CN114425618A - Silver-gold core-shell nanowire doped gel film and preparation method and application thereof - Google Patents
Silver-gold core-shell nanowire doped gel film and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a silver-gold core-shell nanowire doped gel film and preparation and application thereof. The preparation method comprises the following steps: 1) preparing silver nanowires; 2) preparing silver-gold core-shell nanowires by taking the silver nanowires as templates; 3) continuously preparing the Ag @ Au-PEDOT nanowire on the basis; 4) and then preparing poly (styrene sulfonate-co-dimethylaminoethyl acrylate) gel by using a dimethylaminoethyl acrylate monomer and a styrene sulfonate monomer, and doping the poly (styrene sulfonate-co-dimethylaminoethyl acrylate) gel with the Ag @ Au-PEDOT nanowire to obtain a self-healing high-conductivity extensible gel film Ag @ Au-PEDOT/p (SS-co-DMA). The gel film is analyzed and tested through a series of mechanical properties, micro-morphology, electric conductivity and self-healing performance, and the prepared gel film is determined to have excellent self-healing performance, high electric conductivity and extensibility and can be applied to flexible wearable equipment integration.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a silver-gold core-shell nanowire doped gel film, and a preparation method and application thereof.
Background
The gel is a three-dimensional polymer network system consisting of a polymer and a solvent, has the characteristics of good biocompatibility, self-healing property, self-adhesion and the like, and has wide application value; in recent years, due to the potential of conductive gels in flexible electronics, sensors, and the like, the conductive gels have attracted much attention, and a great deal of research and great progress have been made on the conductive gels based on various conductive principles. Among many conductive gels, a conductive gel based on a metal material is widely used because of its high conductivity and easy preparation, and a silver nanowire, which is one of metal nanomaterials commonly used in conductive gels, has excellent conductivity, ultra-high stretchability and sensing sensitivity. When the gel uniformly doped with the silver nanowires is stretched, energy can be dissipated on the uniformly distributed silver nanowires, and internal stress is reduced, so that the mechanical properties of the material are improved.
However, since the silver nanowires have poor dispersibility, are incompatible with the polymer matrix and are prone to clustering, stress is concentrated on the aggregated silver nanowires during gel stretching, which aggravates the property failure process, and the silver nanowires are prone to be oxidized on the surface to cause reduced conductivity, thereby reducing the long-term service life of the device.
In view of the above, it is necessary to design a new gel to make up for the deficiencies of the existing gels.
Disclosure of Invention
The invention aims to solve the problems that a silver nanowire doped conductive polymer is easy to cluster in a polymer matrix and easy to oxidize during molding, and provides a silver-gold core-shell nanowire doped gel film and a preparation method and application thereof.
In order to achieve the purpose, the technical solution provided by the invention is as follows:
a silver gold poly 3,4-ethylene dioxythiophene nanowire (Ag @ Au-PEDOT Nanowires, Ag @ Au-PEDOT NWs) is characterized in that: the coating comprises a core layer, a middle layer and an outer coating from inside to outside;
the core layer is a Silver nanowire (AgNWs), and the length-diameter ratio of the AgNWs is 300-374: 1-2;
the middle layer is Gold (Au) with the thickness of 120-150 nm;
the outer coating is Poly (3,4-ethylenedioxythiophene) (PEDOT) with the thickness of 85-95 nm.
The preparation method of the Ag @ Au-PEDOT nanowire is characterized by comprising the following steps of:
1) preparation of silver-gold core-shell nanowire (Ag @ Au Nanowires, Ag @ Au NWs)
2) Dispersing Ag @ Au NWs prepared in the step 1) in a solution with the volume ratio of ultrapure water to methanol being 8.9-9.1: 0.9-1.1 (preferably 9: 1), and carrying out ultrasonic treatment for 4-8min (preferably 5 min);
3) adding 3,4-ethylenedioxythiophene into the solution subjected to the ultrasonic treatment in the step 2) and performing ultrasonic treatment for 7-13min (preferably 10 min);
4) heating the solution subjected to the ultrasonic treatment in the step 3) to 48-52 ℃ (preferably 50 ℃), and adding an iron chloride solution for reaction to obtain the Ag @ Au-PEDOT nanowire. The volume ratio of the ferric chloride solution to the solution obtained after the ultrasonic treatment in the step 3) is 4.8-5.2: 46.59-46.66, wherein the mass concentration of the ferric chloride solution is 0.076-0.079 mol/L; in the method, ferric chloride is used as an oxidizing agent for oxidative polymerization, and PEDOT is prepared and attached to and wraps the surface of the silver-gold core-shell nanowire.
