CN112430394B - Conductive enhanced polypyrrole/graphene/gelatin composite flexible electrode material and preparation method thereof - Google Patents
Conductive enhanced polypyrrole/graphene/gelatin composite flexible electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a conductive enhanced polypyrrole/graphene/gelatin composite flexible electrode material and a preparation method thereof, and belongs to the field of flexible electronic materials. The preparation method specifically comprises the steps of preparing a polypyrrole/reduced graphene oxide/silver nano hybrid material, then preparing a polypyrrole/reduced graphene oxide/silver/gelatin composite sol, then preparing a super-macroporous gel with good openings and uniformly distributed holes by low-temperature freezing, and finally further improving the mechanical property by chemical crosslinking to obtain the conductive enhanced composite flexible electrode material. The conductive enhanced composite flexible electrode material prepared by the invention has excellent conductivity and mechanical flexibility, and has wide application prospect in the field of flexible electronic products.
Description
Technical Field
The invention belongs to the field of flexible electronic materials, and particularly relates to a conductive enhanced polypyrrole graphene composite gelatin flexible electrode material and a preparation method thereof.
Background
Flexible electronic products such as wearable equipment, electronic skins, implantable electronic devices, soft robots, novel flexible human-computer interfaces and the like play more and more important roles in the fields of human health detection, biological medicine and the like, and the interaction relationship between the existing medical health system and human and electronic products is greatly improved. As a key component in flexible electronic products, flexible electrodes have been the focus of research.
The flexible electrode material prepared by compounding the conductive filler and the hydrogel has the advantages of good biocompatibility, mechanical flexibility, wearability, more stable skin contact interface and the like. However, the existing hydrogel-based flexible electrode still has the problems of insufficient fatigue resistance, incapability of keeping a good fit state between the electrode and the skin in the process of human body movement, easy motion artifact, inferior electrical signal conductivity to metal, low signal-to-noise ratio of collected electromyographic signals and the like.
The graphene is in six sp2Hybrid carbon atoms are combined to form a two-dimensional crystal structure, and the electron orbits of the two-dimensional crystal structure are distributed close to the Fermi level, so that the graphene has outstanding electrical properties, mechanical properties, carrier mobility, flexibility and huge specific surface area. In order to solve the problems of mechanical fatigue and electric signal conduction of the flexible electrode material, the graphene is used as the conductive filler of the flexible electrode, so that the electrode material is endowed with good fatigue resistance, conductivity and high sensitivity. Meanwhile, aiming at the problem that the current flexible electrode material is easy to displace with the epidermis in the process of human body movement, so that the capacitance between the electrode and the skin is changed, the conductive filler is compounded with gelatin with good biocompatibility, and the electrode can adapt to various contours of the body surface of the human body by utilizing the affinity of the gelatin component and the human body, so that the electrode and the skin can be kept in a good fit state, and the displacement between the electrode and the skin is avoided; in addition, polypyrrole is used as a conductive polymer with stable performance, and has high conductivity and biocompatibility. The polypyrrole and the gelatin can be compatible with each other through hydrogen bond interaction, and the unsaturated five-membered ring of the polypyrrole can be compatible with sp of graphene2The hybrid plane forms a local network conduction structure through pi bonds and van der waals force, thereby having synergistic conduction effect and enhancing the electrode materialThe impedance and conductivity properties of the material. Meanwhile, the sensitivity and the signal-to-noise ratio of the electrode material can be further improved by depositing the silver nano particles on the conductive hybrid material; aiming at the problems that the prior flexible electrode has poor air permeability and sweat releasing performance, is easy to cause skin allergy and generates motion artifacts, the invention endows the flexible electrode with high air permeability by a low-temperature physical hole making mode, and the regular super-macroporous structure accelerates the transfer of ions, thereby improving the electrochemical performance of the electrode.
