CN113527558A - Nano composite hydrogel and preparation method and application thereof - Google Patents
Nano composite hydrogel and preparation method and application thereof Download PDFInfo
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- 238000000034 method Methods 0.000 claims abstract description 12
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- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 13
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 13
- 229960003237 betaine Drugs 0.000 claims description 13
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- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/38—Esters containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N1/00—Electrostatic generators or motors using a solid moving electrostatic charge carrier
- H02N1/04—Friction generators
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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Abstract
The application discloses a nano composite hydrogel and a preparation method and application thereof, wherein the nano composite hydrogel is a zwitterion/clay composite hydrogel, the tensile strength of the nano composite hydrogel is not less than 90KPa, and the elongation at break is not less than 1200%. The zwitterion nano composite hydrogel can be strongly adhered to the surfaces of various materials through the ion-dipole effect and dipole-dipole interaction of zwitterions and the surfaces of the materials, and the method has the advantages of simple process and low cost of raw materials.
Description
Technical Field
The application relates to a nano composite hydrogel, a hydrogel contact generator, a preparation method and an application thereof, belonging to the field of polymer hydrogel.
Background
Electronic devices have made tremendous progress over the past 50 years. The rapid progress radically changes our lives in the fields of medical care, communication, entertainment, transportation, etc. In the near future, electronic devices will seamlessly integrate into the human body, playing a key role in health monitoring, medical, robotic or artificial skin, and human-machine interfaces, penetrating deeper into human life. Materials that mimic human skin are very popular because of their ability to integrate effectively and establish intimate contact with the human body. Human skin is soft, healable, stretchable, self-renewing, and can detect external environmental stimuli such as temperature and pressure. However, the electronic devices currently in use are rigid and fragile, resulting in difficulties in seamless connection and direct integration into the human body. Conventional materials used in electronic devices (e.g., metals and semiconductors) are capable of withstanding mechanical strains of less than 5% and are not suitable for human mechanical motion. In addition, there is currently an increasing interest in conformal wearable devices and body-implantable electronic devices for advanced real-time health monitoring, medical therapy, sports applications and communications. These needs have triggered the development of new skin inspired electronic materials and devices, and how to provide a safer, more convenient, and more sustainable energy source for devices has become an urgent problem to be solved.
The wangzhining institute topic group reports for the first time a Triboelectric Nanogenerator (TENG), which is the focus of attention because of a series of advantages of light weight, high safety, cleanness, environmental protection, sustainability and the like. Over the past few years, extensive attempts have been made to understand the basic principles, improve its performance and expand its use in a wide range of applications. TENG has higher output voltage and power density, very low cost, high conversion efficiency and lower manufacturing cost than other energy harvesters. In addition, it can generate energy from a variety of random, irregular, and extremely low mechanical pulses. It can also operate at low and high frequencies, thus making it more suitable for generating energy from human voluntary movements, a very good energy harvesting device. For example, TENG has been shown to generate energy by a gentle touch, a heavy mechanical impact (e.g., tapping or walking), and a linear sliding motion (e.g., rubbing two body parts). TENG includes two-layer electrification layer, stretchable conductor layer and wire, the planar dimension of stretchable conductor layer is less than the electrification layer, two-layer the electrification layer is usually pasted on the positive and negative two sides of stretchable conductor layer through the viscose respectively, the wire is fixed two-layerly between the electrification layer, because the viscose goes viscidity in the volatile of used repeatedly in-process, can lead to stretchable conductor layer and the not in close contact with of electrification layer, can influence TENG's electricity generation effect.
Disclosure of Invention
According to a first aspect of the present application, there is provided a nanocomposite hydrogel in which clay and positively charged groups of zwitterions are electrostatically associated to provide excellent mechanical properties to the hydrogel, and the charged groups on the zwitterionic polymer chains can interact repeatedly with polar groups on the tissue surface via dipole-dipole interactions, facilitating intimate association of the hydrogel with the charged surface of the generator, and having good power generation properties after multiple taps or other mechanical impacts.
A nano-composite hydrogel, which is a zwitterion/clay composite hydrogel, and has a tensile strength of not less than 90KPa and an elongation at break of not less than 1200%.
Optionally, the tensile strength of the nanocomposite hydrogel is 90-130 KPa, and the elongation at break is 1200-1700%.
