CN114605674B - Polyaniline composite flexible conductive hydrogel with high specific capacitance and preparation method thereof - Google Patents
Polyaniline composite flexible conductive hydrogel with high specific capacitance and preparation method thereof Download PDFInfo
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Abstract
The invention discloses polyaniline composite flexible conductive hydrogel with high specific capacitance and a preparation method thereof, and belongs to the field of flexible energy storage materials. The polyaniline dispersion liquid is uniformly dispersed in a polyvinyl alcohol solution by virtue of the dispersibility of graphene oxide, a substrate hybridization hydrogel with a first-stage conductive network is formed by utilizing interaction force among the three components and crosslinking action between polyvinyl alcohol and glutaraldehyde, then aniline is adsorbed and induced to self-assemble on the substrate hybridization hydrogel, and then aniline in-situ polymerization is initiated by adding ammonium persulfate under the induction action of the first-stage conductive network to form a polyaniline second-stage conductive network, so that the composite flexible conductive hydrogel with a two-stage conductive network is obtained. The hydrogel obtained by the invention has a multi-stage micropore structure, and the specific capacitance of the hydrogel is as high as 989F g ‑1 The conductive material has excellent conductivity, electrochemical performance and tensile performance, and can be widely applied to manufacturing of wearable electronic equipment such as flexible super capacitors and the like.
Description
Technical Field
The invention belongs to the field of flexible energy storage materials, relates to conductive polymer hydrogel, and in particular relates to polyaniline composite flexible conductive hydrogel with high specific capacitance and a preparation method thereof.
Background
With the development of technology, the demand for 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 common electrode material mainly comprises carbon material, metal oxide, conductive polymer and the like. Among the conductive polymers, polyaniline (PANI) is the first choice of supercapacitor electrode materials because of the advantages of readily available raw materials, simple synthesis, high chemical stability, high theoretical specific capacitance and the like. However, PANI is used as a rigid polymer, has poor flexibility, and can cause continuous expansion and contraction of the volume of the PANI along with the intercalation and deintercalation of ions in the repeated doping and deintercalation processes of the PANI, so that the attenuation of the PANI capacitance is caused, and the recycling of the PANI in the flexible supercapacitor is seriously influenced. Thus, a polymer hydrogel or other material having flexibility can be selected to combine with polyaniline to form a flexible or multi-network composite conductive material.
The three-dimensional water system network structure of the hydrogel is beneficial to the transmission of ions in the electrolyte, and the Graphene Oxide (GO) is rich in various oxygen-containing functional groups, so that the three-dimensional water system network structure not only has the function of dispersing polyaniline, but also is easy to compound with other materials. However, the hydrogel skeleton itself is not conductive, so that most of composite conductive hydrogels have poor electrochemical properties. In the preparation of multiple networks, 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, so that the charge transmission efficiency is effectively improved, and meanwhile, the cycling stability of the material is ensured, so that the method is a key for preparing the flexible conductive hydrogel electrode material with high electrochemical performance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a simple and effective secondary induction assembly in-situ polymerization method for preparing polyaniline composite flexible conductive hydrogel with high specific capacitance, and the obtained hydrogel has excellent conductive performance, electrochemical performance and tensile performance.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a polyaniline composite flexible conductive hydrogel with high specific capacitance is prepared as using dispersity of Graphene Oxide (GO) to make Polyaniline (PANI) dispersion liquid disperse uniformly in polyvinyl alcohol (PVA) solution, utilizing interaction force between three and cross-linking action between PVA and glutaraldehyde to form substrate hybridization hydrogel with primary conductive network, adsorbing and inducing aniline self-assembly on substrate hybridization hydrogel, adding ammonium persulfate to initiate aniline in-situ polymerization to form polyaniline secondary conductive network under induction action of primary conductive network so as to obtain composite flexible conductive hydrogel with two-stage conductive network.
