CN117024782A - Preparation method of hydrophobic ionic liquid conductive gel - Google Patents

Preparation method of hydrophobic ionic liquid conductive gel Download PDF

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CN117024782A
CN117024782A CN202310828996.4A CN202310828996A CN117024782A CN 117024782 A CN117024782 A CN 117024782A CN 202310828996 A CN202310828996 A CN 202310828996A CN 117024782 A CN117024782 A CN 117024782A
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conductive gel
ionic liquid
gel
hydrophobic
preparing
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王頔
许宗灿
张诗悠
傅佳鑫
徐明瑜
张彤
李程鹏
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Guangdong Ocean University
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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
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
    • C08J3/097—Sulfur containing compounds
    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Dispersion Chemistry (AREA)
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Abstract

The application belongs to the technical field of conductive gel, and discloses a preparation method of hydrophobic ionic liquid conductive gel, wherein S1, ethanol, deionized water and ammonia water are stirred to obtain a mixed solution; then dripping tetraethyl silicate into ethanol solution, and then reacting the tetraethyl silicate with the mixed solution; centrifuging after the reaction is finished, discarding supernatant, cleaning sediment, performing ultrasonic treatment and centrifuging, and collecting sediment to obtain silica nanoparticles; s2, firstly dissolving an acrylic ester monomer in the ionic liquid, stirring, and then adding a cross-linking agent and an initiator for stirring; then adding silicon dioxide nano particle powder for ultrasonic dispersion and magnetic stirring; obtaining a precursor solution, and finally, carrying out polymerization reaction to obtain the required hydrophobic ionic liquid conductive gel; the hydrophobic conductive gel with the single network structure prepared by the application has good stability, conductivity, hydrophobicity and underwater conductivity.

Description

Preparation method of hydrophobic ionic liquid conductive gel
Technical Field
The application relates to the technical field of preparation methods of conductive gels, in particular to a preparation method of a hydrophobic ionic liquid conductive gel.
Background
The gel material has excellent flexibility, stretchability and biocompatibility, and has wide application in the fields of flexible sensors, electronic skin, soft robots and the like. The conductive gel plays a general role in the field of flexible electronics, integrates electrochemical and optical properties of metal or semiconductor and viscoelasticity of gel, is an inherent network of a conductive micro/nano structure, and has the excellent collective property of being widely applied to energy conversion and storage, electronic devices, super-hydrophobic coatings and the like.
Currently, the preparation methods of conductive gel include freeze thawing method, binary solvent gel method and photopolymerization method. The freeze thawing method is called repeated freezing-melting method, and according to the physical characteristics of the difference of substances at different temperatures, the freezing can slow down the movement of molecular chains in aqueous solution, the molecular chains contacted with each other are physically crosslinked and tightly combined under the physical actions of Van der Waals force, hydrogen bonds and the like, and then new physical crosslinking is formed when the freezing is repeated. However, the method needs multiple freezing and melting operations, has long preparation period, is difficult to control the temperature and the pressure in the preparation process, and is easy to cause non-uniformity of materials; the binary solvent gel method is a method for forming organic hydrogel by copolymerizing binary organic solvent and monomer, and compared with a freeze thawing method, the conductive gel prepared by the method has better mechanical property and transparency. However, the adjustment of binary solvent gelation is difficult, and the preparation method is too complex; the photopolymerization is a process of initiating the polymerization of monomers by ultraviolet rays or visible light, and is characterized by low polymerization temperature, high reaction selectivity and easy control, and can be used for carrying out the reaction which cannot occur by the traditional molecules, thus expanding the possibility of producing high polymers, but the method needs a light source with specific wavelength such as ultraviolet rays to excite the crosslinking reaction, and the material can be discolored or degraded after long-time exposure to the ultraviolet rays, and the photopolymerization has the advantages of higher speed, higher technical requirement and strict control requirement on reaction conditions.
The ionic conductive gel prepared based on the Ionic Liquid (ILs) maintains the characteristics of non-volatility, high thermal stability, low temperature resistance and the like of the ILs, and has great application potential in the aspects of super capacitors, sensors, electroluminescent devices and the like. Compared with the conductive hydrogel, the ion conductive gel can have higher conductivity without additionally introducing conductive filler; by changing the types of anions and cations of ILs, the physicochemical properties of ILs can be easily adjusted to meet the requirements of related applications; and effectively solves the problems of easy drying and easy freezing of the hydrogel.