Further, the step 1) is specifically as follows:
1.1) respectively dissolving sodium chloride, ferric nitrate, polyvinylpyrrolidone and silver nitrate in ethylene glycol to prepare four raw material solutions;
wherein the mass ratio of the sodium chloride, the ferric nitrate, the polyvinylpyrrolidone and the silver nitrate is 250-260: 80-82: 1040-1060;
preferably, the mass ratio of the sodium chloride, the ferric nitrate, the polyvinylpyrrolidone and the silver nitrate is 256-258: 80-82: 1049-1051, and the sodium chloride, the ferric nitrate, the polyvinylpyrrolidone and the silver nitrate are correspondingly dissolved in the ethylene glycol with the volume ratio of 19-20: 9-11: 24-26 for preparation; the unit of mass is mg, and the unit of volume is mL; preferably, the mass ratio of the sodium chloride to the ferric nitrate to the polyvinylpyrrolidone to the silver nitrate is 257: 81: 1050;
1.2) adding the four raw material solutions prepared in the step 1.1) into ethylene glycol preheated to 138-142 ℃ (preferably 140 ℃) for reaction;
1.3) after the reaction is finished, sequentially cleaning reactants by using acetone and ultrapure water to obtain AgNWs;
1.4) adding the tetrachloroauric acid solution, sodium hydroxide and sodium sulfite into ultrapure water for mixing to prepare a growth solution A, and standing for 11.8-12.3h (preferably 12 h);
mixing AgNWs prepared in the step 1.3), polyvinylpyrrolidone, sodium hydroxide, ascorbic acid and sodium sulfite to prepare a growth solution B;
wherein the mass concentration of the tetrachloroauric acid solution is 73-75 nmol/L;
the mass ratio of the tetrachloroauric acid solution, the sodium hydroxide, the sodium sulfate and the pure water is 2.48-2.55: 1.67-1.69: 3.2-3.4: 3.9-4.1, wherein the mass unit of the sodium hydroxide, the sodium sulfate and the pure water is g, and the mass unit of the tetrachloroauric acid solution is mg;
the mass ratio of AgNWs, polyvinylpyrrolidone, sodium hydroxide, ascorbic acid and sodium sulfite is 2.45-2.55: 91.5-92.4: 6.95-7.03: 30.75-30.83: 1.08-1.12;
1.5) mixing the growth solution A and the growth solution B according to the volume ratio of 277.9-279.8: 120.8-121.5 for reaction;
1.6) cleaning with ethanol after the reaction is finished to obtain the silver-gold core-shell nanowire.
Furthermore, the mass ratio of the Ag @ Au NWs to the 3,4-ethylenedioxythiophene is 19.8-20.1: 19.9-20.1, and preferably 1: 1.
The Ag @ Au-PEDOT nanowire is applied to preparation of gel films.
The invention also provides a gel film Ag @ Au-PEDOT/p (SS-co-DMA), which is characterized in that: the Ag @ Au-PEDOT nanowire is doped in the nanowire, the three-dimensional poly (styrene sulfonate-co-dimethylaminoethyl acrylate) (p (SS-co-DMA)) gel network is adopted as the internal physical structure, and physical reversible dynamic crosslinking is realized through electrostatic interaction. The chemical composition of p (SS-co-DMA) is: styrene sulfonate monomer, dimethylaminoethyl acrylate monomer.