Disclosure of Invention
The invention aims to provide a conductive enhanced polypyrrole/graphene/gelatin composite flexible electrode material and a preparation method thereof aiming at the defects of the prior art, and the electrochemical performance and the mechanical performance of the flexible electrode material can be fully improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a conductive enhanced polypyrrole/graphene/gelatin composite flexible electrode material is prepared by the following steps:
(1) preparing polypyrrole/reduced graphene oxide/silver nano hybrid materials;
(2) preparing polypyrrole/reduced graphene oxide/silver/gelatin composite sol;
(3) preparing ultra-large pore gel with good pores and uniformly distributed pores by low-temperature freezing;
(4) the conductive enhanced composite flexible electrode material is prepared by chemical crosslinking and gelling.
The specific steps of the step (1) are as follows: mixing 12 mL and 1 mg/mL pyrrole ethanol solution, 50 mL and 2 mg/mL graphene oxide ethanol solution and 6 mL and 1 mg/mL silver nitrate aqueous solution at room temperature, ultrasonically stirring for at least 1 h, then transferring the uniformly dispersed mixed solution into a 100 mL autoclave lined with polytetrafluoroethylene, carrying out hydrothermal reaction for 10 h at 120 ℃, slowly cooling at room temperature, carrying out centrifugal filtration at the rotation speed of 5000 rpm, washing for at least 3 times by using methanol, and finally drying in a vacuum drying oven at 50 ℃ to obtain the polypyrrole/reduced graphene oxide/silver nano hybrid material.
The specific steps of the step (2) are as follows: dispersing 1.6 g of gelatin into 17.5 g of deionized water, stirring at 50 ℃ until the gelatin is completely dissolved, adding 0.8 g of polypyrrole/reduced graphene oxide/silver nano hybrid material prepared in the step (1) under the stirring condition, continuously stirring for 30 min, and performing ultrasonic treatment for 30 min to obtain polypyrrole/reduced graphene oxide/silver/gelatin composite sol.
The specific steps of the step (3) are as follows: pouring the composite sol obtained in the step (2) into a required mould, placing the mould in liquid nitrogen for freezing for 6 hours, freeze-drying the mould, and then soaking the mould in deionized water to prepare super-macroporous gel;
the specific steps of the step (4) are as follows: and (3) soaking the ultra-macroporous gel prepared in the step (3) in 0.5 mass percent genipin aqueous solution at room temperature for 8 hours to chemically crosslink the gel, and then soaking and cleaning the obtained product in deionized water to obtain the conductive enhanced composite flexible electrode material.
The invention has the following remarkable advantages:
(1) the polypyrrole/reduced graphene oxide/silver nano hybrid material is prepared by a one-step hydrothermal method, wherein the large specific surface area of graphene provides sufficient active sites for the growth of polypyrrole and silver nanoparticles, the polypyrrole and silver nanoparticles have excellent electrical properties, the impedance characteristic and the conductivity of the flexible electrode material are enhanced by the hybrid composite material, and the sensitivity and the signal-to-noise ratio of the flexible electrode material are further improved;
(2) the invention adopts biocompatible gelatin as the substrate of the flexible electrode, which shows good affinity to human skin, and a large number of hydrophilic functional groups exist in the gelatin, thereby providing reliable support for improving the adhesion of materials;
(3) according to the invention, the gel with uniform holes and a super-macroporous structure is prepared in a low-temperature physical hole making manner, the obtained flexible electrode can be endowed with high air permeability, and the uniform and porous structure can shorten the ion transfer time and improve the electrochemical performance of the electrode material;
(4) the conductive enhanced composite flexible electrode material provided by the invention not only improves the electrochemical performance, but also enhances the mechanical flexibility of the conductive enhanced composite flexible electrode material due to physical crosslinking with gelatin.