Optionally, the clay is a nanoclay; the nano clay is selected from at least one of lithium magnesium silicate, magnesium aluminum silicate and water-based bentonite;
optionally, the zwitterionic monomer is selected from at least one of carboxylate betaine zwitterionic monomer (CBAA), sulfonate betaine zwitterionic monomer (SBMA), phosphate betaine zwitterionic monomer;
optionally, the mass ratio of the clay to the zwitterionic monomer is 0.012-0.08.
The preparation method of the nano composite hydrogel at least comprises the following steps:
adding an initiator into a clay water suspension in which a zwitterionic monomer is dissolved to obtain a mixed solution;
and adding an accelerant into the mixed solution to obtain a gel pre-polymerization solution, and carrying out in-situ free radical polymerization to obtain the nano-composite hydrogel.
Optionally, the clay is a nanoclay; the nano clay is selected from at least one of lithium magnesium silicate, magnesium aluminum silicate and water-based bentonite;
the concentration of the clay in the mixed solution is 1-7 wt/vol%.
Alternatively, the upper limit of the clay concentration can be selected from 1.5 wt/vol%, 2 wt/vol%, 2.5 wt/vol%, 3 wt/vol%, 3.5 wt/vol%, 4 wt/vol%, 4.5 wt/vol%, 5 wt/vol%, 5.5 wt/vol%, 6 wt/vol%, 6.5 wt/vol%, or 7 wt/vol%; the lower limit may be selected from 1 wt/vol%, 1.5 wt/vol%, 2 wt/vol%, 2.5 wt/vol%, 3 wt/vol%, 3.5 wt/vol%, 4 wt/vol%, 4.5 wt/vol%, 5 wt/vol%, 5.5 wt/vol%, 6 wt/vol%, or 6.5 wt/vol%.
Optionally, the zwitterionic monomer is selected from at least one of carboxylate betaine zwitterionic monomer (CBAA), sulfonate betaine zwitterionic monomer (SBMA), phosphate betaine zwitterionic monomer;
optionally, the concentration of the zwitterionic monomer in the mixed solution is 3-5 mol/L.
Optionally, the initiator is a water-soluble free radical polymerization initiator;
the water-soluble free radical polymerization initiator is at least one of potassium persulfate, ammonium persulfate and sodium persulfate;
the accelerant is tetramethylethylenediamine TEMED.
Optionally, the concentration of the initiator in the mixed solution is 0.001-0.003 mol/L;
the dosage of the accelerant is 3.6-5 mu L/mL.
Optionally, the in-situ radical polymerization is performed at room temperature, and the polymerization time is 10-15 h.
According to a second aspect of the present application, there is provided a nanocomposite hydrogel prepared by any one of the above-mentioned preparation methods.
According to a third aspect of the present application, there is provided a hydrogel contact generator comprising a conducting wire, two electrically-generating layers and a conductor layer fixed between the two electrically-generating layers, the conductor layer being selected from at least one of a nanocomposite hydrogel prepared by any one of the above-mentioned preparation methods and a nanocomposite hydrogel described in any one of the above-mentioned preparation methods.
Optionally, the electrification layer is selected from at least one of foam double-sided tape (VHB), Polydimethylsiloxane (PDMS) and silica gel (Silicone Rubber);
alternatively, the wire is a conventional wire, preferably a copper wire.
Preferably, the conductor layer and the electrification layer are fixed by self adhesion.
Optionally, the hydrogel contact generator has a tensile strength of not less than 120KPa and an elongation at break of not less than 1400%; the hydrogel contact generator has a transparency of not less than 80%.
Optionally, the hydrogel contact generator has a tensile strength of 120-170 KPa and an elongation at break of 1400-2400%.
Optionally, the short-circuit current of the hydrogel contact generator is 3-10 muA.
In one embodiment, a method of making a hydrogel contact generator is provided, comprising:
(1) preparing a homogeneous aqueous suspension of clay at room temperature, adding a zwitterionic monomer to the suspension, and stirring at room temperature until the zwitterion is completely dissolved to obtain a mixed solution of zwitterion and clay.