The preparation method of the gel film is characterized by comprising the following steps:
s1, preparing Ag @ Au NWs by adopting the method
S2, preparing Ag @ Au-PEDOT nanowires
S21, dispersing the silver-gold core-shell nanowire prepared in the step S1 in a solution with the volume ratio of ultrapure water to methanol being 8.9-9.1: 0.9-1.1, and carrying out ultrasonic treatment for 4-8 min;
s22, adding 3,4-ethylenedioxythiophene into the solution subjected to the S21 ultrasonic treatment, and performing ultrasonic treatment for 7-13 min;
s23, heating the solution subjected to the S22 ultrasonic treatment to 48-52 ℃, and adding a ferric chloride solution for reaction to obtain an Ag @ Au-PEDOT nanowire;
also, the specific preparation method is the same as the aforementioned method.
S3, preparing a gel film Ag @ Au-PEDOT/p (SS-co-DMA);
s31, dissolving styrene sulfonate monomer (SS) in ultrapure water which is filled with argon and exhausted for 14-16min (preferably 15min), and adding the Ag @ Au-PEDOT nanowire prepared in S2 to obtain a mixture;
s32, performing ultrasonic treatment on the mixture obtained in the step S31 for 4-8min (preferably 5min), adding dimethylaminoethyl acrylate (DMA), and bubbling for 7-10min (preferably 8min) under the condition of filling argon to discharge oxygen;
s33, dissolving potassium persulfate (KPS) in the exhausted ultra-pure water, bubbling for 25-40 seconds (preferably 30 seconds) in the state of filling argon, adding the solution into the mixture of S32 at 68-72 ℃ (preferably 70 ℃) to react for 3.9-4.1 hours (preferably 4 hours);
s34, after the reaction is finished, placing the reaction product in a mold, and standing for 3.8-4.2h (preferably 4h) at 68-72 ℃ (preferably 70 ℃ for gel forming) to obtain a gel film, namely Ag @ Au-PEDOT/p (SS-co-DMA).
Furthermore, in S3, the mass ratio of the SS to the DMA to the potassium persulfate is 213.3-214.7: 107.8-108.2: 2.8-3.1.
Further, in S3, the addition amount of the Ag @ Au-PEDOT nanowire accounts for 1-1.5%, preferably 1%, of the mass of the gel, and the ultimate elongation of the gel reaches up to 2300%.
The invention also provides application of the gel film in preparation of flexible wearable equipment.
The mechanism of the invention is as follows:
in view of the problem that silver nanowires (AgNWs) doped with conductive polymers are easily oxidized and clustered in a polymer matrix during molding, the application considers that poly (3,4-ethylenedioxythiophene) (PEDOT) has good compatibility with polystyrene sulfonic acid (PSS) in a gel network, so that a PEDOT coating is prepared on the surface of the silver nanowires (as shown in fig. 1 a); however, redox polymerization reaction is needed during the synthesis of PEDOT, AgNWs has poor stability in an oxidizing environment, and the structure can be damaged, so that a layer of gold shell with good stability is coated on the surface of AgNWs in advance before PEDOT coating is carried out, and thus, the silver-gold shell nanowire is prepared; on the other hand, the three-dimensional gel network is made of polyampholyte, the polyampholyte is prepared by random copolymerization of DMAEA monomer and SS monomer, the positive charge part of the polyampholyte is DMA, the negative charge part of the polyampholyte is PSS, and the negative charge part of the polyampholyte is good in interaction with the PEDOT-coated nanowire, so that the PEDOT-coated nanowire can be uniformly distributed in the whole gel network; in addition, since the static interaction between the chains is reversible, self-healing of the conductive gel can be achieved (as shown in fig. 1 c).
The invention has the advantages that:
1. the prepared Ag @ Au-PEDOT/p (SS-co-DMA) gel film has super-long ductility, self-healing property and high conductivity, and simultaneously has certain stress sensing capacity, the method solves the problems of clustering and oxidation of the nanowire doped conductive polymer during molding, and simultaneously has the super-long ductility, self-healing property and high conductivity, and the silver-gold core-shell nanowire doped gel film prepared by the method has good prospects in the emerging industrial fields of wearable equipment and the like.
