CN112679753A - Super-soft conductive self-healing hydrogel and preparation method and application thereof - Google Patents
Super-soft conductive self-healing hydrogel and preparation method and application thereof Download PDFInfo
- Publication number
- CN112679753A CN112679753A CN202011404952.1A CN202011404952A CN112679753A CN 112679753 A CN112679753 A CN 112679753A CN 202011404952 A CN202011404952 A CN 202011404952A CN 112679753 A CN112679753 A CN 112679753A
- Authority
- CN
- China
- Prior art keywords
- hydrogel
- healing
- self
- solution
- conductive self
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000017 hydrogel Substances 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 56
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 55
- 239000000243 solution Substances 0.000 claims description 32
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 19
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 17
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 13
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 13
- 229910021538 borax Inorganic materials 0.000 claims description 13
- 239000004328 sodium tetraborate Substances 0.000 claims description 13
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000002048 multi walled nanotube Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 10
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical group CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000010526 radical polymerization reaction Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 229920000144 PEDOT:PSS Polymers 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 230000004044 response Effects 0.000 abstract description 9
- 239000002861 polymer material Substances 0.000 abstract description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 13
- 238000010586 diagram Methods 0.000 description 11
- 230000007774 longterm Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 229920002401 polyacrylamide Polymers 0.000 description 5
- 239000000178 monomer Substances 0.000 description 4
- 230000000638 stimulation Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 1
- -1 borate ions Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 235000008113 selfheal Nutrition 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Images
Landscapes
- Materials For Medical Uses (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and discloses super-soft conductive self-healing hydrogel and a preparation method and application thereof. The super-soft conductive self-healing hydrogel obtained by the invention has lower Young modulus (about 1kPa) and can realize quick and sensitive electrical response to tiny deformation. In addition, the hydrogel prepared by the invention has more efficient mechanical and electrical self-healing capabilities, can realize mechanical property self-healing within 1s, can restore about 96% of the original level within 1s, and has potential application value in preparation of flexible wearable sensors.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, relates to a hydrogel, and particularly relates to a super-soft conductive self-healing hydrogel and a preparation method and application thereof.
Background
Through extensive and intensive research in recent years, flexible sensors have been developed very rapidly, and can be mainly classified into the following three categories: the flexible sensor comprises a multifunctional flexible sensor, a self-driven flexible sensor and a self-healing flexible sensor. At present, both multifunctional sensors and self-driven flexible sensors have a common defect that the structural damage of the device is inevitably caused after repeated bending and stretching cycles or use in severe environment, the quality of detected signals is reduced, and the long-term use of the device is influenced. In order to solve the stability of the long-term use of the flexible device, a new direction is opened in the research of flexible electronics, namely, a flexible sensor taking a self-healing material as a framework is developed. Besides being perfectly compatible with various perception functions, human skin also has an attractive feature: it can recover by itself after being damaged. That is, the skin is essentially a self-healing material, and its ability to repair damage by itself ensures long-term stable use of the skin as an electronic system. Inspired by skin, if a self-healing material similar to skin is adopted as a framework of the flexible sensor, the long-term stability of the flexible electronic system can be improved.
Hydrogels are formed by a hydrophilic polymer network encapsulating water within the pores of the network, while exhibiting both solid and fluid properties. Compared with other traditional materials, the Young modulus of the hydrogel is adjustable in a large range by changing the components of the hydrogel, the span range is generally matched with the Young modulus of biological tissues and organs including skin, and therefore a seamless interface can be formed between the biological tissues and an electronic device, so that the hydrogel is widely applied to the fields of flexible electronics and bioelectronics in recent years. For conductive self-healing (CSH) materials, it is the next development goal to have hydrogel with both conductive and self-healing capabilities. A common strategy is to combine a conductive component with a self-healing hydrogel network. Wearable sensors based on these conductive self-healing (CSH) hydrogels provide a sensitive and reliable electrical response to human body movements, such as bending of a finger, elbow or knee.