The contents of all substances in the mixed solution are as follows:
1-7 wt/vol% of nano clay
Clay 4mol/L
The balance of water;
(2) and adding an initiator into the obtained mixed solution of the zwitterion and the clay, stirring for 30-60 min at room temperature, uniformly mixing, adding TEMED into the mixed solution, stirring for 5min at room temperature to obtain a gel prepolymer, injecting the gel prepolymer into a gel forming die, and carrying out free radical polymerization for 12h in the air at room temperature to obtain the zwitterion nano-composite hydrogel.
(3) And adhering the two sides of the obtained zwitterion nano composite hydrogel with the electrification layers, and inserting a copper wire between the two electrification layers to finally obtain the single-level TENG.
Optionally, the electrification layer is selected from at least one of VHB, PDMS and Silicone Rubber.
As an implementation mode, the method specifically comprises the following steps:
dispersing the nano clay into deionized water at room temperature, uniformly mixing to obtain a nano clay suspension, adding zwitterions into the dispersed nano clay suspension, and stirring for about 1h at room temperature to obtain a transparent zwitterion and clay mixed solution, wherein:
1-7 wt/vol% of nano clay
Zwitterion 4mol/L
The balance of deionized water;
the nano clay is one or more of lithium magnesium silicate, magnesium aluminum silicate or water-based bentonite.
(2) Adding 0.002mol/L of initiator into the obtained mixed solution, stirring for 30-60 min at room temperature, after uniform mixing, adding 3.6-5 mu L/mL of EMED into the mixed solution, stirring for 5min at room temperature, uniformly mixing to obtain gel prepolymer, injecting the gel prepolymer into a gel forming die, and carrying out free radical polymerization for 12h at room temperature in the air to obtain the hydrogel.
Optionally, the zwitterion is at least one selected from carboxylate betaine zwitterionic monomer (CBMA), sulfonate betaine zwitterionic monomer (SBMA), and phosphate betaine zwitterionic monomer.
The water-soluble initiator comprises at least one of potassium persulfate, ammonium persulfate and sodium persulfate.
(3) And adhering the two sides of the obtained zwitterion nano composite hydrogel with the electrification layers, and inserting a copper wire in the middle to finally obtain the single-electrode TENG.
Optionally, the electrification layer is selected from at least one of VHB, PDMS and Silicone Rubber.
According to a fourth aspect of the present application, there is provided a use of at least one of the nanocomposite hydrogel prepared by the preparation method of any one of the above, the nanocomposite hydrogel of any one of the above, and the hydrogel contact generator of any one of the above in a wearable device.
The wearable device may be a wearable bio-energy collector, an optional band flexible input, or other flexible electronic device.
In the present application, "wt/vol%" is a mass volume percentage; for example, "1 wt/vol%" is 100mL of water in which 1g of solute is dissolved. The room temperature is 20-25 ℃.
The beneficial effects that this application can produce include:
1) according to the nano-composite hydrogel provided by the application, clay and positively charged groups of zwitterions are combined through electrostatic interaction, so that excellent mechanical properties are provided for the hydrogel, and the charged groups on the zwitterion polymer chain can repeatedly interact with polar groups on the surface of a tissue through dipole-dipole interaction, so that the hydrogel can be tightly combined with the surface of an electrification layer of a generator, and the hydrogel still has good generation performance after being subjected to beating or other mechanical impacts for many times;
2) the finally obtained hydrogel contains a proper amount of phenolic hydroxyl which can be repeatedly bonded with the surfaces of skin, tissues and the like through hydrogen bond action and the like to obtain repeated and stable adhesion capability;
3) the hydrogel preparation method provided by the application is simple in process and low in raw material cost;
4) the hydrogel has good biocompatibility and can be used as flexible electronic device materials such as wearable bioenergy collectors and wearable flexible input ends.
Drawings
FIG. 1 is a stress-strain plot of a nanocomposite hydrogel prepared in example 4 of the present invention;
figure 2 is a stress-strain plot of a nanocomposite hydrogel contact generator prepared in example 4 of the present invention;
figure 3 is a transparency spectrum of a nanocomposite hydrogel contact generator prepared in example 1 of the present invention.
Detailed Description
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
Wherein: the nano clay is (magnesium lithium silicate) LAPONITE XLG, (magnesium aluminum silicate) Neusilin UFL2, (water-based bentonite) BP-188L.
Betaine methacrylate Sulfonate (SBMA) was purchased from alatin chemicals ltd, model M164461.