2. The synthesized gel film Ag @ Au-PEDOT/p (SS-co-DMA) has excellent conductivity, good self-healing capability, ultrahigh stretchability and induction sensitivity. The gel has good ductility due to dynamic cross-linking among polymer chains, namely static interaction among the zwitterionic polymers, and the gel is more excellent in conductivity due to the existence of Ag @ Au-PEDOT. Fig. 6 shows the change of the ultimate elongation and the resistance value in the self-healing cycle, and it can be seen from (a) of fig. 6 that the gel has the self-healing capability after multiple healing and maintains good mechanical properties. And (b) of FIG. 6 presents the change in resistance value of a p (SS-co-DMA) gel containing 1 wt% Ag @ Au-PEDOT after cutting and self-healing. It can be seen that the sudden change of the resistance value is caused by the breakage of the gel, and the resistance value rapidly returns to the vicinity of the initial value after the great change, indicating that the self-healing speed is high. Fig. 5 shows that the gel maintains a stable resistance value under a certain stretching degree, indicating that the gel has good conductive stability. Fig. 3 presents stress-strain curves of gels at different Ag @ Au-PEDOT contents (0 wt%, 1 wt%, 2.5 wt%, 10 wt%), and it can be seen that the addition of Ag @ Au-PEDOT reduced stiffness but enhanced ultimate elongation, with p (SS-co-DMA) ultimate elongation of 1 wt% Ag @ Au-PEDOT up to 2300% strain, while p (SS-co-DMA) gel ultimate elongation without Ag @ Au-PEDOT of 800% increased by nearly three times, showing good ductility. In summary, the gel film Ag @ Au-PEDOT/p (SS-co-DMA) shows great potential for applications in the field of flexible wearable sensors.
3. In the preparation process, raw materials with high toxicity are not used, and the whole preparation process is relatively environment-friendly.
Drawings
FIG. 1 is a schematic diagram of the present invention; wherein (a) is the preparation of Ag @ Au-PEDOT, (b) is a schematic process of polymerization of SS monomers and DMA monomers to make a gel network, and (c) is an illustration of PEDOT: PSS interactions and reversible static interactions between polymer chains.
FIG. 2 is a microscopic topography; (a) scanning electron microscope images of AgNWs, (b) and (c) are images of a scanning electron microscope and a transmission electron microscope of Ag @ AuNWs, and (d) is EDS element mapping of AgNWs (upper graph) and Au elements (lower graph); (e) and (f) images of a scanning electron microscope and a transmission electron microscope with an Ag @ Au-PEDOT ternary core-shell structure, (g) images of EDS elements of Ag, Au, S and O, (h) images of a scanning electron microscope of Ag-PEDOT without a gold coating on AgNWs, and (i) images of a transmission electron microscope of Ag-PEDOT without a gold coating on AgNWs.
Fig. 3 is a graph of the mechanical properties of the gel, wherein (a) is the stress-strain curve of the gel for different Ag @ Au-PEDOT nanowire contents, and (b) is the stress-strain curve of the gel in the 100% strain range.
FIG. 4 is a graph of the electrical properties of a gel; wherein (a) is the resistance of the gel (the size of the gel is 40mm multiplied by 10mm multiplied by 1mm) with different Ag @ Au-PEDOT nanowire content, and (b) is the conductivity of the gel with different Ag @ Au-PEDOT nanowire content.
FIG. 5 is a graph of gel sensing performance, where (a) is the change in resistance of p (SS-co-DMA) gels at different degrees of stretch, and (b) is the change in resistance of p (SS-co-DMA) gels incorporating 1 wt% Ag @ Au-PEDOT nanowires at different degrees of stretch.
Fig. 6 is a graph of the self-healing performance of the gel, wherein (a) is the final strain level of the gel with a content of 1 wt% Ag @ Au-PEDOT nanowires after self-healing n times, and (b) is the change in resistance of the gel during the healing cycle of cutting.