Drawings
FIG. 1 is a scanning electron micrograph of composite electrode materials prepared in example (a) and comparative example 1 (b);
FIG. 2 is a graph of the AC impedance of composite electrode materials prepared in example (a) and comparative example 1 (b);
FIG. 3 is a tensile stress-strain graph of the composite electrode materials prepared in example (a) and comparative example 1 (b);
fig. 4 is a physical diagram of an electrode element prepared using the composite flexible electrode material prepared in example.
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 (b):
(1) mixing 12 mL and 1 mg/mL pyrrole ethanol solution, 50 mL and 2 mg/mL graphene oxide ethanol solution and 6 mL and 1 mg/mL silver nitrate aqueous solution at room temperature, ultrasonically stirring for 1 h, then transferring the uniformly dispersed mixed solution into a 100 mL autoclave lined with polytetrafluoroethylene, carrying out hydrothermal reaction for 10 h at 120 ℃, slowly cooling at room temperature, centrifuging and filtering at the rotating speed of 5000 rpm, washing for 3 times by using methanol, and finally drying in a vacuum drying oven at 50 ℃ to prepare the polypyrrole/reduced graphene oxide/silver nano hybrid material.
(2) Dispersing 1.6 g of gelatin into 17.5 g of deionized water, stirring at 50 ℃ until the gelatin is completely dissolved, adding 0.8 g of polypyrrole/reduced graphene oxide/silver nano hybrid material prepared in the step (1) under the stirring condition, continuously stirring for 30 min, and performing ultrasonic treatment on the uniformly stirred composite solution for 30 min to obtain polypyrrole/reduced graphene oxide/silver/gelatin composite sol.
(3) Pouring the composite sol obtained in the step (2) into a required mould, placing the mould in liquid nitrogen for freezing for 6 hours, freeze-drying the mould, and then soaking the mould in deionized water to prepare super-macroporous gel with uniformly distributed holes;
(4) and (3) soaking the ultra-macroporous gel prepared in the step (3) in 0.5 mass percent genipin aqueous solution at room temperature for 8 hours to chemically crosslink the gel, and then soaking and cleaning the obtained product in deionized water to obtain the conductive enhanced composite flexible electrode material.
Comparative example 1
(1) Mixing 12 mL and 1 mg/mL pyrrole ethanol solution, 50 mL and 2 mg/mL graphene oxide ethanol solution and 6 mL and 1 mg/mL silver nitrate aqueous solution at room temperature, ultrasonically stirring for 1 h, then transferring the uniformly dispersed mixed solution into a 100 mL autoclave lined with polytetrafluoroethylene, carrying out hydrothermal reaction for 10 h at 120 ℃, slowly cooling at room temperature, centrifuging and filtering at the rotating speed of 5000 rpm, washing for 3 times by using methanol, and finally drying in a vacuum drying oven at 50 ℃ to prepare the polypyrrole/reduced graphene oxide/silver nano hybrid material.
(2) Dispersing 1.6 g of gelatin into 17.5 g of deionized water, stirring at 50 ℃ until the gelatin is completely dissolved, adding 0.8 g of polypyrrole/reduced graphene oxide/silver nano hybrid material prepared in the step (1) under the stirring condition, continuously stirring for 30 min, and performing ultrasonic treatment on the uniformly stirred composite solution for 30 min to obtain polypyrrole/reduced graphene oxide/silver/gelatin composite sol.
(3) And (3) adding 20 mu l of 0.5 mass percent genipin aqueous solution into the composite sol prepared in the step (2) in a constant-temperature water bath at 40 ℃, quickly stirring for 2 min, then pouring the mixture into a required mould, and standing at room temperature for 16 h to crosslink and form gel, thereby obtaining the polypyrrole graphene composite gelatin electrode material.
FIG. 1 is a scanning electron micrograph of composite electrode materials prepared in example (a) and comparative example 1 (b). As can be seen from the figure, the composite flexible electrode material prepared by low-temperature freezing in the example has a super-macroporous structure with regular arrangement and uniform distribution, while the composite electrode material prepared in the comparative example 1 has no obvious pore structure.