VBH double sided tape was purchased from 3M company model 4905, PDMS was prepared according to the method described in "TRANSPARENT and available communicating communicators based on self-clear triboelectric nanogenerators" published by Younghoon Lee.
The analysis method in the examples of the present application is as follows:
and (3) utilizing a universal testing machine (three thoughts) to test the mechanical property of the nano-composite hydrogel contact generator.
And (3) carrying out transparency test on the nano composite hydrogel contact generator by using an ultraviolet visible near infrared spectrophotometer (LAMBDA).
And (3) carrying out the power generation performance test of the nano composite hydrogel contact generator by adopting a Gishili 6514 electrometer.
Example 1
Uniformly dispersing the nano clay into deionized water to obtain a nano clay suspension, adding a zwitterionic monomer SBMA into the dispersed nano clay suspension, and stirring for 1h at room temperature to obtain a transparent and clear amphoteric ion and nano clay mixed solution.
The content of each substance in the mixed solution is as follows:
magnesium lithium silicate 5 wt/vol%
Zwitterionic monomer 4mol/L
The balance of deionized water;
(2) adding potassium persulfate into the obtained mixed solution of the nano clay and the zwitter-ion monomer, stirring for 30min at room temperature, uniformly mixing to obtain a mixed solution, wherein the concentration of the potassium persulfate in the mixed solution is 0.002mol/L, adding TEMED into the mixed solution, the concentration of the TEMED in the mixed solution is 3.6 mu L/mL, stirring for 5min at room temperature, uniformly mixing to obtain a gel pre-polymerization solution, injecting the gel pre-polymerization solution into a gel forming die, and performing free radical polymerization for 12h in air at room temperature to obtain the zwitter-ion nano composite hydrogel with the thickness of 20mm 2mm 20 mm.
(3) And (3) adhering 30 mm-30 mm transparent VHB double-sided adhesive tapes to two sides of the obtained zwitter-ion nano-composite hydrogel, and inserting a copper wire between the two layers of VHB double-sided adhesive tapes to finally obtain the single-electrode nano-composite hydrogel contact generator TENG.
Example 2
Uniformly dispersing the nano clay into deionized water to obtain a nano clay suspension, adding a zwitterionic monomer SBMA into the dispersed nano clay suspension, and stirring at room temperature for 1h to obtain a transparent and clear amphoteric ion and nano clay mixed solution.
The content of each substance in the mixed solution is as follows:
magnesium lithium silicate 4 wt/vol%
Zwitterionic monomer 4mol/L
The balance of deionized water;
(2) adding potassium persulfate into the obtained mixed solution of the nano clay and the zwitterionic monomer, stirring for 60min at room temperature, uniformly mixing to obtain a mixed solution, wherein the concentration of the potassium persulfate in the mixed solution is 0.002mol/L, adding TEMED into the mixed solution, the concentration of the TEMED in the mixed solution is 3.6 mu L/mL, stirring for 5min at room temperature, uniformly mixing to obtain a gel pre-polymerized solution, injecting the gel pre-polymerized solution into a gel forming die, and performing free radical polymerization for 12h in air at room temperature to obtain the zwitterionic nano composite hydrogel with the thickness of 20mm 2mm 20 mm.
(3) And (3) adhering 30 mm-30 mm transparent VHB double-sided adhesive tapes to two sides of the obtained zwitter-ion nano-composite hydrogel, and inserting a copper wire between the two layers of VHB double-sided adhesive tapes to finally obtain the single-electrode nano-composite hydrogel contact generator TENG.
Example 3
Uniformly dispersing the nano clay into deionized water to obtain a nano clay suspension, adding a zwitterionic monomer SBMA into the dispersed nano clay suspension, and stirring at room temperature for 1h to obtain a transparent and clear amphoteric ion and nano clay mixed solution.
The content of each substance in the mixed solution is as follows:
6 wt/vol% of lithium magnesium silicate
Zwitterionic monomer 4mol/L
The balance of deionized water;
(2) adding potassium persulfate into the obtained mixed solution of the nano clay and the zwitterion, stirring for 60min at room temperature, uniformly mixing to obtain a mixed solution, wherein the concentration of the potassium persulfate in the mixed solution is 0.002mol/L, adding TEMED into the mixed solution, the concentration of the TEMED in the mixed solution is 3.6 mu L/mL, stirring for 5min at room temperature, uniformly mixing to obtain a gel pre-polymerization solution, injecting the gel pre-polymerization solution into a gel forming die, and performing free radical polymerization for 12h in air at room temperature to obtain the zwitterion nano composite hydrogel with the thickness of 20mm 2mm 20 mm.
