CN108822548B - Highly-stretchable high-sensitivity 3D printing graphene-based flexible sensor and preparation method thereof - Google Patents
Highly-stretchable high-sensitivity 3D printing graphene-based flexible sensor and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a highly stretchable and highly sensitive 3D printing graphene-based flexible sensor and a preparation method thereof. According to the invention, the controllable design of the macroscopic shape of the primary sensing structure is realized by using a 3D printing technology, the highly stretchable characteristic of the sensor is realized by using the macroscopic grid filling structure, and meanwhile, the sensitivity of the sensor in a wide strain interval is greatly improved by using the two-stage sensing structure. The method disclosed by the invention is simple to operate, and the prepared graphene-based flexible sensor has the characteristics of high sensitivity and high stretchability, and has the potential to be widely applied to the fields of intelligent medical treatment, health monitoring, human-computer interaction and the like.
Description
Technical Field
The invention relates to a flexible strain sensor and a preparation method thereof, in particular to a graphene-based flexible sensor with high sensitivity coefficient and high strain induction range, belonging to the fields of flexibility and wearable electronics and the technical field of composite materials.
Background
In recent years, with the introduction of concepts such as smart medical treatment, health monitoring, human-computer interaction and the like, the market has made higher requirements on flexible wearable electronic equipment, andthe performance of flexible sensors as a core component of wearable devices is critical in determining the performance of the final device and product. Generally, the flexible sensor can output the detected deformation of the material in the form of an electrical signal (for example, the change of the resistance R value), so as to monitor different physiological activities of the human body (for example, small strains such as respiration, heartbeat, pulse and the like, large strains such as bending and rotation of hands, arms, legs and spine). Over the last few years, research on flexible sensors has mainly focused on structural design and new material development, and the like, and sensors in the form of conductive fabrics, conductive fillers filled or coated with elastomers, conductive polymer gels and the like have been developed endlessly; conductive materials such as metal nanoparticles, nanowires, carbon nanotubes and graphene are also sequentially applied to the preparation of flexible sensors. Liu et al adhered multiple layers of reduced graphene oxide films on elastic tapes in different stretching states to prepare a flexible sensor with a scale-like structure, wherein the flexible sensor has a tensile strain of up to 82% and a sensitivity GF factor (the sensitivity GF factor is defined as delta R/R)0And the slope of the strain epsilon curve) reached 150 (ACS Nano, DOI: 10.1021/acsnano.6b03813). Yin et al, a flexible sensor prepared by pyrolyzing a cotton bandage coated with Graphene Oxide (GO) had a GF value of 416 when the tensile strain was 0-40%, and reached a GF value of 3667 when the tensile strain was 48-57% (ACS appl. mater. Interfaces, DOI: 10.1021/acsami.7b 09652). Tao et al reduced GO coated on the surface of silicone rubber by one step through laser direct writing, and the GF value of the prepared sensor reaches 457 at 35% strain and is 268 at 100% maximum strain (Nanoscale, DOI: 10.1039/c7nr01862 b). Patent CN 107655397 a utilizes graphene fiber to weave a mesh graphene film, and further attaches the graphene film to a flexible substrate to prepare a sensor having high sensitivity coefficient and large strain induction range. In patent CN 107655398A, graphene and a cracked nickel film are sequentially coated with polyurethane sponge from inside to outside to form a composite material, and further, a sensor prepared by PDMS encapsulation can greatly improve the sensitivity of the sensor in the stretching process.
Despite the significant research results, the contradiction between high sensitivity and high tensile property still exists in the current flexible sensor, that is, the flexible sensor which obtains high tensile property and high sensitivity at the same time is still a common problem. On one hand, the large measurement range requires that the material still keeps the communication of the conductive network when being greatly deformed, and on the other hand, the high sensitivity requires that the structure of the conductive network of the material is remarkably changed in the strain process. It follows that solving the above contradiction, achieving simultaneous improvement in sensitivity and measurable strain range of flexible sensors is a very challenging issue.