The preparation method comprises the following steps:
(1) Preparation of substrate hybrid hydrogels (PPG) with primary conductive network (with inductive function)
(1) Dispersing graphene oxide in water to form a graphene oxide dispersion liquid with the concentration of 3 mg/ml;
(2) 1.2959-2.5918g of aniline hydrochloride and 0.2-0.6ml of 70wt% phytic acid solution are dissolved in 20-40ml of deionized water and marked as solution a; 2.282-4.564g of ammonium persulfate is dissolved in 5-20ml of deionized water and is marked as a solution b; cooling the solution a and the solution b to 0-5 ℃, then rapidly pouring the solution b into the solution a, stirring uniformly, sealing a film, and reacting for 8-15h in an environment of 0-5 ℃ to obtain polyaniline dispersion liquid;
(3) 1-6g PVA is dissolved in 10-30ml deionized water to obtain PVA solution; uniformly mixing 150-200 mu graphene oxide dispersion liquid and 60-80 mu L polyaniline dispersion liquid, adding 300-700 mu L PVA solution into the mixture, stirring and mixing for 5min to uniformly, adding 200-300 mu L glutaraldehyde solution with concentration of 1vol% into the mixture, and crosslinking and curing for 1-10min to obtain a substrate hybridized hydrogel PPG;
(2) Preparation of aniline self-assembled 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 directionally self-assemble to form a mixed system;
(3) Preparation of polyaniline composite flexible conductive hydrogel (PPG-P) with high specific capacitance
Dissolving 0.1141-0.4564g of ammonium persulfate in 1-10ml of deionized water, rapidly pouring the solution into the aniline self-assembly mixed system obtained in the step (2), sealing a film, and reacting for 10-15h in an environment of 0-5 ℃ to polymerize aniline in situ to obtain the hydrogel PPG-P with a two-stage conductive network.
Firstly, uniformly blending a GO solution and polyaniline dispersion liquid by utilizing the dispersion effect of Graphene Oxide (GO) to obtain a mixed solution, then sequentially adding PVA and glutaraldehyde for crosslinking and curing, and preparing a substrate hybridization hydrogel PPG with a primary conductive network by utilizing the interaction force between two molecules of PANI, PVA and GO and the crosslinking effect between PVA and glutaraldehyde, wherein GO mainly plays a role of a dispersing agent, so that PANI can be uniformly distributed in PVA; then on the basis of the induction effect of the primary conductive network, the PPG hydrogel adsorbs and induces aniline self-assembly (the functional groups of various components contained on the primary conductive network have strong interaction force with aniline, so that the aniline can be induced to directionally self-assemble 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-stage conductive networks are mutually interwoven and penetrated to form a multi-stage micropore 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 not only provides a good transportation channel for charge transfer, but also enhances the circulation stability of the material, so that the polyaniline composite flexible conductive hydrogel has excellent conductive performance and electrochemical performance.
Compared with the prior art, the invention has the following advantages:
(1) The PPG-P conductive hydrogel with a two-stage conductive network (a first-stage conductive network and a polyaniline second-stage conductive network) is prepared by adopting a simple secondary induction assembly in-situ polymerization method. Wherein, the primary conductive network with special induction function is prepared by utilizing the interaction force between molecules of PANI, PVA and GO and the crosslinking action between PVA and glutaraldehyde; the functional groups of various components (such as PANI, GO, PVA) contained on the primary conductive network have strong interaction force with the aniline, so that the aniline can be induced to finish directional self-assembly on the functional groups, and then the formed polyaniline secondary conductive network can grow on the primary conductive network in a directional manner by initiating in-situ polymerization of the aniline. The two-stage conductive networks are interwoven with each other, and finally the high-specific-capacitance polyaniline composite flexible conductive hydrogel PPG-P is obtained.
