CN108752815B - Preparation method and application of through hole phase transfer type IPMC (Ionic Polymer Metal composite) with PVDF (polyvinylidene fluoride)/PVP (polyvinyl pyrrolidone)/IL (IL) as base film - Google Patents
Preparation method and application of through hole phase transfer type IPMC (Ionic Polymer Metal composite) with PVDF (polyvinylidene fluoride)/PVP (polyvinyl pyrrolidone)/IL (IL) as base film Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a high-performance through-hole phase-transfer type IPMC (Ionic Polymer) taking PVDF (polyvinylidene fluoride)/PVP (polyvinyl pyrrolidone)/IL (IL) as a base film, wherein the base film consists of the base film, carbon nanotube film electrodes fixed on two sides of the base film and an externally-connected electric signal input system; since the pore-transition type IPMC has hydrophobicity, IPMC driving by Ion Liquid (IL) driving is more stable. The through-hole phase-transfer type IPMC has a large number of channels, improves the ion migration volume in the material, and forms larger pressure difference and ion flow in the material, thereby being beneficial to forming larger drive for an electric actuator and simultaneously providing larger mechanical property.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a preparation method and application of a high-performance through-hole phase transfer type IPMC (Ionic Polymer Metal composite) with PVDF (polyvinylidene fluoride)/PVP (polyvinyl pyrrolidone)/IL (IL) as a base film.
Background
The perfluorosulfonic acid product mainly comprises a fluorocarbon main chain and a sulfonate side chain, and has the following chemical structure:
the structure of the fluorocarbon main chain is similar to the chemical structure of polytetrafluoroethylene, and the fluorocarbon main chain has hydrophobic performance, while the perfluorinated sulfonic acid has hydrophilic performance due to the hydrophilicity of the sulfonate functional group of the side chain. Currently, mainly DuPont in the United states produces perfluorosulfonic acid products including Nafion membranes and Nafion solution series products.
The Ionic Polymer Metal Composite (IPMC) can be prepared by plating noble metals such as platinum and gold on both sides of the Nafion membrane by chemical plating, and is also called artificial muscle. The material can bend under the action of an electric field, can generate a micro electric field in an alternating bending state, can be applied to an actuator and a sensor, and is widely researched and applied to the actuator at present due to the light weight, low driving voltage and performance similar to that of biological muscles. The driving mechanism is as follows:
under the action of electric field, positive ions (Na)+,Li+,K+) Carrying some water molecules towards the cathode causing shrinkage of the anode and expansion of the cathode so that the material bends. Such a materialThe driving voltage of the material is low, usually about 1-3V, however, the driving of the ionic polymer metal compound is that the cations in the substrate material (Nafion) drive water molecules to move to the cathode under the action of an electric field, so that the material bends to the anode. Therefore, in the braking process, water molecules play a key role, and the loss of moisture can influence the output force and displacement of the IPMC artificial muscle material, so that the IPMC artificial muscle is mainly applied in water or a wet environment at present, and the working time of the IPMC artificial muscle is quite short in a dry environment.
In recent years, in order to improve the mechanical output performance of the IPMC artificial muscle, a lot of studies have been made by domestic and foreign scholars, including improving the preparation method of chemical plating, i.e. using PVP to improve the dispersion of the surface nano metal electrode during the chemical plating process, thereby reducing the loss of moisture and improving the mechanical performance of IPMC. As the thickness of the commercial Nafion membrane is between 100-300 um, a thicker Nafion membrane can be prepared by a Nafion solution casting method, so that the mechanical output performance of the IPMC artificial muscle is improved, but the drive voltage of the IPMC prepared by the thicker Nafion membrane is correspondingly higher, so that the hydrolysis process is increased, and the hydrolysis voltage of water is generally 1.23V. At present, the better method is to modify a substrate material (Nafion) and use the modified Nafion membrane to prepare the IPMC, so that the mechanical property and the working time of the IPMC can be better improved.
In terms of modification, a korean scholars Vinh khanhan Nguyen et al adds nanoparticle (nanoparticles) silicate such as hyperphosphatite (montmorillonite) or silica (fumed silica) to a Nafion solution to form Nafion in a nanocomposite state, and can change the performance of Nafion internal network channels (Nafion matrix) to improve the mechanical characteristics of Nafion.
The IPMC made of Nafion has the characteristics of small voltage, quick reverberation and the like, is deeply applied to various fields of science and technology, but has the defects of low porosity, poor water absorption, short displacement distance, short displacement period, small mechanical property and the like.