However, the self-healing (especially electrical) time of these materials is too long (several minutes to several hours) to meet the requirement of fast and continuous physical signal detection. And their tensile properties and long-term stability still need to be further improved. In addition, the young modulus of these materials still needs to be further reduced to increase the deformation response degree of the materials to micro mechanical stimulation and improve the response capability of the materials to weak physiological signals. The invention aims to synthesize the CSH hydrogel with low Young modulus (super-soft) and high mechanical electricity self-healing efficiency.
Disclosure of Invention
In light of the problems set forth in the background above, the present invention is directed to developing an ultra-soft, highly efficient self-healing electrically conductive hydrogel material. The hydrogel material is prepared by taking the conductive self-healing material as a framework to serve as a flexible sensor, so that the damage of devices caused by long-term recycling of the sensor is overcome, the service life of the sensor is prolonged, and the signal detection stability is improved.
The invention provides a super-soft conductive self-healing hydrogel, which is prepared by mixing a polyvinyl alcohol aqueous solution, a carboxyl functionalized multi-walled carbon nanotube (MWCNT-COOH) and a poly (3, 4-ethylenedioxythiophene)/poly (styrene sulfonate) (PEDOT/PSS) as conductive framework materials, and an acrylamide, PEDOT and PSS aqueous solution with a polyvinyl alcohol aqueous solution to obtain a hydrogel precursor solution and performing a free radical polymerization method.
In the technical scheme of the invention, the free radical polymerization method is to polymerize a hydrogel precursor by adding an initiator, a cross-linking agent, an auxiliary agent and borax to obtain a hydrogel compound.
In the technical scheme of the invention, the initiator is ammonium persulfate, the cross-linking agent is N, N' -methylene bisacrylamide, and the auxiliary agent is tetramethylethylenediamine.
The second aspect of the present invention provides a preparation method of the super-soft conductive self-healing hydrogel, comprising the following steps:
step one, dissolving polyvinyl alcohol powder in ionized water, and uniformly stirring at 80-120 ℃ to obtain a polyvinyl alcohol solution;
step two, cooling the polyvinyl alcohol solution obtained in the step one to room temperature, mixing the polyvinyl alcohol solution with PEDOT and PSS to obtain a mixed solution A, ultrasonically dispersing the carboxylated multi-walled carbon nanotubes and acrylamide in deionized water to obtain a mixed solution B, adding the mixed solution B into the mixed solution A, and uniformly stirring to obtain a hydrogel precursor solution;
dissolving borax, ammonium persulfate N, N' -methylene bisacrylamide and tetramethylethylenediamine in deionized water, adding the deionized water into the hydrogel precursor solution, uniformly stirring, and reacting at 50-100 ℃ for 6-12 hours in an oxygen-free environment to obtain the super-soft conductive self-healing hydrogel.
In the technical scheme of the invention, in the step one, the stirring time is 20-40min, and the concentration of the polyvinyl alcohol solution is 0.02-0.2 g/ml.
In the technical scheme of the invention, in the second step, the mass ratio of the polyvinyl alcohol solution, PEDOT to PSS, the carboxylated multi-walled carbon nanotube and acrylamide is 1-10: 12.5: 0.05: 2.
in the technical scheme of the invention, in the second step, the concentration of the carboxylated multi-wall carbon nano tube is 1-2 wt%.
In the technical scheme of the invention, in the third step, the mass ratio of borax, ammonium persulfate N, N' -methylene bisacrylamide and tetramethylethylenediamine is 0.1g to 0.006 g: 0.03 g: 1000ppm:1 ml.