(2) Based on the special function of the primary conductive network, which is used for inducing the aniline to self-assemble, the distribution of the polyaniline secondary conductive network is not random any more, but is regularly distributed on the primary conductive network framework, so that the formed two-stage conductive network not only provides a good transportation channel for charge transfer and improves the charge transfer efficiency and the utilization rate of electroactive substances, but also enhances the stability of the material, so that the PPG-P has excellent conductive performance and electrochemical performance.
(3) The polyaniline composite flexible conductive hydrogel PPG-P with high specific capacitance has a multi-stage micropore structure, and the specific capacitance is as high as 989F g -1 The conductive material has excellent conductivity, electrochemical performance and tensile performance, and can be widely applied to manufacturing of wearable electronic equipment such as flexible super capacitors and the like.
Drawings
FIG. 1 is a cross-sectional electron micrograph of the substrate hybrid hydrogel PPG (A) and the polyaniline composite flexible conductive hydrogel PPG-P (B) prepared in example 1.
FIG. 2 is a cross-sectional electron microscopic view of the conductive hydrogel PP-P prepared in comparative example 1.
FIG. 3 is a cross-sectional electron microscopic view of the conductive hydrogel PG-P prepared in comparative example 2.
FIG. 4 is a cross-sectional electron microscopic view of the conductive hydrogel PANI/PVA prepared in comparative example 3.
FIG. 5 is a cross-sectional electron microscopic view of the conductive hydrogel prepared in comparative example 4.
FIG. 6 is a cross-sectional electron microscopic view of the conductive hydrogel prepared in comparative example 5.
FIG. 7 shows the current densities of the conductive hydrogels prepared in example 1 and comparative examples 1 to 5 at 0.5 A.g -1 Constant current charge-discharge curve and corresponding mass ratio capacitance.
Fig. 8 is a photograph showing the luminescence of an LED using the polyaniline composite flexible conductive hydrogel obtained in example 1.
Detailed Description
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
Example 1
(1) (1) 1.5551g (12 mmol) of aniline hydrochloride and 0.4ml of 70wt% phytic acid solution were dissolved in 30ml of deionized water, and designated 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 rapidly pouring the solution b into the solution a, stirring uniformly, sealing the film, and reacting for 12 hours in the environment of 0-5 ℃ to obtain the PANI dispersion liquid.
(2) 3g of PVA is dissolved in 20ml of deionized water to obtain PVA solution; 180 μl of 3 mg.ml is first added -1 After uniformly mixing GO dispersion and 65 μl PANI dispersion, adding 500 μl PVA solution, stirring and mixing for 5min to uniformly, and finally adding 250 μl glutaraldehyde solution with concentration of 1vol%, and crosslinking and curing for 5min to obtain the substrate hybridized hydrogel PPG with primary conductive network.
(2) Soaking the PPG prepared in the step (1) in 30ml of 0.03 mol.l -1 In a mixed solution prepared from aniline hydrochloride solution and 0.3ml 70wt% phytic acid solution, aniline self-assembly was adsorbed and induced for 6h.
(3) 0.2282g (1 mmol) of ammonium persulfate is taken and dissolved in 2ml of deionized water, then the solution is rapidly poured into the mixed system of the step (2) to initiate aniline in-situ polymerization, then a film is sealed, the reaction is carried out for 12 hours in an environment of 0-5 ℃, and the PPG-P conductive hydrogel with a two-stage conductive network is obtained after the reaction.
FIG. 1 is a cross-sectional electron micrograph of the resulting substrate hybrid hydrogel PPG (A) and conductive hydrogel PPG-P (B). The graph shows that the PPG-P conductive hydrogel prepared by taking PPG as a substrate has a good micropore structure, and the three-dimensional network skeleton in the PPG-P conductive hydrogel is thickened due to the fact that more polyaniline is uniformly loaded, so that the prepared polyaniline secondary conductive network is fully illustrated to be successfully compounded on the primary conductive network structure of the substrate and uniformly distributed on the primary conductive network skeleton.