Disclosure of Invention
In view of the problems in the prior art, the present invention provides a high performance through-hole phase-transfer type IPMC using PVDF/PVP/IL as a base film, wherein the PVDF/PVP/IL composite film has high porosity and large pore size due to phase transfer and hypochlorous acid immersion, and the finger-shaped pores and large porosity can form a large number of ion channels, which is beneficial to the migration of ions in the ionic liquid environment of the electric actuator, thereby having high displacement characteristics.
In order to solve the technical problems, the invention adopts the following technical scheme:
the high-performance through-hole phase transfer type IPMC with PVDF/PVP/IL as a base film consists of the base film, carbon nanotube film electrodes fixed on two sides of the base film and an external electric signal input system, wherein the base film is made of polyvinylidene fluoride, polyvinylpyrrolidone and 2-imidazole-1-yl ethylamine ionic liquid, the carbon nanotube film electrodes are formed by dispersing the polyvinylidene fluoride doped with carbon nanotubes through the ionic liquid, and the electric signal input system is a sine wave, a square wave or a triangular wave of 0.1-10Hz and 0.5-5V.
The thickness of the basement membrane is 100-800 microns, and the thickness of the carbon nanotube electrode is 10-60 microns.
The surface resistance of the carbon nano tube membrane electrode is 0.5-300 omega.
The preparation method of the high-performance through hole phase transfer type IPMC with PVDF/PVP/IL as a base film comprises the following steps:
(1) preparation of PVDF/PVP/IL basement membrane solution: adding a DMF solvent into a mixture of PVDF and PVP, heating, stirring and mixing, then adding 1-ethyl-3-methylimidazole tetrafluoroborate ionic liquid, uniformly mixing, standing, vacuumizing and removing air bubbles in the solution to obtain a PVDF/PVP/IL membrane solution;
(2) preparation of PVDF/PVP/IL basement membrane: quantitatively dripping the PVDF/PVP/IL membrane solution prepared in the step (1) on a glass plate, then flatly spreading the PVDF/PVP/IL membrane solution on a spin coater, standing the PVDF/PVP/IL membrane solution for 80s, then putting the PVDF/PVP/IL membrane solution in 20% ethanol solidification liquid, completing the phase inversion process, precipitating and forming a membrane, putting the membrane in deionized water, changing water every 5-8h, removing the residual solvent on the membrane, and finally drying the membrane in a 70 ℃ drying oven to obtain a PVDF/PVP/IL basement membrane;
(3) removal of PVP from PVDF/PVP/IL basement membrane: putting the PVDF/PVP/IL basement membrane prepared in the step (2) into a hypochlorous acid solution with the mass concentration of 0.5%, adjusting the pH value of the solution to 5-7, heating in a water bath at 50 ℃, and heating at a constant temperature for 48 hours; checking the pH change condition of the solution once every five hours, then adjusting the pH change condition to a specified range, periodically adding water like a water bath kettle to avoid the water in the water bath kettle from being dried, and taking out and drying the solution for later use;
(4) PVDF/PVP/IL basement membrane chimerism preparation of IPMC: and uniformly coating the prepared carbon nano tube/ionic liquid gel integrated electrode liquid on two sides of the surface of the dried base film, then putting the base film into an oven, adjusting the temperature to 70 ℃, and drying to obtain the IPMC taking PVDF/PVP/IL as the base film.
In the PVDF/PVP/IL membrane solution in the step (1), the mass fraction of PVDF is 14%, the mass fraction of 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid is 5%, and the mass of PVP accounts for 15% of the mass of PVDF.
In the step (2), 2-7mL of PVDF/PVP/IL membrane solution is dripped on a glass plate, and the rotating speed of a spin coater is 40-80 r/min.
In the step (3), the remaining porogen PVP is removed by chloric acid to make the total pore volume (P/P) of the membrane00.954) is 0.5-0.85.
The preparation method of the carbon nanotube/ionic liquid gel integrated electrode liquid in the step (4) comprises the following steps: weighing original MWCNTs by adopting a carbon nano tube oxidation grafting method, adding the weighed original MWCNTs into a mixed solution of concentrated sulfuric acid and concentrated nitric acid, refluxing for 5 hours at the temperature of 100 ℃, cooling, diluting, performing suction filtration by using a polytetrafluoroethylene filter membrane, and washing by using distilled water until filtrate is neutral; drying in a vacuum drying oven at 100 ℃ for 4h, oxidizing to obtain CNT-COOH, adding dioxane as a solvent to ultrasonically disperse the CNT-COOH for 15min, adding EDC/NHS to react for 30min, centrifugally separating to obtain CNT-NHS, adding triethylamine as a solvent, adjusting the pH value of the solution to 6-7, adding dried 2-imidazole-1-ethylamine ionic liquid, mixing and stirring uniformly, reacting for 6h to form a carbon nanotube/ionic liquid gel integrated electrode liquid, and finally storing at low temperature for later use.