In the technical scheme of the invention, the mass ratio of the polyvinyl alcohol solution in the step two to the borax in the step three is 1-10: 0.1.
the invention also provides application of the conductive self-healing hydrogel or the conductive self-healing hydrogel prepared by the preparation method of the conductive self-healing hydrogel in preparation of a flexible wearable sensor.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention introduces carbon nanotubes and conductive polymers into the physical and chemical crosslinking hydrogel with an interpenetrating network structure to obtain a CSH hydrogel material. Polyvinyl alcohol (PVA) is used to provide the basic hydrogel backbone. Self-healing capability is provided by borax providing a number of easily cleavable and re-formable hydrogen bonds formed by tetrafunctional borate ions with hydroxyl groups on the PVA chain. Hydroxyl-functionalized multi-walled carbon nanotubes (MWCNT-COOH) and poly (3, 4-ethylenedioxythiophene)/poly (styrenesulfonate) (PEDOT/PSS) were added to the hydrogel network as conductive backbones to provide the hydrogel with electrical conductivity. In addition, Acrylamide (AM) monomers are polymerized in the presence of Ammonium Persulfate (APS) and then chemically cross-linked with N, N' -Methylene Bisacrylamide (MBAA) to form a Polyacrylamide (PAM) network with interpenetration of PEDOT and PVA chains. The network can enhance the strength of the hydrogel, and the prepared hydrogel material is more stable. The amine groups on the PAM can also interact with PVA and MWCNT-COOH to form hydrogen bonds, which can increase the self-healing efficiency of the hydrogel. The multi-wall carbon nano tube-poly (3, 4-ethylenedioxythiophene)/poly (styrene sulfonate) -polyacrylamide-poly (vinyl alcohol)/borax (CNT-PEDOT-PAM-PVA) hydrogel compound which is super-soft and has the conductivity and the high-efficiency self-healing capability is obtained.
2. The super-soft conductive self-healing hydrogel (CNT-PEDOT-PAM-PVA hydrogel) obtained by the invention has lower Young modulus (about 1kPa) and can realize quick and sensitive electrical response to tiny deformation. In addition, the CNT-PEDOT-PAM-PVA hydrogel prepared by the invention has high-efficiency mechanical and electrical self-healing capabilities, can realize mechanical property self-healing within 1s, can restore about 96% of the original level within 1s, and has potential application value in preparation of flexible wearable sensors.
Drawings
FIG. 1 is a photograph of a CNT-PEDOT-PAM-PVA hydrogel of the present invention;
FIG. 2 is a stress-strain test chart of the CNT-PEDOT-PAM-PVA hydrogel of the present invention, wherein a is a stress-strain test diagram, and b is a stress-strain test result graph;
FIG. 3 is a schematic diagram of a deformation response detection result of the CNT-PEDOT-PAM-PVA hydrogel, wherein a is a schematic diagram of contact between the hydrogel and an electrode plate, and b is a schematic diagram of a detection result of the hydrogel responding to pressure;
FIG. 4 is a schematic diagram of the mechanical self-healing performance of the CNT-PEDOT-PAM-PVA hydrogel, wherein a is a schematic diagram of the mechanical performance of the hydrogel after undergoing structural damage and b is a schematic diagram of the simulation of the hydrogel self-healing;
FIG. 5 is a schematic diagram of the electrical self-healing performance of the CNT-PEDOT-PAM-PVA hydrogel of the present invention, wherein a is a schematic diagram of the impedance change in one "cut-contact" process; graph b is a schematic diagram of the change in impedance (f ═ 100kHz) during the "open-contact" cycle; c is a schematic view of an LED light bulb that can be lit before cutting into two parts and after healing.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The reagents and starting materials used in the following examples have the following meanings:
PVA represents polyvinyl alcohol; MWCNT-COOH represents a carboxyl-functionalized multi-walled carbon nanotube; PEDOT/PSS stands for poly (3, 4-ethylenedioxythiophene)/poly (styrenesulfonate); APS represents ammonium persulfate; AM represents acrylamide; PAM refers to polyacrylamide.