(3) And (3) adhering 30 mm-30 mm transparent VHB double-sided adhesive tapes to two sides of the obtained zwitter-ion nano-composite hydrogel, and inserting a copper wire between the two layers of VHB double-sided adhesive tapes to finally obtain the single-electrode nano-composite hydrogel contact generator TENG.
Example 4
Uniformly dispersing the nano clay into deionized water to obtain a nano clay suspension, adding a zwitterionic monomer SBMA into the dispersed nano clay suspension, and stirring at room temperature for 1h to obtain a transparent and clear amphoteric ion and nano clay mixed solution.
The content of each substance in the mixed solution is as follows:
magnesium lithium silicate 2 wt/vol%
Zwitterionic monomer 4mol/L
The balance of deionized water;
(2) adding potassium persulfate into the obtained mixed solution of the nano clay and the zwitterion, stirring for 60min at room temperature, uniformly mixing to obtain a mixed solution, wherein the concentration of the potassium persulfate in the mixed solution is 0.002mol/L, adding TEMED into the mixed solution, the concentration of the TEMED in the mixed solution is 3.6 mu L/mL, stirring for 5min at room temperature, uniformly mixing to obtain a gel pre-polymerization solution, injecting the gel pre-polymerization solution into a gel forming die, and performing free radical polymerization for 12h in air at room temperature to obtain the zwitterion nano composite hydrogel with the thickness of 20mm 2mm 20 mm.
(3) And (3) adhering 30 mm-30 mm transparent VHB double-sided adhesive tapes to two sides of the obtained zwitter-ion nano-composite hydrogel, and inserting a copper wire between the two layers of VHB double-sided adhesive tapes to finally obtain the single-electrode nano-composite hydrogel contact generator TENG.
Example 5
The preparation method is the same as that of example 3, except that magnesium lithium silicate is replaced by magnesium aluminum silicate, and the content of the magnesium lithium silicate is 4 wt/vol% of the pre-polymerization solution.
The resulting nanocomposite hydrogel contact generators were all similar to those of example 1.
Example 6
The preparation method is the same as that of example 1, except that the magnesium lithium silicate is replaced by aqueous bentonite, and the content of the magnesium lithium silicate is 3 wt/vol% of the pre-polymerization solution.
The resulting nanocomposite hydrogel contact generators were all similar to those of example 1.
Example 7
The preparation method is the same as example 1, except that the VHB double-sided adhesive tape is replaced by PDMS.
The resulting nanocomposite hydrogel contact generators were all similar to those of example 1.
Example 8
The preparation method is the same as that of example 1, except that the VHB double faced adhesive tape is replaced by Silicone Rubber.
The resulting nanocomposite hydrogel contact generators were all similar to those of example 1.
Testing the adhesion performance of the nanocomposite hydrogel provided in the step 2) of the example 1-8
A universal testing machine is used, the lap shear test is adopted to measure the adhesion performance of the nano-composite hydrogel on the surfaces of glass, Cu sheets, polytetrafluoroethylene and pigskin materials, the nano-composite hydrogel provided in the embodiment 4 is taken as a typical representative, the adhesion strength of the nano-composite hydrogel provided in the embodiment 4 and the surface of the pigskin is 11.93kPa, the nano-composite hydrogel and other materials have good self-adhesion performance, and the adhesion strength of other embodiments is within the range of 6-10 kPa.
Carrying out performance test on the nano-composite hydrogel contact generator provided by the embodiment 1-8 and the nano-composite hydrogel provided by the step 2):
1) mechanical Property test
A universal testing machine is used, the mechanical properties of the nano-composite hydrogel and the nano-composite hydrogel contact generator are measured by adopting a tensile test, the nano-composite hydrogel provided in the embodiment 4 is taken as a typical representative, as shown in fig. 1, the tensile stress and the elongation at break of the nano-composite hydrogel provided in the embodiment 4 are 90kPa, 1250%, the tensile stress and the elongation at break of other embodiments are 90-130 kPa, and the elongation at break is 1200% -1700%; as shown in FIG. 2, the nano-composite hydrogel contact generator has a tensile stress of 120kPa and an elongation at break of 2400%, and the tensile stress of other examples is 120 to 170kPa and the elongation at break is 1400 to 2400%.