The mass ratio of the CNT-NHS to the 2-imidazole-1-yl ethylamine ionic liquid is 13: 54.
The high-performance IPMC using PVDF/PVP/IL as a base film is applied to an electric actuator.
The PVDF/PVP/IL basement membrane is prepared by adopting the phase transfer, the exchange between an organic solvent DMF in a membrane solution and water and ethanol in a coagulating bath can be realized in the phase transfer process, PVP is transferred to the coagulating liquid along with the organic solvent, the coagulating bath enters the membrane, the PVP is lost, a large number of gaps are formed in the membrane, and the membrane is highly porous.
Because the phase transfer mode cannot obtain the wanted through hole structure, the research finds that the hypochlorous acid can be used for partially removing PVP in the PVDF/PVP/IL base film again according to the difference of concentration and pH, and carrying out secondary pore-forming, so that the wanted highly porous through hole structure is obtained, the formation of a hydrated ion channel is facilitated, and the actuating performance of the IPMC is improved.
Preparing the carbon nano tube/ionic liquid gel integrated electrode solution: the imidazole cation-based ionic liquid is a good carbon nano tube dispersant. The ionic liquid is fluid at room temperature, is crosslinked with pi electrons on the surface of the carbon nano tube in a cation-pi or pi-pi form, can disperse the carbon nano tube, does not agglomerate, forms a gel substance easy to process, has strong stability, and can maintain the physical property at low temperature. In addition, the ionic liquid can be used as a dispersing agent and can be crosslinked with the carbon nano tube to form more stable gel. The following 2 techniques were used to prepare carbon nanotube/ionic liquid gels: a carbon nano tube oxidation grafting method. As shown in fig. 3, the carbon nanotubes are first oxidized, then activated by EDC, NHS, and then coupled with amine-based ionic liquid to form a gel; b electrochemical grafting method of carbon nanotube. And (3) placing the alkenyl ionic liquid cations and the carbon nano tubes in an electric field for crosslinking, and then reacting with ionic liquid anions to generate the carbon nano tube/ionic liquid gel. Weighing 2.0g of original MWCNTs, adding the weighed original MWCNTs into a mixed solution of 150mL of concentrated sulfuric acid and 50mL of concentrated nitric acid, refluxing for 5 hours at 100 ℃, cooling, diluting, performing suction filtration by using a 0.22 mu m polytetrafluoroethylene filter membrane, and washing by using distilled water until the filtrate is neutral; drying for 4h in a vacuum drying oven at 100 ℃. And oxidizing to obtain CNT-COOH, adding dioxane serving as a solvent to ultrasonically disperse the CNT-COOH for 15min, adding EDC/NHS to react for 30min, centrifugally separating to obtain CNT-NHS, adding triethylamine serving as a solvent, adjusting the pH value of the solution to be 6-7, drying the 2-imidazole-1-ethylamine Ionic Liquid (IL) in an oven at 80 ℃, adding the 2-imidazole-1-ethylamine ionic liquid, mixing and stirring uniformly, reacting for 6h to form the carbon nanotube/ionic liquid gel integrated electrode, and finally storing at low temperature for later use.
The invention has the beneficial effects that: 1. the IPMC provided by the invention has high porosity, and the PVDF/PVP/IL basement membrane is obtained by double treatment of a phase transfer process and hypochlorous acid PVP removal, so that the porosity is high, the IPMC can absorb more ionic liquid, and the stable driving of the IPMC for a long time can be maintained.
2. The through hole phase transfer type IPMC taking PVDF/PVP/IL as a basement membrane provided by the invention has hydrophobicity, so that the IPMC can be driven by Ionic Liquid (IL), the obtained IPMC is driven more stably, and the driving time is longer.
3. The through-hole phase transfer type IPMC taking PVDF/PVP/IL as a base film provided by the invention has a large number of channels, the ion transfer amount in the material can be greatly improved by the large number of channels, and larger pressure difference and ion flow are formed in the material, so that larger driving of an electric actuator can be formed, and larger mechanical property can be provided.
4. The IPMC of the invention has wider application field. For example, because the IPMC of the present invention has light weight and low energy consumption, it can be used in flapping wing aircraft, and can greatly reduce the weight of the aircraft itself, and its high maneuverability can provide enough power for flight, and its excellent mechanical properties can provide enough mechanical support for flight, and its highly porous structure and ionic liquid driving also provide continuous endurance guarantee for flight (see fig. 1).