Example 1
3g of PVA powder was weighed into 50 ml of deionized water and stirred at 100 ℃ for 40min to form a clear, homogeneous solution. After the PVA solution was cooled to room temperature, 6.7 g of the PVA solution was weighed out and mixed with 12.5 g of a 1.1% PEDOT/PSS solution by mass and 2g of AM monomer. 50 mg MWCNT-COOH was dispersed in 3 ml deionized water and added to the above solution. And meanwhile, dissolving 0.1g of borax, 0.006g of APS, 0.03g of MBAA and TEMED (1000ppm) which are weighed into 1ml of deionized water, adding the deionized water into the mixed solution, stirring the mixture uniformly by a large force, and reacting the mixture for 12 hours at 50 ℃ in an oxygen-free environment to obtain the CNT-PEDOT-PAM-PVA hydrogel.
As shown in the attached FIG. 1, the CNT-PEDOT-PAM-PVA hydrogel prepared in example 1 is shown, and it can be seen from the figure that the hydrogel prepared is placed in a sample bottle and does not slide down along the bottle wall after being inverted, so that the hydrogel prepared is a black colloidal elastomer with good viscosity.
Example 2
3g of PVA powder was weighed into 80 ml of deionized water and stirred at 120 ℃ for 20min to form a clear, homogeneous solution. After the PVA solution was cooled to room temperature, 6.7 g of the PVA solution was weighed out and mixed with 12.5 g of a 1.1% PEDOT/PSS solution by mass and 2g of AM monomer. 50 mg MWCNT-COOH was dispersed in 3 ml deionized water and added to the above solution. And meanwhile, dissolving 0.1g of borax, 0.006g of APS, 0.03g of MBAA and TEMED (1000ppm) which are weighed into 1ml of deionized water, adding the deionized water into the mixed solution, stirring the mixture uniformly by a large force, and reacting the mixture for 12 hours at 80 ℃ in an oxygen-free environment to obtain the CNT-PEDOT-PAM-PVA hydrogel.
Example 3
6g of PVA powder was weighed into 80 ml of deionized water and stirred at 80 ℃ for 120min to form a clear, homogeneous solution. After the PVA solution was cooled to room temperature, 6.7 g of the PVA solution was weighed out and mixed with 12.5 g of a 1.1% PEDOT/PSS solution by mass and 2g of AM monomer. 50 mg MWCNT-COOH was dispersed in 3 ml deionized water and added to the above solution. And meanwhile, dissolving 0.1g of borax, 0.006g of APS, 0.03g of MBAA and TEMED (1000ppm) which are weighed into 1ml of deionized water, adding the deionized water into the mixed solution, stirring the mixture uniformly by a large force, and reacting the mixture for 6 hours at 50 ℃ in an oxygen-free environment to obtain the CNT-PEDOT-PAM-PVA hydrogel.
First, testing and analyzing
The preparation method comprises the following steps of taking example 1 as an example to verify the softness degree, the corresponding capacity to weak mechanical stimulation and the mechanical self-healing capacity of the prepared CNT-PEDOT-PAM-PVA hydrogel;
1. the CNT-PEDOT-PAM-PVA hydrogel prepared in example 1 was first subjected to a tensile test, and the hydrogel was subjected to a tensile test in an electronic universal tester, and the stress-strain curve thereof was measured as shown in a graph a in FIG. 2. The hydrogel sample selected by us had an original length of 20mm and a diameter of 2mm, and the tensile speed of the universal tester was 100 mm/min. From the experimental results, it can be seen that it can be finally stretched to 440mm without breaking at room temperature, and the deformation amount is 2200% as shown in fig. 2b, which indicates that it has superior stretching ability. The stress-strain curve in b of fig. 2 shows that the hydrogel has an ultra-low young's modulus (1.09 ± 0.19kPa, n is 3, fig. 2b), indicating that it is extremely soft and deforms significantly in response to external mechanical stimuli.
2. In order to verify that the CNT-PEDOT-PAM-PVA hydrogel can have sensitive electrical signal response to weak mechanical stimulation, a piece of hydrogel is placed between two circular electrode plates, good contact between the hydrogel and the electrode plates is guaranteed as shown in a diagram in figure 3 a, weak pressure is gradually applied to the position right above an upper electrode plate, and it can be seen that the hydrogel presents linear response to the applied pressure as shown in figure 3b, so that the CNT-PEDOT-PAM-PVA hydrogel can be used for quantitatively detecting the weak mechanical stimulation.