Detailed Description
The invention is described in further detail below with reference to the following figures and specific examples:
the Ag @ Au-PEDOT/p (SS-co-DMA) gel film provided by the invention has the following chemicals: ethylene Glycol (EG), sodium chloride (NaCl), ferric nitrate (Fe (NO)3)3) Polyvinylpyrrolidone (PVP), non-hydrated ferric nitrate (Fe (NO)3)399.999%), silver nitrate (AgNO)3) Acetone (acetone), purified water (Milli-Q water), tetrachloroauric acid (HAuCl)474nmol/mL), sodium hydroxide (NaOH, 96%), sodium sulfite (Na)2SO398%), ascorbic acid (L-AA), methanol (methane), iron chloride (FeCl)399.9%), 3, 4-Ethyldioxythiophene (EDOT), sodium Styrene Sulfonate (SS), ethyl dimethyl acrylamide (DMA), potassium persulfate (KPS).
The preparation method comprises the following steps:
(1) the preparation of the silver nanowire AgNWs is carried out by a simple one-pot synthesis method:
first 140mL of Ethylene Glycol (EG) was placed in a three-necked flask and preheated at 140 ℃ for one hour with a reflux condenser. 257mg of sodium chloride (NaCl) and 81mg of ferric nitrate (Fe (NO)3)3) 1050mg polyvinylpyrrolidone (PVP) and 1050mg silver nitrate (AgNO)3) The four prepared solutions were dissolved in Ethylene Glycol (EG) respectively, and then added to preheated Ethylene Glycol (EG) to react for 4 hours, and the resulting mixture was washed with acetone and ultrapure water in this order.
The method specifically comprises the following steps:
257mg of NaCl was added to 20mL of EG solution (a), and 81mg of Fe (NO) was added3)310mL of EG solution (b) was added, 1.05mg of PVP was added to 25mL of EG solution (c), and 1.05mg of AgNO was added325mL of EG was added to prepare a solution (d); 0.2mL of the solution (a), 0.1mL of the solution (b), 20mL of the solution (c), and 20mL of the solution (d) were added to EG in an oil bath for 1 hour at intervals of 30s, and the mixture was reacted at 140 ℃ for 2 hours. Uniformly distributing the reacted filamentous solution in 6 centrifuge tubes, adding 10mL of acetone into each centrifuge tube, and centrifuging at the speed of 2500rpm for 1 hour after uniform dispersion; taking supernatant, redispersing in deionized water, and performing one round at 2500rpmAnd (4) centrifuging for 1 hour to obtain AgNWs.
(2) Preparing silver-gold core-shell nanowires Ag @ Au NWs:
100mL of tetrachloroauric acid (HAuCl)4) Solution (74nmol/L), 1.68mg sodium hydroxide (NaOH) and 3.3mg sodium sulfite (Na)2SO3) The growth solution A was prepared by mixing in 4mL of ultrapure water, and left to stand for twelve hours. 2.5mg AgNWs, 92mg PVP, 7mg NaOH, 30.8mg ascorbic acid and 1.1mg Na2SO3To prepare growth solution B. And then adding the growth solution A into the growth solution B, reacting for one hour, and cleaning with ethanol after the reaction is finished to obtain the silver-gold core-shell nanowire Ag @ Au NWs.
(3) Preparing the Ag @ Au-PEDOT nanowire with the three-layer core-shell structure:
20mg of Ag @ AuNWs were dispersed in a solution of ultrapure water to methanol in a ratio of 9:1 and sonicated for 5 min. Further 20mg of 3,4-Ethylenedioxythiophene (EDOT) were added to the solution and sonicated for 10 min. After the solution was heated to 50 ℃, a ferric chloride (FeCl3) solution was added to continue the reaction, and the volume ratio of the ferric chloride solution to the solution was 5: 46.6 (wherein, the concentration of the ferric chloride solution was 0.077 mol/L). After reacting for 8 hours, washing with ultrapure water to obtain the Ag @ Au-PEDOT nanowire.
(4) Preparation of gel film Ag @ Au-PEDOT/p (SS-co-DMA):
ultrapure water was first degassed for 15min prior to use, followed by dissolution of styrene sulfonate monomer in the degassed ultrapure water, and addition of varying amounts of silver-gold nanowires (0 wt%, 1 wt%, 2.5 wt%, 5 wt%, 10 wt%). The mixture was sonicated for 5min, dimethylaminoethyl acrylate (DMAEA) was added and the mixture bubbled under argon for 8 min. While potassium persulfate (KPS) was dissolved in the exhausted ultrapure water, it was placed in an argon atmosphere and bubbled for 30 seconds. KPS was added to the mixture at 70 deg.C for 4 hours, then moved to a mold, allowed to stand at 70 deg.C for 4 hours, and finally the mold was left to stand overnight by exposure to air to give a gel film Ag @ Au-PEDOT/p (SS-co-DMA).