Disclosure of Invention
The invention aims to solve the problem that the existing flexible sensor cannot simultaneously obtain the contradiction between a high sensitivity coefficient and a high strain induction range, so as to meet the requirements of the flexible sensor on a larger strain induction range and higher monitoring precision required in the fields of intelligent medical treatment, health monitoring, human-computer interaction and the like. Therefore, the invention provides the graphene-based flexible sensor with high sensitivity coefficient and high strain induction range and the preparation method thereof.
In order to achieve the above object, according to a first aspect of the present invention, there is provided a material for manufacturing a graphene-based flexible sensor, the graphene-based flexible sensor having a two-stage sensing structure, wherein the one-stage sensing structure is formed by a conductive filler filled elastomer composite material, and the two-stage sensing structure is formed by coating graphene on the surface of the one-stage sensing structure. In the primary sensing structure, the existence of the conductive filler effectively forms a conductive path in the elastic polymer on one hand, and the conductive filler is used as a rheological modifier of the 3D printing material on the other hand, so that the smooth proceeding of the 3D printing process is ensured, and the controllable design of the macroscopic structure of the sensor is further realized. The formation of the filling type conductive network in the primary sensing structure can not only ensure that the sensing material has a higher GF value under large deformation, but also can assist the graphene sheets which are arranged in a laminated manner and separated from each other in the secondary sensing structure to form a partial conductive loop by utilizing the graphene network in the elastic polymer matrix during medium deformation, thereby effectively increasing the sensitivity of the sensor under medium strain. And under small strain, the sensitivity of the sensor mainly comes from the slip separation and recovery between graphene sheets of the laminated structure.
The invention provides a highly stretchable and highly sensitive 3D printing graphene-based flexible sensor, which has a two-stage sensing structure, wherein: the primary sensing structure is formed by filling an elastomer composite material with a conductive filler, and the secondary sensing structure is formed by coating reduced graphene oxide on the surface of the primary sensing structure; the mass ratio of the conductive filler to the elastomer composite material is 1:20-1: 1; the rheological property of the 3D printing material after the solvent is volatilized is as follows: at a shear rate of 0.1s-1The apparent viscosity at 25 ℃ is 1000-50000 Pa.s, preferably 10000-20000 Pa.s.
In the invention, the conductive filler selected by the primary sensing structure is carbon conductive filler.
In the invention, the carbon-based conductive filler is one or more of carbon black, carbon nano tube or graphene.
In the invention, the elastomer selected by the primary sensing structure is one or more of thermoplastic polyurethane elastomer (TPU), Polydimethylsiloxane (PDMS) or silicone rubber (Ecoflex).
The invention provides a preparation method of a highly stretchable and highly sensitive 3D printing graphene-based flexible sensor, which comprises the following specific steps:
(1) solution mixing is carried out on the conductive filler and the elastomer composite material according to a proportion at normal temperature, after the solvent is further volatilized, a 3D printing material is formed, a related printing structure is designed through a computer, and a primary sensing structure is printed out in a 3D mode;
(2) printing the primary sensing structure printed by the 3D printing in the step (1) for curing and crosslinking, and performing plasma treatment on the surface of the cured and crosslinked material;
(3) further coating the surface of the primary sensing structure subjected to the plasma surface treatment with water-soluble polymer electrolyte with positive electricity;
(4) coating Graphene Oxide (GO) on the surface of the primary sensing structure coated with the polymer electrolyte through electrostatic interaction, and reducing the coated GO into RGO through a chemical reduction method to obtain a sensing material with a secondary sensing structure;
(5) and (5) packaging the sensing material of the secondary sensing structure obtained in the step (4) on an extraction electrode to form the graphene-based flexible sensor.
In the invention, the preparation method of the graphene-based flexible sensor according to claim 5, wherein the mass ratio of the conductive filler to the elastomer material is 1:20-1: 1.
In the invention, the solvent for mixing the elastomer composite material and the conductive filler in the solution comprises one or more of ethyl acetate, xylene, tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetone or cyclohexane.