3. We performed a strain scanning experiment of alternating cycles of high (600%) and low (1%) strain on a rotational rheometer to verify the mechanical self-healing capability of CNT-PEDOT-PAM-PVA hydrogels. The hydrogel, when subjected to a small amplitude strain of 1%, has a storage modulus (G') greater than the loss modulus (G "), consistent with previous experimental results. When subjected to a large amplitude strain of 600%, its G' drops rapidly and is less than G ", indicating that the hydrogel network is disrupted and the material exhibits fluid behavior. When the strain is recovered to 1%, G' is rapidly recovered to the original level and is greater than G ", and the material is changed into an elastomer again, which shows that the hydrogel can rapidly recover the original mechanical properties after undergoing structural damage, as shown in fig. 4 a. Furthermore, during this experiment, G' increased over time, which is a result of hydrogel loss of water. Furthermore, we pulled a small piece of CNT-PEDOT-PAM-PVA hydrogel into two parts and left them to touch again, and found that they were able to successfully self-heal at 1s and regained stretch capability, as shown in figure 4 b. The results show that the CNT-PEDOT-PAM-PVA hydrogel has the rapid mechanical self-healing capability.
To evaluate the electrical self-healing ability of the hydrogel, we cut the hydrogel sample at room temperature and its impedance exhibited a short circuit characteristic. Subsequently, we re-contact the separated samples and the impedance quickly returns to its original level as shown in fig. 5 a. The hydrogel, after undergoing multiple "incision-contact" cycles, recovered its impedance to about 96% of its original level within 1s of re-contact after incision, as shown in figure 5 b. Next, we designed a demonstration experiment for the electrical self-healing capability of hydrogel. The result shows that the CNT-PEDOT-PAM-PVA hydrogel has stable and efficient electric self-healing capability, and the CNT-PEDOT-PAM-PVA hydrogel is beneficial to continuous use and stable detection of flexible devices.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (9)
1. The super-soft conductive self-healing hydrogel is characterized in that polyvinyl alcohol is used as a hydrogel framework material, carboxyl functionalized multi-walled carbon nanotubes and PEDOT (PSS) are used as conductive framework materials, a hydrogel precursor solution is obtained by mixing an aqueous solution of the polyvinyl alcohol with an aqueous solution of the carboxyl functionalized multi-walled carbon nanotubes, acrylamide, the PEDOT (PSS), and the hydrogel precursor solution is prepared by a free radical polymerization method.
2. The electrically conductive self-healing hydrogel according to claim 1, wherein the radical polymerization process is a process of polymerizing a hydrogel precursor solution to obtain a hydrogel composite by adding an initiator, a crosslinking agent, an auxiliary agent, and borax.
3. The electrically conductive self-healing hydrogel according to claim 2, wherein the initiator is ammonium persulfate, the cross-linking agent is N, N' -methylenebisacrylamide, and the auxiliary agent is tetramethylethylenediamine.
4. The method for preparing the electrically conductive self-healing hydrogel according to claim 3, comprising the steps of:
step one, dissolving polyvinyl alcohol powder in ionized water, and uniformly stirring at 80-120 ℃ to obtain a polyvinyl alcohol solution;
step two, cooling the polyvinyl alcohol solution obtained in the step one to room temperature, mixing the polyvinyl alcohol solution with PEDOT, PSS and acrylamide to obtain a mixed solution A, dispersing the carboxylated multi-walled carbon nanotubes in deionized water to obtain a mixed solution B, adding the mixed solution B into the mixed solution A, and uniformly stirring to obtain a hydrogel precursor solution;
dissolving borax, ammonium persulfate, N' -methylene bisacrylamide and tetramethylethylenediamine in deionized water, adding the deionized water into the hydrogel precursor solution, uniformly stirring, and reacting at 50-100 ℃ for 6-12 hours in an oxygen-free environment to obtain the super-soft conductive self-healing hydrogel.