To further verify the invention, the following performance tests were performed on the gel film prepared in example 1 of the invention:
morphological, microstructural and elemental characterization
The microstructure was characterized using a Scanning Electron Microscope (SEM) (ZEISS Geini 300) and a Transmission Electron Microscope (TEM) (Talos F200X). Elemental characterization was observed by energy dispersive X-ray spectroscopy (EDS) elemental mapping.
FIG. 2 (a) is a scanning electron microscope image of AgNWs, and it can be seen that the prepared AgNWs are very thin, have excellent aspect ratio, have a length of about 15 μm and an average width of about 50-80nm, and are uniformly dispersed in pure water; (b) and (c) are respectively the scanning electron microscope image and the transmission electron microscope image of the Ag @ Au nanowire, and the width of the Ag @ Au nanowire is larger than that of the silver nanowire; (d) EDS element mapping of Ag (top) and Au (bottom) further shows that Au and Ag have the same trend, indicating formation of a silver-gold core-shell structure; (e) and (f) are respectively scanning electron microscope and transmission electron microscope images of the Ag @ Au-PEDOT ternary core-shell structure, the scanning electron microscope images show that the surface of the nanowire becomes more rough and has obvious spherical protrusions, and compared with Ag-Au NWs, the diameter of the nanowire is increased to about 200nm, wherein the aspect ratio of the silver nanowire is 300-374: 1-2, the middle layer is gold, the thickness is 120-150nm, the outer coating is PEDOT, and the thickness is 85-95 nm. (g) Is EDS element mapping of Ag, Au, S, O (from left to right), the EDS element mapping in the figure further demonstrates the Ag @ Au-PEDOT ternary core-shell structure, wherein the carbon (C), silver (Ag) and gold (Au) elements exhibit the same trend. Panel (h) is a scanning electron microscope image of Ag-PEDOT without a gold coating on the AgNWs, the dark spot in the TEM image is a silver spot, because the gold coating is not uniform and part of the silver is oxidized by ferric chloride; (i) transmission electron microscopy images of Ag-PEDOT without gold coating on AgNWs.
Second, mechanical properties
The mechanical properties of the gel were measured at room temperature with a strain rate of 60mm/min using a universal tester (INSTRON 3344). A stress-strain curve was obtained. The modulus is calculated from the equation:
where E is modulus, σ is stress, and ε is strain. In FIG. 3 (a) stress-strain curves for different Ag @ Au-PEDOT nanowire contents, gels at 0 wt%, 1 wt%, 2.5 wt%, and 10 wt%. (b) Modulus of gels at different Ag @ Au-PEDOT nanowire contents, 0 wt%, 1 wt%, 2.5 wt%, and 10 wt%. As can be seen from the figure, the addition of the Ag @ Au-PEDOT nanowire reduces the rigidity, but enhances the ultimate tensile value, the p (SS-CO-DMA) gel tensile strain rate of the Ag @ Au-PEDOT nanowire containing 1-1.5 wt% reaches more than 1900%, and the p (SS-CO-DMA) gel tensile strain rate of the Ag @ Au-PEDOT nanowire containing 1 wt% is the highest and reaches 2300% of strain. And the p (SS-co-DMA) gel limit elongation of the 0 wt% Ag @ Au-PEDOT nanowire is 800%, which is improved by almost three times. This is because Ag @ Au-PEDOT nanowires increase the free volume between polymer chains, reducing chain-to-chain interactions and entanglement.