The ion-conducting gel may be classified into a single-network ion-conducting gel and a double-network ion-conducting gel according to its three-dimensional network structure. Wherein, the single network ion conductive gel is formed by cross-linking ILs (PILs) of polymerized monomers or polymerizable double bonds as monomers in the ILs. However, hydrophilic ion-conducting gels are unstable in environments with different humidity levels, and their liquid components (i.e., ILs) tend to leak from the polymer matrix under mechanical loading, resulting in degraded device performance; the double-network gel is firstly used for synthesizing the hydrogel with high mechanical property, and is formed by interweaving polymer networks with two different network structures, wherein one network structure is a rigid network and provides high strength and toughness; another network structure is a deformable network with large deformability, which results in a dual network gel with excellent properties of high strength, high ductility and large deformability. However, the tight network structure prevents migration of the conductive ions, resulting in a decrease in ion conductivity of the double network ion conductive gel.
Therefore, it is important to develop a conductive gel that can remain stable for a long period of time. The hydrophobic conductive gel has been widely studied as a substitute functional material due to its excellent properties such as high transparency, adjustable mechanical properties, biocompatibility and multifunctionality, and has a considerable development prospect.
Disclosure of Invention
The application aims to provide a preparation method of hydrophobic ionic liquid conductive gel, which comprises the steps of preparing an ionic liquid ([ BMIm)]TFSI), polymerized monomer (TBMA), crosslinker (EGDMA), photo-thermal initiator (AIBN), nanofiller (SiO) 2 NPs) to obtain a hydrophobic conductive gel with a single network structure [ BMIm ]]Hydrogen bonding, dipole-dipole and ion-dipole interactions between TFSI and TBMA can lock ILs in the polymer network; the hydrophobic group-tertiary butyl on the monomer can also construct a hydrophobic layer on the surface of the gel structural domain, and the conductive gel has good stability, conductivity, hydrophobicity and underwater conductivity. The problems are effectively solved.
In order to achieve the above object, the present application provides the following technical solutions:
the preparation method of the hydrophobic ionic liquid conductive gel comprises the following steps:
s1, preparing silicon dioxide nano particles
Firstly stirring ethanol, deionized water and ammonia water in an ice water bath to obtain a mixed solution by utilizing a sol-gel method; dripping tetraethyl silicate into ethanol solution, stirring for 1-3 seconds, pouring the tetraethyl silicate into the mixed solution, and stirring and reacting in ice water bath for 5-7 hours; centrifuging after the reaction is finished, discarding supernatant, repeatedly cleaning precipitate, performing ultrasonic treatment and centrifugation, collecting precipitate to obtain silica nanoparticles, drying the silica nanoparticles, and grinding the silica nanoparticles into powder for later use;
s2, preparing hydrophobic ionic liquid conductive gel
Firstly, dissolving an acrylic ester monomer in ionic liquid for magnetic stirring, then adding a cross-linking agent and an initiator, and carrying out magnetic stirring again; then adding the silicon dioxide nano particle powder prepared in the step S1, and sequentially carrying out ultrasonic dispersion and magnetic stirring; and performing ultrasonic dispersion again to obtain a precursor solution, and finally transferring the precursor solution into a sealed container, and heating in a water bath to perform polymerization reaction to obtain the required hydrophobic ionic liquid conductive gel.
Further, in S1, the volume ratio of ethanol, deionized water and ammonia water in the mixed solution is 5.5:10.2:1; the volume ratio of the tetraethyl silicate to the ethanol is 1:15.75.
Further, in S1, the ambient temperature for preparing the silica nanoparticles is20 ℃; centrifuging the mixed solution at 8000r/min for 10min, and alternately cleaning the centrifugal precipitate for three times by using ethanol and deionized water; the silica nanoparticles were baked in an oven at 70 ℃ for 5h.
Further, in S2, the acrylate monomer is tert-butyl methacrylate, the ionic liquid is 1-butyl-3-methylimidazole bistrifluoromethanesulfonimide salt, the cross-linking agent is ethylene glycol dimethacrylate, and the initiator is2, 2-azobisisobutyronitrile; wherein the mass ratio of the tert-butyl methacrylate to the 1-butyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt to the ethylene glycol dimethacrylate to the 2, 2-azodiisobutyronitrile is 36-89.5:228.5:52.5:1.