Comparative example 1
(1) (1) 1.5551g (12 mmol) of aniline hydrochloride and 0.4ml of 70wt% phytic acid solution were dissolved in 30ml of deionized water, and designated 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 rapidly pouring the solution b into the solution a, stirring uniformly, sealing the film, and reacting for 12 hours in the environment of 0-5 ℃ to obtain the PANI dispersion liquid.
(2) 3g of PVA is dissolved in 20ml of deionized water to obtain PVA solution; after 180. Mu.l of deionized water and 65. Mu.l of PANI dispersion were uniformly mixed, 500. Mu.l of PVA solution was added thereto and stirred and mixed for 5 minutes to uniformly, and 250. Mu.l of 1vol% glutaraldehyde solution was further added thereto for crosslinking and curing for 5 minutes to prepare a substrate-hybridized hydrogel PP.
(2) Soaking the PP prepared in the step (1) in 30ml of a solution of 0.03 mol.ml -1 An aniline hydrochloride solution and 0.3ml 70wt% phytic acid solution were mixed for 6 hours to fully absorb aniline monomer.
(3) 0.2282g (1 mmol) of ammonium persulfate is taken and dissolved in 2ml of deionized water, then the solution is rapidly poured into the mixed system of the step (2) to initiate aniline in-situ polymerization, then a film is sealed, the reaction is carried out for 12 hours in an environment of 0-5 ℃, and the conductive hydrogel is obtained after the reaction, and is marked as PP-P.
As can be seen from fig. 2, the conductive hydrogel PP-P has an irregular network of many filaments inside, and has a certain pore structure, but PANI is significantly agglomerated. The PANI is not well dispersed due to the fact that GO is not added into the PP-P substrate, so that a large amount of PANI is aggregated, a two-stage conductive network cannot be effectively formed, and the charge transmission efficiency and the utilization rate of electroactive substances cannot be effectively improved.
Comparative example 2
(1) 3g of PVA is dissolved in 20ml of deionized water to obtain PVA solution; 180 μl of 3 mg.ml -1 After uniformly mixing GO dispersion with 65. Mu.l deionized water, adding 500. Mu.l PVA solution into the mixture, stirring and mixing the mixture for 5min to uniformly, adding 250. Mu.l 1vol% glutaraldehyde solution, and crosslinking and curing the mixture for 5min to obtain the substrate hybrid hydrogel PG.
(2) Immersing PG prepared in step (1) in a solution of 30ml of 0.03 mol.l -1 An aniline hydrochloride solution and 0.3ml 70wt% phytic acid solution were mixed for 6 hours to fully 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 film is sealed, the reaction is carried out for 12 hours in an environment of 0-5 ℃, and the conductive hydrogel is obtained after the reaction, and is marked as PG-P.
As can be seen from FIG. 3, the conductive hydrogel PG-P has a large area of adhesion, the pore structure is severely destroyed, and a large amount of polyaniline is mixed in the pores. This is due to the fact that PANI is not present in the PG-P substrate, a primary conductive network based on PANI cannot be formed, and thus a two-stage conductive network cannot be formed, and charge transport efficiency and utilization rate of electroactive materials cannot be improved, resulting in poor electrochemical performance.
Comparative example 3
(1) 3g of PVA is dissolved in 20ml of deionized water to obtain PVA solution; to 254. Mu.l of deionized water, 500. Mu.l of PVA solution was added and stirred and mixed for 5 minutes to homogenize the solution, and 250. Mu.l of 1vol% glutaraldehyde solution was added and crosslinked and cured for 5 minutes to prepare PVA hydrogel.
(2) Soaking the PVA prepared in the step (1) in 30ml of 0.03 mol.l -1 Benzene hydrochlorideThe aniline monomer was fully absorbed by 6 hours in a mixture of an amine solution and 0.3ml 70wt% phytic acid solution.