Third, conductivity
The conductivity of the gel film was measured with a Source Measuring Unit (SMU) instrument (Keithley 2400). The resistance of the gel was measured at a constant voltage (1V). The conductivity of the gel is calculated from the following equation:
where σ is the conductivity, l is the length of the gel, A is the cross-sectional area, and R is the resistance of the gel. FIG. 4 (a) shows the magnitude of the resistance of the gel (the size of the gel is 40 mm. times.10 mm. times.1 mm) at different Ag @ Au-PEDOT nanowire contents (0 wt%, 1 wt%, 2.5 wt%, 5 wt%, 10 wt%). (b) The conductivity of gels with different Ag @ Au-PEDOT nanowire contents is presented. In FIG. 5 (a) shows the change in the resistance of the p (SS-co-DMA) gel at different degrees of stretch, and (b) shows the change in the resistance of the p (SS-co-DMA) gel incorporating 1 wt% Ag @ Au-PEDOT nanowires at different degrees of stretch. Comparing the two graphs, the resistance value of the gel added with the Ag @ Au-PEDOT nanowire is changed greatly under the condition of the same stretching degree, and the resistance value is changed from 250k omega to 2750k omega.
Fourth, self-healing property
FIG. 6 (a) presents the ultimate elongation of a p (SS-co-DMA) gel containing 1 wt% Ag @ Au-PEDOT nanowires during different cycles of fracture and self-healing. The gel in the initial state was stretched at a strain rate of 180mm/min, with an ultimate stretch of 639%. After 8 times of healing, the ultimate elongation is reduced to 473%, and the result shows that the gel still has the self-healing capability and maintains good mechanical property after multiple times of healing. FIG. 6 (b) presents the change in resistance of a p (SS-co-DMA) gel containing 1 wt% Ag @ Au-PEDOT nanowires after cutting and self-healing. It can be seen that the sudden change in resistance is due to the breaking of the gel, and the resistance rapidly returns to near the initial value after a large change, which represents a rapid self-healing process.
In each step of preparing the gel film, the invention selects endpoint values in the range according to different raw material proportions and reaction conditions, and performs performance test, and the test result is better than that of the existing gel and has the self-healing capability, so that the gel film prepared by the invention has good application prospect.
While the invention has been described with reference to specific embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
Claims (10)
1. An Ag @ Au-PEDOT nanowire, which is characterized in that: the core layer, the middle layer and the outer coating are arranged from inside to outside;
the core layer is AgNWs, and the length-diameter ratio of the AgNWs is 300-374: 1-2;
the intermediate layer is Au, and the thickness is 120-150 nm;
the external coating is PEDOT with the thickness of 85-95 nm.
2. The method of making Ag @ Au-PEDOT nanowires of claim 1, comprising the steps of:
1) preparation of Ag @ Au NWs
2) Dispersing Ag @ Au NWs prepared in the step 1) in a solution with the volume ratio of ultrapure water to methanol being 8.9-9.1: 0.9-1.1, and carrying out ultrasonic treatment for 4-8 min;
3) adding 3,4-ethylenedioxythiophene into the solution subjected to the ultrasonic treatment in the step 2) and performing ultrasonic treatment for 7-13 min;
4) heating the solution subjected to the ultrasonic treatment in the step 3) to 48-52 ℃, and adding a ferric chloride solution for reaction to obtain the Ag @ Au-PEDOT nanowire.
3. The preparation method of the Ag @ Au-PEDOT nanowire according to claim 2, wherein the step 1) is specifically as follows:
1.1) respectively dissolving sodium chloride, ferric nitrate, polyvinylpyrrolidone and silver nitrate in ethylene glycol to prepare four raw material solutions;
wherein the mass ratio of the sodium chloride, the ferric nitrate, the polyvinylpyrrolidone and the silver nitrate is 250-260: 80-82: 1040-1060;
1.2) adding the four raw material solutions prepared in the step 1.1) into ethylene glycol preheated to the temperature of 138-142 ℃ for reaction;
1.3) after the reaction is finished, sequentially cleaning reactants by using acetone and ultrapure water to obtain AgNWs;
1.4) adding the tetrachloroauric acid solution, sodium hydroxide and sodium sulfite into ultrapure water for mixing, preparing a growth solution A, and standing for 11.8-12.3 h;
mixing AgNWs prepared in the step 1.3), polyvinylpyrrolidone, sodium hydroxide, ascorbic acid and sodium sulfite to prepare a growth solution B;
wherein the mass concentration of the tetrachloroauric acid solution is 73-75 nmol/L;
the mass ratio of the tetrachloroauric acid solution, the sodium hydroxide, the sodium sulfate and the pure water is 2.48-2.55: 1.67-1.69: 3.2-3.4: 3.9-4.1, wherein the mass unit of the sodium hydroxide, the sodium sulfate and the pure water is g, and the mass unit of the tetrachloroauric acid solution is mg;
the mass ratio of AgNWs, polyvinylpyrrolidone, sodium hydroxide, ascorbic acid and sodium sulfite is 2.45-2.55: 91.5-92.4: 6.95-7.03: 30.75-30.83: 1.08-1.12;
1.5) mixing the growth solution A and the growth solution B according to the volume ratio of 277.9-279.8: 120.8-121.5 for reaction;
1.6) washing with ethanol after the reaction is finished to obtain Ag @ Au NWs.