In the invention, the surface of the primary sensing structure after plasma surface treatment is further coated with a water-soluble polymer electrolyte with positive electricity, wherein the water-soluble polymer electrolyte comprises one or more of Polyethyleneimine (PEI), poly (diallyldimethylammonium chloride) (PDDA) or poly (N, N-dimethylacrylamide) (PDMA).
In the invention, the reducing agent selected in the chemical reduction process for coating GO in the step (4) comprises one or more of hydrazine hydrate, hydroiodic acid, sodium borohydride, ascorbic acid, ethylenediamine and ammonia water; the reduction conditions are as follows: and (3) placing the obtained GO-coated sensing material in the chemical reducing agent solution or steam atmosphere at the temperature of 25-100 ℃, and carrying out reduction treatment for 2-72 hours.
The invention has the beneficial effects that: by applying the technical scheme, the two-stage sensing structure design is carried out on the graphene-based flexible sensor through the 3D printing technology and the surface coating technology, wherein the first-stage sensing structure is formed by filling the conductive filler with the elastomer composite material, the second-stage sensing structure is formed by coating the graphene on the surface of the first-stage sensing structure, and finally the sensing material is packaged after the electrode is led out to form the flexible sensor, so that the graphene-based flexible sensor has the characteristics of high sensitivity and high stretchability. The method disclosed by the invention is simple to operate, and the prepared flexible sensor is excellent in comprehensive performance and has the potential to be widely applied to the fields of intelligent medical treatment, health monitoring, human-computer interaction and the like.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention without limiting the invention. In the drawings:
FIG. 1 shows a flow chart of a manufacturing scheme for a flexible sensor according to the present invention;
fig. 2 shows the variation of modulus with shear stress for PDMS/graphene 3D printing materials with different graphene addition ratios prepared according to the method in example 1 of the present invention;
fig. 3 shows photographs of PDMS/graphene materials with different macrostructures printed in 3D according to the method of example 1 before and after coating graphene;
fig. 4 shows a graph of the relative resistance change with strain for a 3D printed square grid structure flexible sensor prepared according to the method of example 1 of the present invention.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
Example 1
Solution mixing 100 parts (by mass) of a PDMS main agent and different parts of graphene in an ethyl acetate solvent, and adding 10 parts of a PDMS curing agent into the system after the solvent is evaporated, wherein fig. 2 shows the change curve of the modulus of PDMS/graphene 3D printing materials with different graphene addition ratios, which are prepared according to the method in embodiment 1 of the present invention, along with the shear stress; 3D printing is carried out by using the mixed material to form a corrugated net-shaped three-dimensional structure. Placing the printed three-dimensional structure in an oven at 80 ℃ for curing for 6 hours, then placing the cured three-dimensional structure in oxygen plasma for processing for 2 minutes, further immersing the material in a PEI solution of 2.5 mg/ml for 10 minutes, taking out the material for drying, immersing the material in a GO solution of 3mg/ml for 10 minutes, taking out the material for drying and cleaning, then placing the material in a HI acid solution for reducing for 30 minutes at 60 ℃, taking out the material for cleaning, then connecting an electrode, and impregnating and packaging the above materials by using a PDMS solution diluted by n-hexane to prepare the flexible sensor. Fig. 3 shows photographs of 3D-printed PDMS/graphene materials with different macrostructures before and after coating graphene prepared according to the method of example 1 of the present invention. Fig. 4 shows a graph of the change of the relative resistance value of the flexible sensor of the 3D-printed mesh structure prepared according to the method of example 1 of the present invention as a function of strain, and it can be seen that the sensitivity factor of the flexible sensor at a strain range of 85% to 160% is 364, and the maximum tensile set is 210%.