(3) 0.2282g (1 mmol) of ammonium persulfate is taken and dissolved in 2ml of deionized water, then the solution is rapidly poured into the mixed system of the step (2) to initiate aniline in-situ polymerization, then a film is sealed, the reaction is carried out for 12 hours in an 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 a certain number of pore structures exist in the PANI/PVA conductive hydrogel, PANI is severely agglomerated, which cannot fully exert the conductive ability of PANI. The PANI/PVA substrate is not added with PANI and GO, and a first-stage conductive network with induction effect constructed by PVA, PANI, GO intermolecular interaction force in PPG-P is not present, so that a two-stage conductive network cannot be formed, and in addition, PANI is easy to agglomerate, so that the electrochemical performance of PANI/PVA is poor.
Comparative example 4
(1) (1) preparation of pani dispersion the same as in example 1 (1).
(2) 3g of PVA is dissolved in 20ml of deionized water to obtain PVA solution; 180 μl of 3 mg.ml is first added -1 After the GO dispersion liquid and 500 mu l of PVA solution are uniformly mixed, 65 mu l of PANI dispersion liquid is added into the mixture and stirred and mixed for 5min to uniformly, and finally 250 mu l of 1vol% glutaraldehyde solution is added into the mixture to crosslink and cure for 5min to prepare the substrate hybridization hydrogel PPG with the primary conductive network.
(2) Soaking the PPG prepared in the step (1) in 30ml of 0.03 mol.l -1 In a mixed solution prepared from aniline hydrochloride solution and 0.3ml 70wt% phytic acid solution, aniline self-assembly was adsorbed and induced for 6h.
(3) 0.2282g (1 mmol) of ammonium persulfate is taken and dissolved in 2ml of deionized water, then the solution is rapidly poured into the mixed system of the step (2) to initiate aniline in-situ polymerization, then a film is sealed, the reaction is carried out for 12 hours in an environment of 0-5 ℃, and the PPG-P conductive hydrogel with a two-stage conductive network is obtained after the reaction.
In this comparative example, GO solution and PVA solution were mixed first, and then PANI dispersion and glutaraldehyde were sequentially added, and as can be seen from fig. 5, the network structure of the obtained conductive hydrogel has an aggregation phenomenon of polyaniline in the internal structure, and the network structure is not penetrated, and a lamellar structure is partially shown, so that the number of pores is reduced, compared with example 1. The PANI is added after the GO and the PVA are mixed, so that the dispersion effect of the GO on the PANI cannot be fully exerted, the PANI in the substrate hydrogel is unevenly dispersed, and a large amount of agglomeration is generated, and therefore, the addition sequence is unfavorable for the formation of a primary conductive network, and further, the directional growth of a polyaniline secondary conductive network pair cannot be induced, so that the conductive hydrogel is poor in performance.
Comparative example 5
(1) (1) preparation of PANI dispersion the same as in example 1(1).
(2) 3g of PVA is dissolved in 20ml of deionized water to obtain PVA solution; after mixing 65. Mu.l of PANI dispersion with 500. Mu.l of PVA solution uniformly, 180. Mu.l of 3 mg.ml of PVA solution was added thereto -1 And (3) uniformly mixing the GO dispersion liquid for 5 minutes, and finally adding 250 mu l of 1vol% glutaraldehyde solution, and crosslinking and curing for 5 minutes to prepare the substrate hybridized hydrogel PPG with the primary conductive network.
(2) Soaking the PPG prepared in the step (1) in 30ml of 0.03 mol.l -1 In a mixed solution prepared from aniline hydrochloride solution and 0.3ml 70wt% phytic acid solution, aniline self-assembly was adsorbed and induced for 6h.
(3) 0.2282g (1 mmol) of ammonium persulfate is taken and dissolved in 2ml of deionized water, then the solution is rapidly poured into the mixed system of the step (2) to initiate aniline in-situ polymerization, then a film is sealed, the reaction is carried out for 12 hours in an environment of 0-5 ℃, and the PPG-P conductive hydrogel with a two-stage conductive network is obtained after the reaction.