Further, in S2, the time of magnetic stirring is 15 minutes; the ultrasonic dispersion time is2 minutes; the polymerization conditions were: the polymerization was carried out for 24 hours in a 60℃water bath.
Further, in S2, the mass ratio of the ionic liquid to the silica nanoparticles is 228.5:1.
The technical proposal has the beneficial effects that:
1. the application prepares the hydrophobic conductive gel with a single network structure by utilizing fluorine-rich ionic liquid ([ BMim ] TFSI) and hydrophobic acrylic ester monomer (TBMA), and the conductive gel has good stability, conductivity, hydrophobicity and underwater conductivity;
2. the method for preparing the hydrophobic conductive gel is simple, and provides theoretical reference for preparing the hydrophobic conductive gel which can stably work for a long time;
3. the hydrophobic conductive gel prepared by the application effectively prevents the loss of conductive ions and water, and provides theoretical basis for underwater application.
Drawings
FIG. 1 is a schematic flow chart of a preparation method of a hydrophobic ionic liquid conductive gel for preparing silica nanoparticles;
FIG. 2 is a schematic diagram of the synthesis of a hydrophobic conductive gel prepared by the preparation method of the hydrophobic ionic liquid conductive gel of the present application;
FIG. 3 is a diagram of SiO according to an embodiment of the present application 2 FTIR, XRD, SEM and TEM images of NPs;
in the figure, (a) is SiO 2 FTIR spectra of NPs; (b) Is SiO 2 XRD spectrum of NPs; (c) (d) and (e) are SiO 2 SEM of NPs; (f) Is SiO 2 TEM of NPs
FIG. 4 is a bar/line graph of the conductivity of hydrophobic conductive gels at different TBMA levels in accordance with a second embodiment of the present application;
in the figure, (a) is the gel resistance; (b) Is ion conductivity
FIG. 5 shows a second embodiment of the application of different SiO 2 A column/line plot of the conductivity of the gel at NPs addition;
in the figure, (a) is the gel resistance; (b) Is ion conductivity
FIG. 6 is a bar/line graph of the mechanical properties of hydrophobic conductive gels at different TBMA levels in example three of the present application;
in the figure, (a) is a tensile stress-strain curve; (b) For stress-elongation at break change pattern
FIG. 7 shows a third embodiment of the application of different SiO 2 A mechanical property column/line graph of the hydrophobic conductive gel at NPs addition;
in the figure, (a) is a tensile stress-strain curve; (b) For stress-elongation at break change pattern
FIG. 8 is a tensile stress-strain plot of a hydrophobic conductive gel of example III of the present application for 50 cycles at 200% strain;
FIG. 9 shows a fourth embodiment of the application of different SiO 2 A hydrophobic property line graph of the hydrophobic conductive gel at the NPs addition level;
FIG. 10 shows a fourth embodiment of the application of different SiO 2 Schematic of contact angle of hydrophobic conductive gel at NPs addition;
in the figure, (a) is 0g; (b) 0.002g; (c) 0.005g; (d) 0.008g; (e) 0.01g; (f) 0.02g; (g) 0.03g; (h) 0.04g; (i) 0.05g
FIG. 11 is a schematic diagram showing the contact angle of the hydrophobic conductive gel at different soaking times in the fourth embodiment of the present application;
in the figure, (a) is 0h; (b) is 24 hours; (c) 48 hours; (d) For 72h
FIG. 12 is a schematic illustration of a fifth embodiment of the application with 1.5mL TBMA and 0.02g SiO 2 Swelling behavior curve graph of the hydrophobic conductive gel with NPs proportion;
FIG. 13 is an optical image of a hydrophobic conductive gel at different soak times in a fifth embodiment of the present application;
in the figure, (a) is 0h; (b) is 24 hours; (c) 48 hours; (d) For 72h
FIG. 14 is a bar/line graph showing leakage behavior of the hydrophobic conductive gel at various soak times in a sixth embodiment of the present application;
in the figure, (a) is the conductivity change of the gel soaking solution; (b) is a change in gel resistance; (c) For variation of gel conductivity
Detailed Description
The application is described in further detail below with reference to the attached drawings and embodiments:
the raw materials required for preparing the hydrophobic conductive gel are shown in table 1;
TABLE 1 Experimental reagents
The experimental equipment used during the experiment is shown in table 2.