2) Transparency test
The ultraviolet-visible near-infrared spectrophotometer is used, the transparency of the nanocomposite hydrogel contact generator is tested in a transmission mode, the nanocomposite hydrogel provided in example 4 is taken as a typical representative, as shown in fig. 3, the transparency of the nanocomposite hydrogel provided in example 4 is about 80%, and the transparency of other examples is more than 80%.
3) Power generation performance test
The test method comprises the following steps: the nanocomposite hydrogel contact generator TENG was tested for short circuit current using a gischili electrometer 6514. One end of a measuring wire of the electrometer 6514 is connected to a Cu lead of the nano-composite hydrogel contact generator TENG, the other end of the measuring wire is grounded, and the nano-composite hydrogel contact generator TENG is continuously tapped by hands to carry out testing;
taking the nanocomposite hydrogel provided in example 4 as a typical representative, as shown in fig. 1, the short-circuit current of the nanocomposite hydrogel provided in example 4 is about 5 μ a, and the short-circuit currents of other examples are 3 to 10 μ a.
As can be seen from fig. 1 and 2, the nanocomposite hydrogel contact generator provided in embodiments 1 to 7 of the present invention has good mechanical properties, can withstand large deformation, and can be applied in various situations, such as elbow joints and knee joints; and the transparency is high, so that the contact generator can be used as a wearable device on the surface of human skin.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A nano-composite hydrogel, which is a zwitterion/clay composite hydrogel, and is characterized in that the tensile strength of the nano-composite hydrogel is not less than 90KPa, and the elongation at break is not less than 1200%.
2. The method for preparing a nanocomposite hydrogel according to claim 1, comprising at least the following steps:
adding an initiator into a clay water suspension in which a zwitterionic monomer is dissolved to obtain a mixed solution;
and adding an accelerant into the mixed solution to obtain a gel pre-polymerization solution, and carrying out in-situ free radical polymerization to obtain the nano-composite hydrogel.
3. The method of claim 1, wherein the clay is a nanoclay;
the nano clay is selected from at least one of lithium magnesium silicate, magnesium aluminum silicate and water-based bentonite;
the concentration of the clay in the mixed solution is 1-7 wt/vol%.
4. The method for preparing a nanocomposite hydrogel according to claim 1, wherein the zwitterionic monomer is at least one selected from the group consisting of carboxylate betaine zwitterionic monomers, sulfonate betaine zwitterionic monomers, and phosphate betaine zwitterionic monomers;
the concentration of the zwitterionic monomer in the mixed solution is 3-5 mol/L.
5. The method for preparing a nanocomposite hydrogel according to claim 1, wherein the initiator is a water-soluble radical polymerization initiator;
the water-soluble free radical polymerization initiator is at least one of potassium persulfate, ammonium persulfate and sodium persulfate;
the accelerant is tetramethyl ethylene diamine.
6. The method for preparing a nanocomposite hydrogel according to claim 1, wherein the concentration of the initiator in the mixed solution is 0.001 to 0.003 mol/L;
the dosage of the accelerant is 3.6-5 mu L/mL;
7. the method of claim 1, wherein the in situ free radical polymerization is performed at room temperature.
8. A hydrogel contact generator, which comprises a conducting wire, two layers of electrification layers and a conductor layer fixed between the two layers of electrification layers, and is characterized in that the conductor layer is at least one selected from the nano-composite hydrogel disclosed in claim 1 and the nano-composite hydrogel prepared by the preparation method disclosed in any one of claims 2 to 7.
9. The hydrogel contact generator of claim 8, wherein the generating layer is selected from at least one of foam double-sided tape, polydimethylsiloxane, and silica gel;
preferably, the conductor layer and the electrification layer are fixed through self adhesion;
preferably, the hydrogel contact generator has the tensile strength of not less than 120KPa and the elongation at break of not less than 1400%;
preferably, the hydrogel contact generator has a transparency of not less than 80%.
10. Use of at least one of a nanocomposite hydrogel according to claim 1, a nanocomposite hydrogel prepared by the preparation method according to any one of claims 2 to 7, and a hydrogel contact generator according to claim 8 or 9 in a wearable device.
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