In this comparative example, the PANI dispersion was first mixed with the PVA solution, and then GO solution and glutaraldehyde were added sequentially. As can be seen from fig. 6, the conductive hydrogel has a large amount of polyaniline aggregates in the internal structure, has a small number of micropore structures, has a fine and discontinuous network structure, and is unfavorable for charge transmission. This is due to the fact that when PANI is first mixed with PVA, PANI is largely agglomerated in PVA solution without the dispersion of GO, and even if GO solution is added later, the dispersion effect is greatly impaired, and PANI cannot be well and uniformly dispersed in PVA. Therefore, the charging sequence is unfavorable for 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 conductive hydrogel has poor performance.
FIG. 7 shows the current densities of the conductive hydrogels prepared in example 1 and comparative examples 1 to 5 at 0.5 A.g -1 Constant current charge-discharge curve and corresponding mass ratio capacitance. As can be seen, the electrically conductive hydrogel PPG-P obtained in example 1 has a viscosity of up to 989F g -1 Meanwhile, the mass ratio capacitor of the capacitor is detected to have good cycling stability, and the capacitor retention rate is 87% after 1000 constant current charge and discharge cycles. In addition, PPG-P also exhibits excellent conductivity (conductivity 5.47S. Mu.m -1 ) And excellent mechanical properties (elongation at break 186%, tensile strength 0.5 MPa). The substrate hybrid hydrogel of the conductive hydrogel PP-P of comparative example 1 was free of GO and had a mass specific capacitance (458 F.g -1 ) Much lower than example 1. In comparative examples 2 and 3, the substrate hybrid hydrogels were not added with PANI dispersion or PANI dispersion and GO dispersion, resulting in poor electrochemical properties (mass specific capacities of 299f·g, respectively) -1 、388F·g -1 ). Comparative examples 4 and 5, in which the order of addition was changed, resulted in the electrochemical properties of the formed conductive hydrogels (mass specific capacitances of 670 F.g, respectively -1 、600F·g -1 ) Nor is it as in example 1.
From the above, only the PPG-P prepared by the method has excellent conductivity, electrochemical performance and tensile performance, and can be widely applied to manufacturing wearable electronic devices such as flexible supercapacitors.
Example 2
(1) (1) 2.5918g (20 mmol) of aniline hydrochloride and 0.4ml of 70wt% phytic acid solution were dissolved in 30ml of deionized water, and designated as solution a; 4.564g (20 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 rapidly pouring the solution b into the solution a, stirring uniformly, sealing the film, and reacting for 12 hours in the environment of 0-5 ℃ to obtain the PANI dispersion liquid.
(2) 3g of PVA is dissolved in 17ml of deionized water to obtain PVA solution; 160 μl of 3 mg.ml was first prepared -1 After uniformly mixing GO dispersion and 65 μl PANI dispersion, adding 500 μl PVA solution, stirring and mixing for 5min to uniformly, and finally adding 250 μl glutaraldehyde solution with concentration of 1vol%, and crosslinking and curing for 5min to obtain the substrate hybridized hydrogel PPG with primary conductive network.
(2) Soaking the PPG prepared in the step (1) in 30ml of 0.03 mol.l -1 In a mixed solution prepared from aniline hydrochloride solution and 0.3ml 70wt% phytic acid solution, aniline self-assembly was adsorbed and induced for 6h.
(3) 0.2282g (1 mmol) of ammonium persulfate is taken and dissolved in 4ml of deionized water, then the solution is rapidly poured into the mixed system of the step (2) to initiate aniline in-situ polymerization, then a film is sealed, the reaction is carried out for 12 hours in an environment of 0-5 ℃, and the PPG-P conductive hydrogel with a two-stage conductive network is obtained after the reaction.