Table 2 laboratory apparatus
The preparation method of the hydrophobic ionic liquid conductive gel comprises the following steps:
silica nanoparticles (SiO) 2 NPs) are prepared
As shown in fig. 1, by a sol-gel method, 20.50mL of ethanol, 38.25mL of deionized water and 3.75mL of ammonia water are stirred and mixed in an ice water bath in sequence at an ambient temperature of 20 ℃; then 3.73mL of tetraethyl silicate (TEOS) is dripped into 58.77mL of ethanol solution, stirred in an ice-water bath for 2 seconds, quickly poured into the mixed solution containing ammonia water, and stirred in the ice-water bath for reaction for 6 hours; after the reaction is finished, centrifuging the mixed solution for 10min at the speed of 8000r/min, discarding supernatant, alternately cleaning three times by using ethanol and deionized water, and collecting precipitate after ultrasonic and centrifugal treatment; siO obtained 2 NPs were baked in an oven at 70 ℃ for 5h and ground to powder for future use.
Preparation of hydrophobic conductive gel
As shown in FIG. 2, the different monomer (TBMA) contents (0.8 mL, 1.1mL, 1.4mL, 1.5mL, 1.6mL, 1.7mL, 2.0 mL) were first dissolved in 3.176mL of [ BMIm]In TFSI, magnetically stirring for 15min; then 0.004mL of crosslinker (EGDMA) and 0.02g of initiator (AIBN) are added and magnetically stirred for 15min; next, 0.04g of SiO was added 2 NPs are dispersed for 2min by ultrasonic and stirred for 15min by magnetic force; dispersing for 2min by ultrasonic to obtain a precursor solution; finally, transferring the precursor solution into a sealed centrifuge tube, and thermally initiating polymerization in a constant temperature water bath (BWS-10, shanghai Blueguard) for 24 hours, wherein the temperature is set to 60 ℃, thus obtaining the hydrophobic conductive gel with different monomer contents. After the optimal monomer proportion is obtained, siO is changed 2 NPs addition amount (0 g, 0.002g, 0.005g, 0.008g, 0.01g, 0.02g, 0.03g, 0.04g, 0.05 g), and repeating the above steps to obtain different SiO 2 NPs added amount of hydrophobic conductive gel.
Example 1
SiO 2 Structural characterization test of NPs
SiO was observed by Scanning Electron Microscopy (SEM) (Regulus 8100, hitachi, japan) and Transmission Electron Microscopy (TEM) (Talos F200s, U.S. FEI) 2 Morphology of NPs. The SEM acceleration voltage was 5kV. Prior to SEM measurementThe sample was oven dried, ground and directly glued to a conductive adhesive. The TEM accelerating voltage was 200kV. Prior to TEM measurements, the samples were oven dried, ground and dispersed in ethanol with ultrasound for 5min. Then, a few drops of the dispersion were dropped onto a common copper mesh and dried at room temperature. Using KBr pellet test method, fourier transform Infrared spectrometer (FTIR) (Nicolet iS20, U.S. Thermo Scientific) was used at 4000-400 cm -1 Recording SiO over wavenumber range 2 Vibration of NPs. SiO by X-ray diffraction (XRD) (Ultima IV, japan Rigaku) 2 The crystalline phase of NPs was characterized.
As can be seen from FIG. 3 (a), 3420cm -1 The broad peak at the position corresponds to an antisymmetric telescopic vibration peak of-OH group of 1630cm -1 The peak at the point is the bending vibration peak of H-O-H, 955cm -1 The peak at which belongs to the bending vibration peak of Si-OH. 1110cm -1 The strong and wide absorption band is Si-O-Si antisymmetric telescopic vibration, 801cm -1 And 475cm -1 The peak at the position is attributed to the symmetrical stretching vibration and bending vibration of Si-O bond, belonging to SiO 2 Characteristic peaks of NPs;
from fig. 3 (b), it can be seen that there is a strong diffraction peak at 2θ= 21.604 ° with SiO 2 The characteristic peaks of the standard card (PDF # 27-0605) correspond to the (111) crystal plane, and the crystallinity is 96.97%. SiO was observed by SEM image 2 The surface morphology of NPs was a uniform sphere as shown in fig. 3 (c);
as shown in FIGS. 3 (d), (e) and (f), siO 2 The particle size of NPs is about 210-225 nm.
