rate of electroactive substances, but also enhances the stability of the material, and ensures that PPG-P has excellent conductivity and electrochemical performance.

(3) The high specific capacitance polyaniline composite flexible conductive hydrogel PPG-P obtained by the invention has a multi-stage micropore structure, and the specific capacitance of the PPG-P is up to 989 F.g^-1The conductive film has excellent conductivity, electrochemical performance and tensile property, and can be widely applied to manufacturing of wearable electronic equipment such as flexible super capacitors.

Drawings

FIG. 1 is a cross-sectional electron microscope image of the base hybrid hydrogel PPG (A) and the polyaniline composite flexible conductive hydrogel PPG-P (B) prepared in example 1.

FIG. 2 is a sectional electron micrograph of a conductive hydrogel PP-P obtained in comparative example 1.

FIG. 3 is a sectional electron micrograph of conductive hydrogel PG-P obtained in comparative example 2.

FIG. 4 is a cross-sectional electron micrograph of the conductive hydrogel PANI/PVA prepared in comparative example 3.

FIG. 5 is a sectional electron micrograph of the electrically conductive hydrogel obtained in comparative example 4.

FIG. 6 is a sectional electron microscope image of the electrically conductive hydrogel prepared in comparative example 5.

FIG. 7 shows the results of the measurements of the conductive hydrogels obtained in example 1 and comparative examples 1 to 5 at a current density of 0.5A g^-1Constant current charging and discharging curve and corresponding mass specific capacitance.

Fig. 8 is a picture of LED luminescence using the polyaniline composite flexible conductive hydrogel obtained in example 1.

Detailed Description

In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.

Example 1

(1) 1.5551g (12 mmol) aniline hydrochloride and 0.4ml 70wt% phytic acid solution are dissolved in 30ml deionized water and are marked as solution a; 2.7384g (12 mmol) of ammonium persulfate was dissolved in 10ml of deionized water and designated as solution b. Cooling the solution a and the solution b to 0-5 ℃, then quickly pouring the solution b into the solution a, uniformly stirring, sealing a membrane, and reacting for 12 hours at the temperature of 0-5 ℃ to obtain the PANI dispersion liquid.

Dissolving 3g of PVA in 20ml of deionized water to obtain PVA solution; first 180. mu.l of 3mg/ml^-1And after uniformly mixing the GO dispersion liquid and 65 mu l of PANI dispersion liquid, adding 500 mu l of PVA solution into the mixture, stirring and mixing for 5min to ensure that the mixture is uniform, finally adding 250 mu l of 1vol% glutaraldehyde solution, and performing crosslinking and curing for 5min to obtain the substrate hybrid hydrogel PPG with the primary conductive network.

(2) Soaking the PPG prepared in the step (1) in 30ml of 0.03 mol.l^-1Aniline is adsorbed and self-assembled for 6h in a mixed solution prepared by aniline hydrochloride solution and 0.3ml 70wt% phytic acid solution.

(3) 0.2282g (1 mmol) of ammonium persulfate is dissolved in 2ml of deionized water, then the solution is quickly poured into the mixed system in the step (2) to initiate aniline in-situ polymerization, then a membrane is sealed, the reaction is carried out for 12 hours in the environment of 0-5 ℃, and the PPG-P conductive hydrogel with the two-stage conductive network is obtained after the reaction is finished.

FIG. 1 is a cross-sectional electron micrograph of the resulting substrate hybrid hydrogel PPG (A) and the conductive hydrogel PPG-P (B). As can be seen from the figure, the PPG-P conductive hydrogel prepared by using PPG as a substrate has a good microporous structure, and the three-dimensional network framework in the PPG-P conductive hydrogel becomes thick due to the fact that more polyaniline is uniformly loaded, which fully indicates that the prepared polyaniline secondary conductive network is successfully compounded on the primary conductive network structure of the substrate and is uniformly distributed on the primary conductive network framework.

Comparative example 1

(1) 1.5551g (12 mmol) aniline hydrochloride and 0.4ml 70wt% phytic acid solution are dissolved in 30ml deionized water and are marked as solution a; 2.7384g (12 mmol) of ammonium persulfate was dissolved in 10ml of deionized water and was designated as solution b. Cooling the solution a and the solution b to 0-5 ℃, then quickly pouring the solution b into the solution a, uniformly stirring, sealing a membrane, and reacting for 12 hours at the temperature of 0-5 ℃ to obtain the PANI dispersion liquid.