Example 2
And (2) carrying out solution mixing on 100 parts (parts are mass parts) of TPU, 10 parts of carbon black and 5 parts of carbon nano tube in a tetrahydrofuran solvent, and evaporating the solvent to obtain the 3D printed material. 3D printing is carried out on the mixed material to form a corrugated net-shaped three-dimensional structure, the printed three-dimensional structure is placed in deionized water for 1 hour and then is placed in a 60 ℃ drying oven for drying for 2 hours, then the three-dimensional structure is placed in oxygen plasma for processing for 2 minutes, the material is further immersed in 3.5 mg/ml PDDA solution for 10 minutes, the material is taken out for drying and then is immersed in 3mg/ml GO solution for 10 minutes, the material is taken out for drying and cleaning and then is placed in HI acid solution for reducing for 30 minutes at 95 ℃, an electrode is taken out for cleaning and then is connected, and the material is soaked and packaged by PDMS solution diluted by n-hexane to prepare the flexible sensor. The sensitivity factor of the 3D printed mesh structured flexible sensor prepared by this method was 275 with a maximum tensile set of 185%.
Example 3
The preparation method comprises the following steps of carrying out solution mixing on 100 parts (in parts by mass) of an agent A of Ecoflex silicon rubber and 20 parts of graphene in a xylene solvent, adding 100 parts of an agent B of Ecoflex silicon rubber into a system after the solvent is evaporated, uniformly mixing, and carrying out 3D printing by using the mixed material to form the corrugated mesh three-dimensional structure. Placing the printed three-dimensional structure in an oven at 80 ℃ for curing for 6 hours, then placing the cured three-dimensional structure in oxygen plasma for processing for 2 minutes, further immersing the material in a PDMA (polymer dispersed MA) solution of 3mg/ml for 10 minutes, taking out the material for drying, immersing the material in a GO solution of 3mg/ml for 10 minutes, taking out the material for drying and cleaning, then placing the material in a HI acid solution for reducing for 30 minutes at 95 ℃, taking out the material for cleaning, then connecting an electrode, and impregnating and packaging the above materials by using a PDMS solution diluted by n-hexane to prepare the flexible sensor. The sensitivity factor of the 3D-printed grid-structured flexible sensor prepared by this method was 489, with a maximum tensile set of 179%.
Comparative example 1
100 parts (in parts by mass) of Ecoflex silicon rubber (including an agent A and an agent B) and 10 parts of graphene are subjected to solution mixing in a xylene solvent, the uniformly mixed solution is evaporated in a watch glass to form a natural film, the natural film is cured for 6 hours in an oven at the temperature of 80 ℃, and the cured film is cut and connected to an electrode to prepare the flexible sensor. The flexible strain sensor of the embodiment has no graphene coating, so the sensitivity factor is very low and is only 31.2, and the maximum strain can be stretched is 75%.
Comparative example 2
Mixing 100 parts (by mass) of PDMS as a main agent with 10 parts of graphene in an ethyl acetate solvent, adding 10 parts of PDMS curing agent into the system after the solvent is evaporated, and performing 3D printing by using the mixed material to form a corrugated mesh three-dimensional structure. And (3) placing the printed three-dimensional structure in an oven at 80 ℃ for curing for 6 hours, taking out the three-dimensional structure, and connecting an electrode to prepare the flexible sensor. The flexible strain sensor of the embodiment has no graphene coating, so the sensitivity factor is very low and is only 15.7, and the maximum strain can be stretched is 245%.
It should be noted that the above-mentioned description is given for illustrating the present invention in more detail with reference to specific preferred embodiments, and it should not be considered that the present invention is limited to the specific embodiments, but rather that several simple deductions or substitutions can be made by those skilled in the art without departing from the spirit of the present invention, which should be regarded as belonging to the patent protection scope defined by the claims filed with the present invention.