Example two
Conductivity of hydrophobic conductive gel
At room temperature (25 ℃ C.), the different (monomer, siO 2 NPs) content of the gel was cut into rectangular strips of 0.2cm thickness, 3cm length and 1cm width. Gel conductivity was tested using a bench digital multimeter (8846A, FLUKE, usa) using an ac impedance method, and the gel conductivity calculation formula was as follows:
σ＝L/AR b
wherein "σ" is the conductivity of the gel, "L" is the thickness of the gel, "A" is the electrode area, "R b "is the bulk resistance of the gel.
As shown in FIG. 4 (b), at 0.04g SiO 2 With increasing amounts of NPs added, the ion conductivity of the hydrophobic conductive gel overall was decreasing with increasing amounts of monomeric TBMA, inversely correlated to the resistance plot of fig. 4 (a). Wherein the gel conductivity of 0.8mL TBMA is highest and is 4.4X10 -1 Mu S/cm; gel conductivity was lowest at 2.0mL TBMA, 3.5X10 -1 Mu S/cm. This is because the more the monomer content increases, the more the TBMA and the polymeric network crosslink and entangle, i.e., the more the ionic-dipole and hydrogen bond interactions between the ionic liquid and the polymeric monomer.
As shown in FIG. 5 (b), when the TBMA content was 1.5mL, the reaction proceeded with SiO 2 The ionic conductivity of the hydrophobic conductive gel tends to decrease first and then increase and then decrease when the addition amount of NPs increases. This trend is consistent with the trend of gel hydrophobicity in fig. 10. Wherein, 0.05g SiO 2 The gel with the addition of NPs had the worst conductivity, and the conductivity was 5.0X10 -1 μS/cm；0.02g SiO 2 The gel with NPs added is preferably of conductivity 6.2X10 -1 μS/cm。
Example III
Mechanical Properties of hydrophobic conductive gel
At room temperature (25 ℃ C.), the different (monomer, siO 2 NPs) content of the gel was cut into 1×3cm rectangular strips, and the mechanical properties of the gel were tested with an electronic universal tester (UTM 2203, shen tens) and a weighing cell of 100N at a stretching speed of 10 mm/min. The tensile test was repeated for 50 cycles at a tensile strain of 200% and a tensile speed of 50mm/min at 10min intervals to test the mechanical properties of the gel. Each sample was tested in duplicate 3 times.
As shown in fig. 6 (a), the tensile strength of the hydrophobic conductive gel increases with the TBMA content. This is because the higher the TBMA content, the more capable the TBMA and polymer crosslink and entangle. This also results in the gel having a high TBMA content becoming stiff and requiring more force to deform to some extent;
as shown in FIG. 6 (b), the gel having a TBMA content of 1.5mLThe toughness of (C) is best, and the elongation at break reaches 573.61 percent. In order to provide the gel with high transparency, good conductivity and flexibility, the hydrophobic conductive gel with TBMA content of 1.5mL was selected as the research object in the subsequent experiment, and the ionic conductivity of the hydrophobic conductive gel is 4.1X10% -1 Mu S/cm, the breaking stress was 41.61kPa, and the breaking elongation was 573.61%.
As shown in FIG. 7 (b), at a TBMA content of 1.5mL, with SiO 2 The tensile stress of the hydrophobic conductive gel overall tends to rise and then fall with increasing NPs addition. Wherein, 0.02g of SiO 2 The tensile stress of the gel of NPs was maximum, 39.83kPa. In order to make the gel exhibit good hydrophobicity, conductivity and strength, 0.02g of SiO was selected in this example based on the above experimental results 2 The hydrophobic conductive gel of NPs was subjected to subsequent studies, with a contact angle of 103.13℃and an ionic conductivity of 6.2X10 -1 Mu S/cm, tensile stress of 39.83kPa and elongation at break of 242.00%.