Dissolving 3g of PVA in 20ml of deionized water to obtain PVA solution; and uniformly mixing 180 mu l of deionized water and 65 mu l of PANI dispersion liquid, adding 500 mu l of PVA solution, stirring and mixing for 5min to ensure that the mixture is uniform, adding 250 mu l of 1vol% glutaraldehyde solution, and performing crosslinking and curing for 5min to obtain the substrate hybrid hydrogel PP.

(2) Soaking the PP prepared in the step (1) in 30ml of 0.03 mol/ml^-1Aniline hydrochloride solution and 0.3ml 70wt% phytic acid solution were mixed for 6 hours to sufficiently absorb aniline monomer.

(3) 0.2282g (1 mmol) of ammonium persulfate is dissolved in 2ml of deionized water, then the solution is quickly poured into the mixed system in the step (2) to initiate aniline in-situ polymerization, then a membrane is sealed, the reaction is carried out for 12 hours at the temperature of 0-5 ℃, and after the reaction is finished, conductive hydrogel is obtained and recorded as PP-P.

As can be seen from FIG. 2, an irregular network consisting of a plurality of filaments exists inside the conductive hydrogel PP-P, and the conductive hydrogel PP-P has a certain pore structure, but PANI is obviously agglomerated. This is due to the fact that the absence of GO in the PP-P substrate does not allow for good dispersion of PANI in the substrate, resulting in a large amount of PANI agglomeration, an inefficient formation of a two-stage conductive network, and an inefficient improvement in charge transport efficiency and utilization of electroactive species.

Comparative example 2

(1) Dissolving 3g of PVA in 20ml of deionized water to obtain a PVA solution; 180. mu.l of 3 mg. ml^-1And uniformly mixing the GO dispersion liquid with 65 mu l of deionized water, adding 500 mu l of PVA solution into the mixture, stirring and mixing for 5min to ensure that the mixture is uniform, adding 250 mu l of 1vol% glutaraldehyde solution, and crosslinking and curing for 5min to prepare the substrate hybrid hydrogel PG.

(2) Immersing PG prepared in step (1) in 30ml of 0.03 mol.l^-1Aniline hydrochloride solution and 0.3ml 70wt% phytic acid solution were mixed for 6 hours to sufficiently absorb aniline monomer.

(3) 0.2282g (1 mmol) of ammonium persulfate is dissolved in 2ml of deionized water, then the solution is quickly poured into the mixed system in the step (2) to initiate aniline in-situ polymerization, then a membrane is sealed, the reaction is carried out for 12 hours at the temperature of 0-5 ℃, and after the reaction is finished, conductive hydrogel is obtained and is recorded as PG-P.

As can be seen from FIG. 3, the conductive hydrogel PG-P has large-area adhesion phenomenon, the pore structure is seriously damaged, and a large amount of polyaniline is mixed with the conductive hydrogel PG-P to agglomerate. This is due to the absence of PANI in the substrate of PG-P, the inability to form a PANI-based primary conductive network, and thus a secondary conductive network, and the inability to improve charge transport efficiency and utilization of electroactive species, resulting in poor electrochemical performance.

Comparative example 3

(1) Dissolving 3g of PVA in 20ml of deionized water to obtain a PVA solution; adding 500 mul PVA solution into 254 mul deionized water, stirring and mixing for 5min to make it uniform, adding 250 mul 1vol% glutaraldehyde solution, and cross-linking and solidifying for 5min to obtain PVA hydrogel.

(2) Soaking the PVA prepared in the step (1) in 30ml of 0.03 mol.l^-1Aniline hydrochloride solution and 0.3ml 70wt% phytic acid solution were mixed for 6 hours to sufficiently absorb aniline monomer.

(3) 0.2282g (1 mmol) of ammonium persulfate is dissolved in 2ml of deionized water, then the solution is quickly poured into the mixed system in the step (2) to initiate aniline in-situ polymerization, then a membrane is sealed, the reaction is carried out for 12 hours in the environment of 0-5 ℃, and the PANI/PVA conductive hydrogel is obtained after the reaction is finished.