Claims (9)
1. A highly stretchable high-sensitivity 3D printed graphene-based flexible sensor, characterized in that the graphene-based flexible sensor has a two-stage sensing structure, wherein: the primary sensing structure is formed by filling an elastomer composite material with a conductive filler, and the secondary sensing structure is formed by coating reduced graphene oxide on the surface of the primary sensing structure; the mass ratio of the conductive filler to the elastomer composite material is 1:20-1: 1; the rheological property of the 3D printing material after the solvent is volatilized is as follows: at a shear rate of 0.1s-1The apparent viscosity at 25 ℃ is 1000-50000Pa & s;
the preparation method of the 3D printing graphene-based flexible sensor comprises the following specific steps:
(1) solution mixing is carried out on the conductive filler and the elastomer composite material according to a proportion at normal temperature, after the solvent is further volatilized, a 3D printing material is formed, a related printing structure is designed through a computer, and a primary sensing structure is printed out in a 3D mode;
(2) printing the primary sensing structure printed by 3D in the step (1) for curing and crosslinking, and performing plasma treatment on the surface of the cured and crosslinked material;
(3) further coating the surface of the primary sensing structure subjected to the plasma surface treatment with a water-soluble polymer electrolyte with positive electricity;
(4) coating graphene oxide GO on the surface of the primary sensing structure coated with the polymer electrolyte through electrostatic interaction, and reducing the coated GO into RGO through a chemical reduction method to obtain a sensing material with a secondary sensing structure;
(5) and (5) packaging the sensing material of the secondary sensing structure obtained in the step (4) on an extraction electrode to form the graphene-based flexible sensor.
2. The graphene-based flexible sensor according to claim 1, wherein the conductive filler selected for the primary sensing structure is a carbon-based conductive filler.
3. The graphene-based flexible sensor according to claim 2, wherein the carbon-based conductive filler is one or more of carbon black, carbon nanotubes or graphene.
4. The graphene-based flexible sensor according to claim 1, wherein the elastomer selected for the primary sensing structure is one or more of thermoplastic polyurethane elastomer (TPU), Polydimethylsiloxane (PDMS), or Ecoflex silicone rubber.
5. The preparation method of the highly stretchable and highly sensitive 3D printed graphene-based flexible sensor according to claim 1, characterized by comprising the following specific steps:
(1) solution mixing is carried out on the conductive filler and the elastomer composite material according to a proportion at normal temperature, after the solvent is further volatilized, a 3D printing material is formed, a related printing structure is designed through a computer, and a primary sensing structure is printed out in a 3D mode;
(2) printing the primary sensing structure printed by 3D in the step (1) for curing and crosslinking, and performing plasma treatment on the surface of the cured and crosslinked material;
(3) further coating the surface of the primary sensing structure subjected to the plasma surface treatment with a water-soluble polymer electrolyte with positive electricity;
(4) coating graphene oxide GO on the surface of the primary sensing structure coated with the polymer electrolyte through electrostatic interaction, and reducing the coated GO into RGO through a chemical reduction method to obtain a sensing material with a secondary sensing structure;
(5) and (5) packaging the sensing material of the secondary sensing structure obtained in the step (4) on an extraction electrode to form the graphene-based flexible sensor.
6. The method for preparing the graphene-based flexible sensor according to claim 5, wherein the mass ratio of the conductive filler to the elastomer material is 1:20-1: 1.
7. The method for preparing the graphene-based flexible sensor according to claim 5, wherein the solvent for solution mixing the elastomer composite and the conductive filler comprises one or more of ethyl acetate, xylene, tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetone or cyclohexane.
8. The preparation method of the graphene-based flexible sensor according to claim 5, wherein the surface of the primary sensing structure after the plasma surface treatment is further coated with a water-soluble polymer electrolyte with positive charges, wherein the water-soluble polymer electrolyte comprises one or more of polyethyleneimine, poly (diallyldimethylammonium chloride) or poly (N, N-dimethylacrylamide).
9. The method for preparing the graphene-based flexible sensor according to claim 5, wherein the reducing agent selected in the chemical reduction process for the coated GO in the step (4) comprises one or more of hydrazine hydrate, hydroiodic acid, sodium borohydride, ascorbic acid, ethylenediamine and ammonia water; the reduction conditions are as follows: and (3) placing the obtained GO-coated sensing material in the chemical reducing agent solution or steam atmosphere at the temperature of 25-100 ℃, and carrying out reduction treatment for 2-72 hours.
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