5. The method for preparing a conductive self-healing hydrogel according to claim 4, wherein in the first step, the stirring time is 20-40min, and the concentration of the polyvinyl alcohol solution is 0.02g/ml-0.2 g/ml.
6. The preparation method of the electrically conductive self-healing hydrogel according to claim 4, wherein in the second step, the mass ratio of the polyvinyl alcohol solution, PEDOT: PSS, carboxylated multi-walled carbon nanotubes and acrylamide is 1-10: 12.5: 0.05: 2;
preferably, in the second step, the concentration of the carboxylated multi-wall carbon nanotubes is 1 to 2 weight percent.
7. The method for preparing the electrically conductive self-healing hydrogel according to claim 4, wherein in step three, the ratio of borax, ammonium persulfate, N' -methylenebisacrylamide, tetramethylethylenediamine and deionized water is 0.1g:0.006 g: 0.03 g: 1000ppm:1 ml.
8. The method for preparing the electrically conductive self-healing hydrogel according to claim 4, wherein the mass ratio of the polyvinyl alcohol solution in the second step to the borax in the third step is 1-10: 0.1.
9. use of the electrically conductive self-healing hydrogel according to any one of claims 1 to 3 or the electrically conductive self-healing hydrogel produced by the method for producing an electrically conductive self-healing hydrogel according to any one of claims 4 to 8 for producing a flexible wearable sensor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011404952.1A CN112679753A (en) | 2020-12-04 | 2020-12-04 | Super-soft conductive self-healing hydrogel and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011404952.1A CN112679753A (en) | 2020-12-04 | 2020-12-04 | Super-soft conductive self-healing hydrogel and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112679753A true CN112679753A (en) | 2021-04-20 |
Family
ID=75447331
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011404952.1A Pending CN112679753A (en) | 2020-12-04 | 2020-12-04 | Super-soft conductive self-healing hydrogel and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112679753A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113185715A (en) * | 2021-04-21 | 2021-07-30 | 华南理工大学 | Self-healing conductive polyvinyl alcohol-based hydrogel and preparation method and application thereof |
| CN113332936A (en) * | 2021-07-02 | 2021-09-03 | 长春工业大学 | High-toughness conductive anti-freezing carbon nanotube organic hydrogel |
| CN116655953A (en) * | 2023-06-26 | 2023-08-29 | 西安理工大学 | Preparation method and application of hydrogel precursor liquid capable of being printed in 3D (three-dimensional) and high-conductivity high-elasticity hydrogel |
| WO2023236475A1 (en) * | 2022-06-08 | 2023-12-14 | 深圳先进技术研究院 | Conductive thin film, method for preparing same, and use thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109111581A (en) * | 2018-06-11 | 2019-01-01 | 中原工学院 | A kind of preparation method of high-strength conductive polyvinyl alcohol composite hydrogel |
| CN109294133A (en) * | 2018-09-25 | 2019-02-01 | 南京工业大学 | Stretchable self-healing hydrogel flexible strain sensor and preparation method thereof |
| CN110105482A (en) * | 2019-04-26 | 2019-08-09 | 厦门大学 | A kind of self-healing hydrogel and preparation method thereof |
-
2020
- 2020-12-04 CN CN202011404952.1A patent/CN112679753A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109111581A (en) * | 2018-06-11 | 2019-01-01 | 中原工学院 | A kind of preparation method of high-strength conductive polyvinyl alcohol composite hydrogel |
| CN109294133A (en) * | 2018-09-25 | 2019-02-01 | 南京工业大学 | Stretchable self-healing hydrogel flexible strain sensor and preparation method thereof |
| CN110105482A (en) * | 2019-04-26 | 2019-08-09 | 厦门大学 | A kind of self-healing hydrogel and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| FENGMING YE ET AL.: "Ultrafast Self-Healing and Injectable Conductive Hydrogel for Strain and Pressure Sensors", 《ADVANCED MATERIALS TECHNOLOGIES》 * |