Example 3
(1) (1) 1.5551g (12 mmol) of aniline hydrochloride and 0.4ml of 70wt% phytic acid solution were dissolved in 30ml of deionized water, and designated 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 rapidly pouring the solution b into the solution a, stirring uniformly, sealing the film, and reacting for 12 hours in the environment of 0-5 ℃ to obtain the PANI dispersion liquid.
(2) 3g of PVA is dissolved in 17ml of deionized water to obtain PVA solution; 170 mu l of 3 mg.ml are firstly added -1 After uniformly mixing GO dispersion with 80. Mu.l PANI dispersion, adding 500. Mu.l PVA solution into the mixture, stirring and mixing the mixture for 5min to uniformly, and finally adding 250. Mu.l 1vol% glutaraldehyde solution, and crosslinking and curing the mixture for 5min to prepare the substrate hybridized hydrogel PPG with the primary conductive network.
(2) Soaking the PPG prepared in the step (1) in 30ml of 0.02 mol.l -1 In a mixed solution prepared from aniline hydrochloride solution and 0.3ml 70wt% phytic acid solution, aniline self-assembly was adsorbed and induced for 6h.
(3) Dissolving 0.1465g (3 mmol) of ammonium persulfate in 4ml of deionized water, rapidly pouring the solution into the mixed system of the step (2) to initiate aniline in-situ polymerization, sealing a film, reacting for 12 hours at the temperature of 0-5 ℃, and obtaining the PPG-P conductive hydrogel with a two-stage conductive network after the reaction is finished.
Example 4
(1) (1) 1.5551g (12 mmol) of aniline hydrochloride and 0.4ml of 70wt% phytic acid solution were dissolved in 30ml of deionized water, and designated 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 rapidly pouring the solution b into the solution a, stirring uniformly, sealing the film, and reacting for 12 hours in the environment of 0-5 ℃ to obtain the PANI dispersion liquid.
(2) 2g of PVA is dissolved in 18ml of deionized water to obtain PVA solution; 180 μl of 3 mg.ml is first added -1 After uniformly mixing GO dispersion with 65 μl PANI dispersion, adding 500 μl PVA solution, stirring and mixing for 5min to uniformly, and finally adding 210 μl glutaraldehyde solution with 1vol% for crosslinking and curing for 5min to obtain the substrate hybridized hydrogel PPG with primary conductive network.
(2) Soaking the PPG prepared in the step (1) in 30ml of 0.04 mol.l -1 In a mixed solution prepared from aniline hydrochloride solution and 0.3ml 70wt% phytic acid solution, aniline self-assembly was adsorbed and induced for 6h.
(3) Dissolving 0.4111g (6 mmol) of ammonium persulfate in 10ml of deionized water, rapidly pouring the solution into the mixed system of the step (2) to initiate aniline in-situ polymerization, sealing a film, and reacting for 12 hours at the temperature of 0-5 ℃ to obtain the PPG-P conductive hydrogel with the two-stage conductive network after the reaction.
Example 5
(1) (1) 1.5551g (12 mmol) of aniline hydrochloride and 0.4ml of 70wt% phytic acid solution were dissolved in 30ml of deionized water, and designated 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 rapidly pouring the solution b into the solution a, stirring uniformly, sealing the film, and reacting for 12 hours in the environment of 0-5 ℃ to obtain the PANI dispersion liquid.
(2) 3g of PVA is dissolved in 17ml of deionized water to obtain PVA solution; 180 μl of 3 mg.ml is first added -1 After the GO dispersion and 65. Mu.l of the PANI dispersion were mixed uniformly, 400. Mu.l of PVA solution was added thereto and mixed with stirring for 5 minutes to uniformly, and finally 270. Mu.l of 1vol% glutaraldehyde solution was added thereto and crosslinked and cured for 5 minutes to obtain a polymer having one phaseThe substrate of the secondary conductive network hybridizes to the hydrogel PPG.