FIG. 2 is a graph showing the AC impedance of the composite electrode materials prepared in example (a) and comparative example 1 (b). As can be seen from the figure, the composite flexible electrode material obtained in the example has almost no semicircle in a high-frequency region, while the composite electrode material obtained in the comparative example 1 has an obvious semicircle in the high-frequency region and a large diameter, which shows that the composite flexible electrode material containing the super-macroporous structure has extremely small charge transfer resistance and high conductivity; meanwhile, the linear slope of the composite flexible electrode material in the low-frequency region obtained in the embodiment is greater than 45 degrees and is obviously greater than that of the composite electrode material prepared in the comparative example 1, and the results show that the composite flexible electrode material containing the super-macroporous structure is high in ion diffusion speed and has excellent ion conductivity.
Fig. 3 is a tensile stress-strain graph of the composite electrode materials prepared in example (a) and comparative example 1 (b). As can be seen from the figure, the composite flexible electrode material prepared in the example can bear the maximum tensile stress of 6.93 MPa, and the elongation at break is up to 356%, while the composite electrode material prepared in the comparative example 1 can bear the maximum tensile stress of 1.78 MPa, and the elongation at break is 195%, which indicates that the composite flexible electrode material containing the super-macroporous structure has excellent electrochemical performance and mechanical performance.
Comparative example 2
(1) Mixing 12 mL and 1 mg/mL pyrrole ethanol solution, 50 mL and 2 mg/mL graphene oxide ethanol solution and 6 mL and 1 mg/mL silver nitrate aqueous solution at room temperature, ultrasonically stirring for 1 h, then transferring the uniformly dispersed mixed solution into a 100 mL autoclave lined with polytetrafluoroethylene, carrying out hydrothermal reaction for 10 h at 120 ℃, slowly cooling at room temperature, centrifuging and filtering at the rotating speed of 5000 rpm, washing for 3 times by using methanol, and finally drying in a vacuum drying oven at 50 ℃ to prepare the polypyrrole/reduced graphene oxide/silver nano hybrid material.
(2) Dispersing 2.4 g of gelatin into 17.5 g of deionized water, stirring at 50 ℃ until the gelatin is completely dissolved, adding 0.8 g of polypyrrole/reduced graphene oxide/silver nano hybrid material prepared in the step (1) under the stirring condition, continuously stirring for 30 min, and performing ultrasonic treatment on the uniformly stirred composite solution for 30 min to obtain polypyrrole/reduced graphene oxide/silver/gelatin composite sol.
(3) Pouring the composite sol obtained in the step (2) into a required mould, placing the mould in liquid nitrogen for freezing for 6 hours, freeze-drying the mould, and then soaking the mould in deionized water to prepare super-macroporous gel with uniformly distributed holes;
(4) and (3) soaking the ultra-macroporous gel prepared in the step (3) in 0.5 mass percent genipin aqueous solution at room temperature for 8 hours to chemically crosslink the gel, and then soaking and cleaning the obtained product in deionized water to obtain the composite flexible electrode material.
Through detection, the charge transfer impedance of the prepared composite flexible electrode material is increased, the ion diffusion rate is reduced, the electronic conductivity and the ionic conductivity of the electrode material are obviously reduced, and the increase of the gelatin content and the reduction of the conductivity of the electrode material are proved; meanwhile, the composite electrode material can bear the maximum tensile stress of 6.01 MPa, and the elongation at break reaches 328%. Electrochemical performance and mechanical performance tests show that the electrochemical performance and the mechanical performance of the prepared flexible electrode material are reduced.