4. The method for preparing Ag @ Au-PEDOT nanowires according to claim 1 or 2, wherein:
the mass ratio of the Ag @ Au NWs to the 3,4-ethylenedioxythiophene is 19.8-20.1: 19.9-20.1.
5. Use of Ag @ Au-PEDOT nanowires as defined in claim 1 for the preparation of gel films.
6. A gel film Ag @ Au-PEDOT/p (SS-co-DMA), characterized by: the Ag @ Au-PEDOT nanowire as claimed in claim 1 is doped inside the nanowire, the physical structure of the nanowire is a three-dimensional p (SS-co-DMA) gel network, and physical reversible dynamic crosslinking is achieved through electrostatic interaction.
7. The method for preparing the gel film Ag @ Au-PEDOT/p (SS-co-DMA) according to claim 6, comprising the steps of:
s1, preparing Ag @ Au NWs
S2, preparing Ag @ Au-PEDOT nanowires
S21, dispersing Ag @ Au NWs prepared by S1 in a solution with the volume ratio of ultrapure water to methanol being 8.9-9.1: 0.9-1.1, and carrying out ultrasonic treatment for 4-8 min;
s22, adding 3,4-ethylenedioxythiophene into the solution subjected to the S21 ultrasonic treatment, and performing ultrasonic treatment for 7-13 min;
s23, heating the solution subjected to the S22 ultrasonic treatment to 48-52 ℃, and adding a ferric chloride solution for reaction to obtain an Ag @ Au-PEDOT nanowire;
s3, preparing a gel film Ag @ Au-PEDOT/p (SS-co-DMA)
S31, dissolving styrene sulfonate monomer in ultrapure water filled with argon and exhausted for 14-16min, and adding the Ag @ Au-PEDOT nanowire prepared in S2 to obtain a mixture;
s32, carrying out ultrasonic treatment on the mixture obtained in the step S31 for 4-8min, adding dimethylaminoethyl acrylate, and bubbling for 7-10min under the condition of filling argon;
s33, dissolving potassium persulfate in the exhausted ultra-pure water, bubbling for 25-40 seconds under the condition of filling argon, and adding the solution into the mixture of S32 at 68-72 ℃ for reaction for 3.9-4.1 hours;
s34, after the reaction is finished, placing the reaction product in a mold, and standing for 3.8-4.2h at 68-72 ℃ to obtain a gel film Ag @ Au-PEDOT/p (SS-co-DMA).
8. The method for preparing the gel film Ag @ Au-PEDOT/p (SS-co-DMA) according to claim 7, wherein: in S3, the mass ratio of the styrene sulfonate monomer to the dimethylaminoethyl acrylate to the potassium persulfate is 213.3-214.7: 107.8-108.2: 2.8-3.1.
9. The method for preparing the gel film Ag @ Au-PEDOT/p (SS-co-DMA) according to claim 8, wherein:
in S3, the addition amount of the Ag @ Au-PEDOT nanowire accounts for 1-1.5% of the mass of the gel.
10. Use of the gel film Ag @ Au-PEDOT/p (SS-co-DMA) according to claim 5 for the manufacture of flexible wearable devices.
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