As shown in FIG. 8, after 50 cycles of continuous stretching to 200% strain and standing for 10 minutes, the film was prepared at TBMA of 1.5mL and SiO 2 Hydrophobic conductive gels with NPs of 0.02g exhibit less hysteresis loops and residual strain. After the 1 st cycle, a significant hysteresis loop drop occurs, but the energy hysteresis loop area thereafter is not large and substantially uniform. This is because under tensile strain, some hydrogen bonds between the polymer networks are rapidly dissociated and re-established, effectively achieving dissipation of energy. In the unloading process, broken hydrogen bonds are rebuilt within enough rest time, so that the hydrophobic conductive gel has certain fatigue resistance.
Example IV
Hydrophobic Properties of hydrophobic conductive gel
8. Mu.L of water were carefully deposited on different SiO's with a syringe at room temperature (25 ℃) 2 The contact angle of the gel was measured on the surface of the gel with NPs added thereto by a contact angle measuring instrument (XG-CAMB 3, shanghai SUNZERN). If the conductive gel is in the conductive gel with different soaking time (0 h, 24h, 48h and 72 h), the excessive water on the surface of the sample is firstly wiped by filter paper, and the steps are repeatedAnd (3) a step.
As shown in FIG. 9, when the TBMA content was 1.5mL, the reaction proceeded with SiO 2 The contact angle of the hydrophobic conductive gel tends to decrease first and then increase and then decrease when the addition amount of NPs increases.
As shown in FIG. 10 (d), 0.008g SiO 2 NPs have the worst gel hydrophobicity with a contact angle of 90.13 °; as shown in FIG. 10 (f), 0.02g of SiO 2 The gel hydrophobicity of NPs is best with a contact angle of 103.13 °.
No SiO is added 2 The contact angle of the hydrophobic conductive gel of NPs is 99.83 ° (. Gtoreq.90°), which indicates that the hydrophobic tert-butyl group of the monomer and the inherent hydrophobicity of the ionic liquid make the gel exhibit a certain hydrophobicity. At the time of adding a small amount of SiO 2 At NPs, the hydrophobic capacity of the gel is reduced. This is because of the small amount of SiO 2 NPs do not achieve uniform cross-linking with the polymer network. When SiO 2 When NPs reaches 0.02g, a certain amount of SiO 2 NPs are combined in a gel with polyacrylate polymer networks and [ BMIm]The hydrogen bond, dipole-dipole and ion-dipole interaction between TFSI ensure good compatibility of gel, help lock ILs in gel network, terminate transportation of most substances across gel boundary, play an important role in inhibiting interface diffusion of water molecules and ions, and improve hydrophobicity of gel. However, when SiO 2 At NPs exceeding 0.02g, the gel water repellency begins to decrease. This is because of SiO 2 NPs are inherently hydrophilic. When SiO 2 When the NPs content is too high, the content of hydrophilic substances in the gel increases, and the hydrophobic interface on the surface of the gel network becomes loose, so that the hydrophobicity decreases.
As shown in fig. 11, as the soaking time increases, the contact angle of the hydrophobic conductive gel decreases from 103.13 ° (fig. 11 (a)) to 90.01 ° (fig. 11 (d)). This change in contact angle is related to the presence of a concentration gradient and osmotic pressure in the microenvironment and aqueous environment within the gel. At the same time, when the gel is immersed in water, siO 2 The NPs surface has a large number of hydroxyl groups, so that the free energy of the surface of the gel is increased, and the hydrophobic capacity of the hydrophobic conductive gel is reduced.
Example five
Swelling Property of hydrophobic conductive gel
At room temperature (25 ℃) the hydrophobic conductive gel was cut into rectangular strips of 0.2cm thickness, 3cm length and 1cm width, and completely immersed in sufficient deionized water until the mass of the gel reached an equilibrium value. Excess water on the surface of the swelled hydrophobic conductive gel sample is wiped off by filter paper before weighing, and then the mass of the sample is weighed by an electronic balance (BSA 124S, beijing Sartorius), and data are recorded every 1h, 2h, 3h, 6h, 9h, 12h, 24h, 36h, 48h and 72h, and three groups are paralleled. The gel swelling degree was calculated as follows:
δ＝(W S -W 0 )/W 0
wherein "δ" is the degree of swelling of the gel; w (W) S "is the mass of the gel after swelling; w (W) 0 "is the mass of the gel before swelling.