(2) Soaking the PPG prepared in the step (1) in 30ml of 0.02 mol.l -1 In a mixed solution prepared from aniline hydrochloride solution and 0.3ml 70wt% phytic acid solution, aniline self-assembly was adsorbed and induced for 6h.
(3) Dissolving 0.1429g (0.6 mmol) of ammonium persulfate in 1ml of deionized water, then rapidly pouring the solution into the mixed system of the step (2) to initiate aniline in-situ polymerization, sealing a film, reacting for 12h in an environment of 0-5 ℃, and obtaining the PPG-P conductive hydrogel with a two-stage conductive network after the reaction is finished.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (5)
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 graphene oxide dispersion liquid and polyaniline dispersion liquid to obtain a mixed solution; then adding polyvinyl alcohol into the mixture and uniformly mixing the mixture; then glutaraldehyde solution is added for crosslinking and curing to prepare the substrate hybridization hydrogel with a primary conductive network;
(2) Soaking the substrate hybridized hydrogel obtained in the step (1) in an aniline solution to obtain an aniline self-assembled mixed system;
(3) And (3) initiating aniline in the aniline self-assembly mixed system obtained in the step (2) to perform in-situ polymerization under the induction action of the primary conductive network to form a polyaniline secondary conductive network which grows on the primary conductive network in a directional manner, thereby obtaining the polyaniline composite flexible conductive hydrogel with the high specific capacitance of the two-stage conductive network.
2. The method for preparing the polyaniline composite flexible conductive hydrogel with high specific capacitance according to claim 1, wherein the method comprises the following steps: the specific preparation steps of the substrate hybridized hydrogel are as follows:
(1) dispersing graphene oxide in water to form a graphene oxide dispersion liquid with the concentration of 3 mg/ml;
(2) 1.2959-2.5918g of aniline hydrochloride and 0.2-0.6ml of 70wt% phytic acid solution are dissolved in 20-40ml of deionized water and marked as solution a; 2.282-4.564g of ammonium persulfate is dissolved in 5-20ml of deionized water and is marked as a solution b; cooling the solution a and the solution b to 0-5 ℃, then rapidly pouring the solution b into the solution a, stirring uniformly, sealing a film, and reacting for 8-15h in an environment of 0-5 ℃ to obtain polyaniline dispersion liquid;
(3) 1-6g of polyvinyl alcohol is dissolved in 10-30ml of deionized water to obtain a polyvinyl alcohol solution; mixing 150-200 mu l of graphene oxide dispersion liquid prepared in the step (1) with 60-80 mu l of polyaniline dispersion liquid prepared in the step (2) uniformly, adding 300-700 mu l of polyvinyl alcohol solution into the mixture, stirring and mixing for 5min to uniformly, adding 200-300 mu l of 1vol% glutaraldehyde solution into the mixture, and crosslinking and curing for 1-10min to obtain the substrate hybridization hydrogel with the primary conductive network.
3. The method for preparing the polyaniline composite flexible conductive hydrogel with high specific capacitance according to claim 1, wherein the method comprises the following steps: the step (2) is specifically to mix 30ml of 0.01-0.05mol/l aniline hydrochloride solution and 0.2-0.6ml of 70wt% phytic acid solution, then soak the substrate hybrid hydrogel in the mixed solution for 4-8h, adsorb and induce aniline to self-assemble in a directional way, so as to form a mixed system.
4. The method for preparing the polyaniline composite flexible conductive hydrogel with high specific capacitance according to claim 1, wherein the method comprises the following steps: and (3) dissolving 0.1141-0.4564g of ammonium persulfate in 1-10ml of deionized water, rapidly pouring the solution into the aniline self-assembly mixed system obtained in the step (2), sealing a film, and reacting for 10-15h in an environment of 0-5 ℃ to obtain the polyaniline composite flexible conductive hydrogel with the high specific capacitance and two-stage conductive network.
5. A high specific capacitance polyaniline composite flexible conductive hydrogel made according to any one of claims 1-4.
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