As can be seen from fig. 4, although there is a certain amount of pore structure in the PANI/PVA conductive hydrogel, PANI is seriously agglomerated, which cannot fully exert the conductive capability of PANI. The PANI/PVA substrate is not added with PANI and GO, a first-level conductive network with induction action built by utilizing interaction force among PVA, PANI and GO molecules in PPG-P does not exist, a two-level conductive network cannot be formed, and the PANI is easy to agglomerate, so that the PANI/PVA electrochemical performance is poor.

Comparative example 4

(1) Preparation of PANI dispersion the same as in example 1.

Dissolving 3g of PVA in 20ml of deionized water to obtain PVA solution; first 180. mu.l of 3mg/ml^-1And uniformly mixing the GO dispersion liquid with 500 mu l of PVA solution, adding 65 mu l of PANI dispersion liquid into the mixture, stirring and mixing for 5min to ensure that the mixture is uniform, finally adding 250 mu l of 1vol% glutaraldehyde solution, and performing crosslinking and curing for 5min to prepare the substrate hybrid hydrogel PPG with the primary conductive network.

In the comparative example, the GO solution and the PVA solution are mixed, and then the PANI dispersion liquid and the glutaraldehyde are added in sequence, as can be seen from FIG. 5, compared with the network structure of the obtained conductive hydrogel in example 1, the aggregation phenomenon of polyaniline exists in the internal structure, the network structure is not communicated, part of places are of a lamellar structure, and the number of pores is reduced. The PANI is added after the GO and the PVA are mixed, so that the dispersing effect of the GO on the PANI cannot be fully exerted, the PANI in the substrate hydrogel is not uniformly dispersed, and a large amount of agglomeration is generated, thereby the charging sequence is not beneficial to the formation of a primary conductive network, the directional growth of a polyaniline secondary conductive network pair cannot be induced, and the performance of the conductive hydrogel is poor.

Comparative example 5

(1) PANI dispersion was prepared as in example 1.

Dissolving 3g of PVA in 20ml of deionized water to obtain PVA solution; first, 65. mu.l of PANI dispersion was mixed with 500. mu.l of PVA solution, and 180. mu.l of 3mg/ml was added thereto^-1And stirring and mixing the GO dispersion liquid for 5min to be uniform, finally adding 250 mu l of 1vol% glutaraldehyde solution, and crosslinking and curing for 5min to obtain the substrate hybrid hydrogel PPG with the primary conductive network.

(2) Soaking the PPG prepared in the step (1) in 30ml of 0.03 mol.l^-1Aniline is adsorbed and self-assembled for 6 hours in a mixed solution prepared by aniline hydrochloride solution and 0.3ml 70wt% phytic acid solution.

(3) 0.2282g (1 mmol) of ammonium persulfate is dissolved in 2ml of deionized water, then the solution is quickly poured into the mixed system in the step (2) to initiate aniline in-situ polymerization, then a membrane is sealed, the reaction is carried out for 12 hours in the environment of 0-5 ℃, and the PPG-P conductive hydrogel with the two-stage conductive network is obtained after the reaction.

In this comparative example, the PANI dispersion was mixed with the PVA solution first, and then the GO solution and glutaraldehyde were added in sequence. As can be seen from FIG. 6, the internal structure of the obtained conductive hydrogel has a large amount of polyaniline agglomeration phenomenon, the number of the microporous structures is small, the network structure is fine and discontinuous, and the charge transmission is not facilitated. This is attributed to the fact that when PANI is mixed with PVA first, since there is no dispersing effect of GO, PANI is agglomerated in the PVA solution in a large amount, and even if GO solution is added later, the dispersing effect is greatly reduced, and PANI cannot be well and uniformly dispersed in PVA. Therefore, the charging sequence is not beneficial to the formation of the primary conductive network, and further the directional growth of the polyaniline secondary conductive network pair cannot be induced, so that the performance of the conductive hydrogel is poor.