As shown in FIG. 12, when TBMA and 0.02g SiO were mixed in a proportion of 1.5mL 2 The hydrophobic conductive gel of NPs was found to assume a contracted state when placed in water. This is due to the concentration gradient and osmotic pressure of the environment within the gel and the aqueous environment. However, the shrinkage was relatively low, only 14.45%.
As shown in fig. 13, the optical contrast plot of the hydrophobic conductive gel before soaking versus soaking for 24h, 48h and 72h, respectively, did not change much in volume.
Example six
Leakage behavior of hydrophobic conductive gels
The hydrophobic conductive gel was cut into rectangular strips of 0.2cm thickness, 3cm length and 1cm width at room temperature (25 ℃) and completely immersed in 1L of deionized water. The ion conductivity of the soaking solution was tested using a conductivity meter (DDSJ-308F, shanghai Lei Ci), data were recorded every 1h, 2h, 3h, 6h, 9h, 12h, 24h, 36h, 48h, 72h, three groups in parallel; the gel conductivity was measured using a bench digital multimeter (8846A, FLUKE, usa), with data recorded every 0h, 3h, 6h, 9h, 12h, 24h, 36h, 48h, 72h, three groups in parallel, and the gel conductivity calculated using equation (1).
As shown in FIG. 14, the hydrophobic conductive gel is immersed after being immersed for 72 hoursThe ionic conductivity of the soaking solution increased from 1.83. Mu.S/cm initially to 22.66. Mu.S/cm (FIG. 14 a). It is apparent from fig. 14 (b) that the gel has a large resistance when immersed in water, and maintains a high impedance in water. The ion conductivity is also from 6.0X10 -1 Mu S/cm drop to 3.8X10 -2 μS/cm, but this value remained stable during the subsequent soaking process (FIG. 14 c). The water molecules can act as donors and acceptors of hydrogen bonds, solvating the ions, i.e. the negative charge of the ionic liquid and the cations in the water are attracted to each other. Although the conductive ions diffuse in the water environment, the conductivity of the hydrophobic conductive gel is still constant within a certain range.
In conclusion, it is known that fluorine-rich ILs 1-butyl-3-methylimidazole bistrifluoromethanesulfonimide salt ([ BMIm) was obtained by thermally initiated polymerization]TFSI) and hydrophobic monomer tert-butyl methacrylate (TBMA) to prepare the hydrophobic conductive gel with a single network structure. The proportion of each component in the gel is optimized by researching the conductivity, the hydrophobicity and the underwater conductivity. Experiments show that when the TBMA content is 1.5mL, siO 2 At an NPs content of 0.02g, the prepared hydrophobic gel has the best performance.
(1) According to the result of the conductivity test of the hydrophobic conductive gel, the ion conductivity of the hydrophobic conductive gel is in a decreasing trend along with the increase of the TBMA content; and when the TBMA content is 1.5mL, the reaction is carried out along with SiO 2 The increase in the amount of NPs added shows a tendency that the ion conductivity decreases first and then increases and then decreases. Wherein, 0.02g of SiO 2 The NPs have the best conductivity of 6.2X10 -1 μS/cm。
(2) According to the mechanical property test result of the hydrophobic conductive gel, the tensile strength of the hydrophobic conductive gel is larger along with the increase of the TBMA content, and the maximum elongation at break of the hydrophobic conductive gel can reach 573.61%; and when the TBMA content is 1.5mL, the reaction is carried out along with SiO 2 The tensile strength of the gel tends to increase and then decrease with increasing NPs addition. Wherein, 0.02g of SiO 2 The tensile stress of NPs is greatest and the elongation at break is smallest, 39.83kPa and 242.00%, respectively. In addition, the gel has a certain fatigue resistance and shows a higher degree of resistance during 50 stretching cyclesSmall hysteresis loops and residual strain.