Comparative example 3
(1) Mixing 12 mL and 1 mg/mL pyrrole ethanol solution, 50 mL and 2 mg/mL graphene oxide ethanol solution and 6 mL and 1 mg/mL silver nitrate aqueous solution at room temperature, ultrasonically stirring for 1 h, then transferring the uniformly dispersed mixed solution into a 100 mL autoclave lined with polytetrafluoroethylene, carrying out hydrothermal reaction for 10 h at 120 ℃, slowly cooling at room temperature, centrifuging and filtering at the rotating speed of 5000 rpm, washing for 3 times by using methanol, and finally drying in a vacuum drying oven at 50 ℃ to prepare the polypyrrole/reduced graphene oxide/silver nano hybrid material.
(2) Dispersing 0.8 g of gelatin into 17.5 g of deionized water, stirring at 50 ℃ until the gelatin is completely dissolved, adding 0.8 g of polypyrrole/reduced graphene oxide/silver nano hybrid material prepared in the step (1) under the stirring condition, continuously stirring for 30 min, and performing ultrasonic treatment on the uniformly stirred composite solution for 30 min to obtain polypyrrole/reduced graphene oxide/silver/gelatin composite sol.
(3) Pouring the composite sol obtained in the step (2) into a required mould, placing the mould in liquid nitrogen for freezing for 6 hours, freeze-drying the mould, and then soaking the mould in deionized water to prepare super-macroporous gel with uniformly distributed holes;
(4) and (3) soaking the ultra-macroporous gel prepared in the step (3) in 0.5 mass percent genipin aqueous solution at room temperature for 8 hours to chemically crosslink the gel, and then soaking and cleaning the obtained product in deionized water to obtain the composite flexible electrode material.
Through detection, the electrochemical performance of the prepared composite flexible electrode material is improved compared with that of the embodiment, which is attributed to the increase of the content of the conductive hybrid material; the electrode material can bear the maximum tensile stress of 3.72 MPa, the elongation at break is 256%, namely the mechanical flexibility of the material is obviously reduced, so that the content of the conductive hybrid material is increased, the electrochemical performance of the electrode material is improved, and the excellent mechanical performance cannot be maintained.
Comparative example 4
(1) Mixing 12 mL and 1 mg/mL pyrrole ethanol solution, 50 mL and 2 mg/mL graphene oxide ethanol solution and 6 mL and 1 mg/mL silver nitrate aqueous solution at room temperature, ultrasonically stirring for 1 h, then transferring the uniformly dispersed mixed solution into a 100 mL autoclave lined with polytetrafluoroethylene, carrying out hydrothermal reaction for 10 h at 120 ℃, slowly cooling at room temperature, centrifuging and filtering at the rotating speed of 5000 rpm, washing for 3 times by using methanol, and finally drying in a vacuum drying oven at 50 ℃ to prepare the polypyrrole/reduced graphene oxide/silver nano hybrid material.
(2) Dispersing 1.6 g of gelatin into 17.5 g of deionized water, stirring at 50 ℃ until the gelatin is completely dissolved, adding 2 g of the polypyrrole/reduced graphene oxide/silver nano hybrid material prepared in the step (1) under the stirring condition, continuously stirring for 30 min, and performing ultrasonic treatment on the uniformly stirred composite liquid for 30 min to obtain polypyrrole/reduced graphene oxide/silver/gelatin composite sol.
(3) Pouring the composite sol obtained in the step (2) into a required mould, placing the mould in liquid nitrogen for freezing for 6 hours, freeze-drying the mould, and then soaking the mould in deionized water to prepare super-macroporous gel with uniformly distributed holes;
(4) and (3) soaking the ultra-macroporous gel prepared in the step (3) in 0.5 mass percent genipin aqueous solution at room temperature for 8 hours to chemically crosslink the gel, and then soaking and cleaning the obtained product in deionized water to obtain the conductive enhanced composite flexible electrode material.
Through detection, the prepared composite flexible electrode material has excellent electrochemical performance; however, the electrode material can only bear the maximum tensile stress of 1.62 MPa, and the elongation at break is only 149%, which shows that the electrode material has high rigidity and poor flexibility due to excessive content of the conductive hybrid material.