FIG. 7 shows the results of the measurements of the conductive hydrogels obtained in example 1 and comparative examples 1 to 5 at a current density of 0.5A g^-1Constant current charging and discharging curve and corresponding mass specific capacitance. As can be seen from the figure, the conductive hydrogel PPG-P obtained in example 1 has a structure of up to 989F g^-1The mass specific capacitance of the capacitor is good, and the capacitance retention rate is 87% after 1000 times of constant current charge-discharge cycles. Furthermore, PPG-P also exhibits excellent conductivity (conductivity 5.47 S.m)^-1) And excellent mechanical properties (elongation at break 186%, tensile strength 0.5 MPa). Comparative example 1 base hybrid hydrogel of conductive hydrogel PP-P without GO and its specific mass capacitance (458F g)^-1) Much lower than in example 1. In contrast, in comparative examples 2 and 3, the PANI dispersion liquid or the PANI dispersion liquid and the GO dispersion liquid are not added into the substrate hybrid hydrogel, so that the electrochemical performance is not good (the mass specific capacitance is 299F g. g respectively)^-1、388F·g^-1). Comparative examples 4 and 5 change the order of addition, resulting in electrochemical properties (mass specific capacitance of 670F g, respectively) of the conductive hydrogel formed^-1、600F·g^-1) Also less so than in example 1.

As can be seen from the above, only PPG-P prepared by the method of the invention has excellent conductivity, electrochemical performance and excellent tensile property, and can be widely applied to the manufacture of wearable electronic devices such as flexible supercapacitors.

Example 2

(1) 2.5918g (20 mmol) aniline hydrochloride and 0.4ml 70wt% phytic acid solution are dissolved in 30ml deionized water and are marked as solution a; 4.564g (20 mmol) of ammonium persulfate was dissolved in 10ml of deionized water and was designated as solution b. And cooling the solution a and the solution b to 0-5 ℃, then quickly pouring the solution b into the solution a, uniformly stirring, sealing a film, and reacting for 12 hours at the temperature of 0-5 ℃ to obtain the PANI dispersion liquid.

Dissolving 3g of PVA in 17ml of deionized water to obtain a PVA solution; 160. mu.l of 3mg/ml^-1And after uniformly mixing the GO dispersion liquid and 65 mu l of PANI dispersion liquid, adding 500 mu l of PVA solution into the mixture, stirring and mixing for 5min to ensure that the mixture is uniform, finally adding 250 mu l of 1vol% glutaraldehyde solution, and performing crosslinking and curing for 5min to obtain the substrate hybrid hydrogel PPG with the primary conductive network.

(3) 0.2282g (1 mmol) of ammonium persulfate is dissolved in 4ml of deionized water, then the solution is quickly poured into the mixed system in the step (2) to initiate aniline in-situ polymerization, then a membrane is sealed, the reaction is carried out for 12 hours in the environment of 0-5 ℃, and the PPG-P conductive hydrogel with the two-stage conductive network is obtained after the reaction.

Example 3

Dissolving 3g of PVA in 17ml of deionized water to obtain a PVA solution; first 170. mu.l of 3mg/ml^-1And after uniformly mixing the GO dispersion liquid and 80 mu l of PANI dispersion liquid, adding 500 mu l of PVA solution into the mixture, stirring and mixing for 5min to ensure that the mixture is uniform, finally adding 250 mu l of 1vol% glutaraldehyde solution, and performing crosslinking and curing for 5min to obtain the substrate hybrid hydrogel PPG with the primary conductive network.

(2) Soaking the PPG prepared in the step (1) in 30ml of 0.02 mol.l^-1Aniline is adsorbed and self-assembled for 6h in a mixed solution prepared by aniline hydrochloride solution and 0.3ml 70wt% phytic acid solution.

(3) And (3) dissolving 0.1465g (3 mmol) of ammonium persulfate in 4ml of deionized water, then quickly pouring the solution into the mixed system in the step (2) to initiate aniline in-situ polymerization, then sealing the membrane, reacting for 12 hours in an environment at 0-5 ℃, and obtaining the PPG-P conductive hydrogel with the two-stage conductive network after the reaction is finished.

Example 4

Dissolving 2g of PVA in 18ml of deionized water to obtain PVA solution; first 180. mu.l of 3mg/ml^-1And uniformly mixing the GO dispersion liquid with 65 mu l of PANI dispersion liquid, adding 500 mu l of PVA solution into the mixture, stirring and mixing for 5min to ensure that the mixture is uniform, finally adding 210 mu l of 1vol% glutaraldehyde solution, and performing crosslinking and curing for 5min to prepare the substrate hybrid hydrogel PPG with the primary conductive network.

(2) Soaking the PPG prepared in the step (1) in 30ml of 0.04 mol.l^-1Aniline is adsorbed and self-assembled for 6h in a mixed solution prepared by aniline hydrochloride solution and 0.3ml 70wt% phytic acid solution.