(3) According to the construction result of the hydrophobic layer on the surface of the hydrophobic conductive gel, it is found that along with SiO 2 The contact angle of the hydrophobic conductive gel tends to decrease first and then increase and then decrease when the addition amount of NPs increases. Wherein, 0.02g of SiO 2 The gel hydrophobicity of NPs is best with a contact angle of 103.13 °. When 1.5mL TBMA and 0.02g SiO 2 When the hydrophobic conductive gel prepared by NPs is placed in water, the gel conductivity reaches equilibrium under a certain time. The shrinkage of the hydrophobic conductive gel is 14.45%, the ionic conductivity of the soaking solution is 22.66 mu S/cm, the contact angle is reduced to 90.01 DEG, and the ionic conductivity of the gel is reduced to 3.8X10 -2 μS/cm。
The foregoing is merely exemplary embodiments of the present application, and detailed technical solutions or features that are well known in the art have not been described in detail herein. It should be noted that, for those skilled in the art, several variations and modifications can be made without departing from the technical solution of the present application, and these should also be regarded as the protection scope of the present application, which does not affect the effect of the implementation of the present application and the practical applicability of the patent. The protection scope of the present application is subject to the content of the claims, and the description of the specific embodiments and the like in the specification can be used for explaining the content of the claims.

Claims (6)

1. The preparation method of the hydrophobic ionic liquid conductive gel is characterized by comprising the following steps of:
s1, preparing silicon dioxide nano particles
Firstly stirring ethanol, deionized water and ammonia water in an ice water bath to obtain a mixed solution by utilizing a sol-gel method; dripping tetraethyl silicate into ethanol solution, stirring for 1-3 seconds, pouring the tetraethyl silicate into the mixed solution, and stirring and reacting in ice water bath for 5-7 hours; centrifuging after the reaction is finished, discarding supernatant, repeatedly cleaning precipitate, performing ultrasonic treatment and centrifugation, collecting precipitate to obtain silica nanoparticles, drying the silica nanoparticles, and grinding the silica nanoparticles into powder for later use;
s2, preparing hydrophobic ionic liquid conductive gel
Firstly, dissolving an acrylic ester monomer in ionic liquid for magnetic stirring, then adding a cross-linking agent and an initiator, and carrying out magnetic stirring again; then adding the silicon dioxide nano particle powder prepared in the step S1, and sequentially carrying out ultrasonic dispersion and magnetic stirring; and performing ultrasonic dispersion again to obtain a precursor solution, and finally transferring the precursor solution into a sealed container, and heating in a water bath to perform polymerization reaction to obtain the required hydrophobic ionic liquid conductive gel.
2. The method for preparing the hydrophobic ionic liquid conductive gel according to claim 1, wherein the method comprises the following steps: in S1, the volume ratio of ethanol, deionized water and ammonia water in the mixed solution is 5.5:10.2:1; the volume ratio of the tetraethyl silicate to the ethanol is 1:15.75.
3. The method for preparing the hydrophobic ionic liquid conductive gel according to claim 1, wherein the method comprises the following steps: in S1, the ambient temperature for preparing the silica nanoparticles is20 ℃; centrifuging the mixed solution at a speed of 8000r/min for 10min; alternately cleaning the centrifugal precipitate for three times by using ethanol and deionized water; the silica nanoparticles were baked in an oven at 70 ℃ for 5h.
4. The method for preparing the hydrophobic ionic liquid conductive gel according to claim 1, wherein the method comprises the following steps: in S2, the acrylic ester monomer is tert-butyl methacrylate, the ionic liquid is 1-butyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, the cross-linking agent is ethylene glycol dimethacrylate, and the initiator is2, 2-azobisisobutyronitrile; wherein the mass ratio of the tert-butyl methacrylate to the 1-butyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt to the ethylene glycol dimethacrylate to the 2, 2-azodiisobutyronitrile is 36-89.5:228.5:52.5:1.
5. The method for preparing the hydrophobic ionic liquid conductive gel according to claim 1, wherein the method comprises the following steps: in S2, the magnetic stirring time is 15 minutes; the ultrasonic dispersion time is2 minutes; the polymerization conditions were: the polymerization was carried out for 24 hours in a 60℃water bath.
6. The method for preparing the hydrophobic ionic liquid conductive gel according to claim 1, wherein the method comprises the following steps: in S2, the mass ratio of the ionic liquid to the silica nanoparticles is 228.5:1.
CN202310828996.4A 2023-07-07 2023-07-07 Preparation method of hydrophobic ionic liquid conductive gel Pending CN117024782A (en)

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