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 (3)
1. A preparation method of a conductive enhanced polypyrrole/graphene/gelatin composite flexible electrode material is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing polypyrrole/reduced graphene oxide/silver nano hybrid materials;
(2) preparing polypyrrole/reduced graphene oxide/silver/gelatin composite sol;
(3) preparing ultra-large pore gel with good pores and uniformly distributed pores by low-temperature freezing;
(4) preparing a conductive enhanced composite flexible electrode material by chemical crosslinking and gelling;
the preparation steps of the polypyrrole/reduced graphene oxide/silver nano hybrid material in the step (1) are as follows: mixing 12 mL of pyrrole ethanol solution, 1 mg/mL of pyrrole ethanol solution, 50 mL of graphene oxide ethanol solution, 2 mg/mL of graphene oxide ethanol solution, 6 mL of silver nitrate aqueous solution and 1 mg/mL of silver nitrate aqueous solution at room temperature, ultrasonically stirring for at least 1 h, then transferring the obtained mixed solution into an autoclave lined with polytetrafluoroethylene, carrying out hydrothermal reaction for 10 h at 120 ℃, slowly cooling at room temperature, carrying out centrifugal filtration at the rotating speed of 5000 rpm, washing for at least 3 times with methanol, and carrying out vacuum drying at 50 ℃ to obtain the polypyrrole/reduced graphene oxide/silver nano hybrid material;
the preparation method of the polypyrrole/reduced graphene oxide/silver/gelatin composite sol in the step (2) comprises the following specific steps: dispersing 1.6 g of gelatin into 17.5 g of deionized water, stirring at 50 ℃ until the gelatin is completely dissolved, adding 0.8 g of polypyrrole/reduced graphene oxide/silver nano hybrid material prepared in the step (1) under the stirring condition, continuously stirring for 30 min, and performing ultrasonic treatment for 30 min to obtain polypyrrole/reduced graphene oxide/silver/gelatin composite sol;
the preparation steps of the super macroporous gel in the step (3) are as follows: and (3) pouring the composite sol obtained in the step (2) into a required mould, putting the mould into liquid nitrogen for freezing for 6 hours, freeze-drying the mould, and then soaking the mould into deionized water to obtain the composite sol.
2. The preparation method of the conductive enhanced polypyrrole/graphene/gelatin composite flexible electrode material according to claim 1, wherein the preparation method comprises the following steps: and (4) chemically crosslinking and gelling, namely soaking the super-macroporous gel prepared in the step (3) in 0.5 mass percent genipin aqueous solution at room temperature for 8 h to chemically crosslink the gel, and then soaking and cleaning the obtained product in deionized water to obtain the conductive enhanced composite flexible electrode material.
3. The conductive reinforced polypyrrole/graphene/gelatin composite flexible electrode material prepared by the method of claim 1 or 2.
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| CN107737370A (en) * | 2017-11-20 | 2018-02-27 | 西南交通大学 | It is a kind of to be used for the high-strength of repair of cartilage, superlastic, the preparation method of conductive hydrogel |
| CN111768976A (en) * | 2020-07-20 | 2020-10-13 | 桂林理工大学 | Polypyrrole/silver/graphene oxide composite material and preparation method and application thereof |
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| CN107737370A (en) * | 2017-11-20 | 2018-02-27 | 西南交通大学 | It is a kind of to be used for the high-strength of repair of cartilage, superlastic, the preparation method of conductive hydrogel |
| CN111768976A (en) * | 2020-07-20 | 2020-10-13 | 桂林理工大学 | Polypyrrole/silver/graphene oxide composite material and preparation method and application thereof |
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| Title |
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| Self-healing conductive hydrogels based on alginate, gelatin and polypyrrole serve as a repairable circuit and a mechanical sensor;Kai Ren等;《Journal of Materials Chemistry B》;20190925(第7期);全文 * |
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