(3) And (3) dissolving 0.4111g (6 mmol) of ammonium persulfate in 10ml of deionized water, then quickly pouring the solution into the mixed system in the step (2) to initiate aniline in-situ polymerization, then sealing a film, reacting for 12 hours in an environment at 0-5 ℃, and obtaining the PPG-P conductive hydrogel with the two-stage conductive network after the reaction is finished.

Example 5

Dissolving 3g of PVA in 17ml of deionized water to obtain a PVA solution; first 180. mu.l of 3mg/ml^-1GO dispersion ofAnd after 65 mu l of PANI dispersion liquid is uniformly mixed, adding 400 mu l of PVA solution into the mixture, stirring and mixing for 5min to ensure that the mixture is uniform, finally adding 270 mu l of 1vol% glutaraldehyde solution, and performing crosslinking and curing for 5min to prepare the substrate hybrid hydrogel PPG with the primary conductive network.

(3) And (3) dissolving 0.1429g (0.6 mmol) of ammonium persulfate in 1ml of deionized water, then quickly pouring the solution into the mixed system in the step (2) to initiate aniline in-situ polymerization, then sealing the membrane, reacting for 12 hours in an environment at 0-5 ℃, and obtaining the PPG-P conductive hydrogel with the two-stage conductive network after the reaction is finished.

The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims

1. A preparation method of polyaniline composite flexible conductive hydrogel with high specific capacitance is characterized by comprising the following steps: the method comprises the following steps:

(1) uniformly blending the graphene oxide dispersion liquid and the polyaniline dispersion liquid to obtain a mixed solution; then adding polyvinyl alcohol into the mixture and uniformly mixing the mixture; adding glutaraldehyde solution for crosslinking and curing to prepare substrate hybrid hydrogel with a primary conductive network;

(2) soaking the substrate hybrid hydrogel obtained in the step (1) in an aniline solution to obtain an aniline self-assembly mixed system;

(3) and (3) initiating the aniline in the aniline self-assembly mixed system obtained in the step (2) to carry out in-situ polymerization under the induction action of the primary conductive network to form a polyaniline secondary conductive network which directionally grows on the primary conductive network, thereby obtaining the high specific capacitance polyaniline composite flexible conductive hydrogel with the two-stage conductive network.

2. The preparation method of the polyaniline composite flexible conductive hydrogel with high specific capacitance according to claim 1, which is characterized by comprising the following steps: the specific preparation steps of the substrate hybrid hydrogel are as follows:

dissolving 1-6g of polyvinyl alcohol in 10-30ml of deionized water to obtain a polyvinyl alcohol solution; and (2) uniformly mixing 150 plus 200 mu l of graphene oxide dispersion liquid prepared in the step I with 60-80 mu l of polyaniline dispersion liquid prepared in the step II, adding 300 plus 700 mu l of polyvinyl alcohol solution, stirring and mixing for 5min to ensure that the mixture is uniform, finally adding 200 plus 300 mu l of glutaraldehyde solution with the concentration of 1vol%, and performing crosslinking and curing for 1-10min to obtain the substrate hybrid hydrogel with the primary conductive network.

3. The preparation method of the polyaniline composite flexible conductive hydrogel with high specific capacitance according to claim 1, which is characterized by comprising the following steps: the step (2) is to mix 30ml of 0.01 to 0.05mol/l aniline hydrochloride solution and 0.2 to 0.6ml of 70wt% phytic acid solution, then soak the substrate hybrid hydrogel in the mixed solution for 4 to 8 hours, adsorb and induce the aniline to directionally self-assemble to form a mixed system.

4. The preparation method of the polyaniline composite flexible conductive hydrogel with high specific capacitance according to claim 1, which is characterized by comprising the following steps: and (3) specifically, 0.1141-0.4564g of ammonium persulfate is dissolved in 1-10ml of deionized water, then the solution is quickly poured into the aniline self-assembly mixed system obtained in the step (2), a film is sealed, and the reaction is carried out for 10-15h in the environment of 0-5 ℃, so that the high specific capacitance polyaniline composite flexible conductive hydrogel with the two-stage conductive network is obtained.

5. A high specific capacitance polyaniline composite flexible conductive hydrogel prepared by any one of the methods described in claims 1-4.