| 叶丰明: "用于生理信号检测的柔性传感器", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113185715A (en) * | 2021-04-21 | 2021-07-30 | 华南理工大学 | Self-healing conductive polyvinyl alcohol-based hydrogel and preparation method and application thereof |
| CN113332936A (en) * | 2021-07-02 | 2021-09-03 | 长春工业大学 | High-toughness conductive anti-freezing carbon nanotube organic hydrogel |
| WO2023236475A1 (en) * | 2022-06-08 | 2023-12-14 | 深圳先进技术研究院 | Conductive thin film, method for preparing same, and use thereof |
| CN116655953A (en) * | 2023-06-26 | 2023-08-29 | 西安理工大学 | Preparation method and application of hydrogel precursor liquid capable of being printed in 3D (three-dimensional) and high-conductivity high-elasticity hydrogel |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112679753A (en) | Super-soft conductive self-healing hydrogel and preparation method and application thereof | |
| Yu et al. | Carbon Dots‐Based Ultrastretchable and Conductive Hydrogels for High‐Performance Tactile Sensors and Self‐Powered Electronic Skin | |
| Xia et al. | A flexible, adhesive and self-healable hydrogel-based wearable strain sensor for human motion and physiological signal monitoring | |
| CN113549175B (en) | Multifunctional conductive ionic liquid gel and preparation method and application thereof | |
| Gao et al. | Bio-inspired adhesive and self-healing hydrogels as flexible strain sensors for monitoring human activities | |
| CN111040194A (en) | Conductive hydrogel and preparation method and application thereof | |
| CN108440772A (en) | A kind of selfreparing conduction dual network structure hydrogel and preparation method thereof | |
| CN110760075B (en) | Ti3C2TxComposite double-network hydrogel and preparation and application thereof | |
| Fan et al. | Self-healing carrageenan-driven Polyacrylamide hydrogels for strain sensing | |
| CN113773445B (en) | Preparation method and application of hydrogel flexible touch sensor | |
| Deng et al. | From carbon nanotubes to ultra-sensitive, extremely-stretchable and self-healable hydrogels | |
| Chang et al. | Ionic conductive hydrogels toughened by latex particles for strain sensors | |
| Gao et al. | A hydrogel sensor driven by sodium carboxymethyl starch with synergistic enhancement of toughness and conductivity | |
| JP7063485B2 (en) | Composite material and its manufacturing method | |
| CN114349980B (en) | Conductive hydrogel and preparation method and application thereof | |
| CN113372492B (en) | High-performance polyion liquid gel, multi-mode flexible sensor and preparation method thereof | |
| Han et al. | Ultra-stretchable, self-healing, bonding, and skin-inspired conductive triple network hydrogel for wearable strain sensors and friction nanogenerators | |
| CN113185715B (en) | Self-healing conductive polyvinyl alcohol-based hydrogel and preparation method and application thereof | |
| CN113150326B (en) | Preparation method of transparent self-adhesive conductive hydrogel | |
| CN111892721B (en) | AgNWs composite conductive antibacterial hydrogel and preparation and use methods thereof | |
| Khan et al. | Multi-role conductive hydrogels for flexible transducers regulated by MOFs for monitoring human activities and electronic skin functions | |
| Ren et al. | Polyionic liquid ionogels formed via hydrophobic association for flexible strain sensors | |
| CN113336971B (en) | Nano-structure polyaniline composite hydrogel and preparation method and application thereof | |
| Shu et al. | A synergistic enhancement strategy for mechanical and conductive properties of hydrogels with dual ionically cross-linked κ-carrageenan/poly (sodium acrylate-co-acrylamide) network | |
| Wang et al. | Thermal responsive sodium alginate/polyacrylamide/poly (N-isopropylacrylamide) ionic hydrogel composite via seeding calcium carbonate microparticles for the engineering of ultrasensitive wearable sensors |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210420 |
|
| RJ01 | Rejection of invention patent application after publication |