5. The IPMC is driven by 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid, the ionic liquid drive enables the motion state of the IPMC to be more stable, and meanwhile, the ionic liquid is not volatilized and consumed in the motion process, so that the IPMC can stably work for 2.2 hours for a long time, and the time is 2 times of that under the water drive.
Drawings
FIG. 1 is a model of an ornithopter.
FIG. 2 is a schematic diagram of the structure of four samples of the present invention (a is PVDF/PVP/IL basement membrane, b is SWCNT/ionic liquid electrode).
FIG. 3 shows the synthetic route of the ionic liquid for the oxidation grafting of carbon nanotubes.
FIG. 4 SEM image of cross-section, electrode plane of SWCNT/IL electrode IPMC.
Fig. 5 is a schematic view of an electric actuator arrangement. 1. -a signal generating module, 2, -a force measuring module, 3, -a signal processing module, 4, -an ion-exchange polymer.
FIG. 6 specific surface area and porosity plots of PVDF/PVP/IL base membranes
FIG. 7 deflection plots of sample four at different voltages: a working condition of 0.5Hz 2.5V
b the working condition is 0.5Hz 3V.
FIG. 8 is a comparison of the infrared spectra of sample one, sample two, sample three, and sample four, for a, b, c, and d.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
Example 1 (casting method for preparing base film)
The base film of IPMC was prepared by casting: weighing 2.196g of PVDF solution, 0.3876g of PVP and 20ml of DMF solvent, adding 1ml of 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid into a beaker, mixing and stirring uniformly, vacuumizing the mixed membrane solution at low pressure, placing the vacuumed solution in air for standing for one minute to obtain a membrane solution, then coating the membrane solution on a glass slide to be spread out, and placing the glass slide in an oven at 70 ℃ for drying for 6 hours to obtain the PVDF/PVP/IL basement membrane.
Example 2 (phase transfer mode preparation of base film)
Preparing a PVDF/PVP/IL basement membrane by adopting a phase transfer mode: weighing 2.196g of PVDF powder (14 percent of the mass of the solution), 0.3876g of PVP powder (15 percent of the content of the PVDF powder) and 20ml of DMF solvent, adding 1ml of ionic liquid, mechanically stirring for 10 hours at 60 ℃, uniformly mixing, removing bubbles from the mixed membrane solution in vacuum, then placing the solution with the bubbles in the air for standing for one minute to obtain a transparent and uniform membrane casting solution, quantitatively dripping the prepared PVDF/PVP/IL membrane casting solution on a glass plate, uniformly paving the membrane on the glass plate on a spin coater to obtain a membrane solution with uniform thickness, standing for 30 seconds in the air, placing the membrane solution in 20 percent ethanol solidification solution to finish the phase conversion process, and separating out a membrane, wherein the thickness of the obtained membrane is about 100-800 microns. And (3) putting the membrane into deionized water, and replacing water every 5-8h to remove residual solvent on the membrane. And finally, drying the membrane in an oven at 70 ℃ to obtain the IPMC base membrane prepared in a phase transfer mode.
Example 3 (preparation of Via-cast type IPMC base film)
Selecting a sodium chlorate solution with the secondary concentration of 5000ppm to remove a pore-forming agent PVP in the PVDF/PVP/IL casting film, preparing the PVDF/PVP/IL casting film obtained in the example 1 into a shape of 2x2cm, putting the PVDF/PVP/IL casting film into a prepared sodium hypochlorite solution with the concentration of 5000ppm, heating to 50 ℃, soaking for 3 days, taking out, washing with ionized water for three times, soaking in deionized water for 6 hours, and drying in an oven at 70 ℃. The through-hole IPMC base film with high performance actuation type required by us is manufactured.
Example 4 (preparation of Via hole transferred type IPMC base film)
Selecting the PVDF/PVP/IL phase transfer membrane obtained in the example 2, making the PVDF/PVP/IL phase transfer membrane into a shape of 2x2cm, then selecting sodium hypochlorite with the concentration of 5000ppm according to the example 3, putting the PVDF/PVP/IL phase transfer membrane into a sodium hypochlorite solution, heating the PVDF/PVP/IL phase transfer membrane and soaking the PVDF/IL phase transfer membrane in the sodium hypochlorite solution for 3d, washing the PVDF/PVP/IL phase transfer membrane with deionized water for three times, taking out the PVDF/IL phase transfer membrane and soaking the PVDF/PVP/IL phase transfer membrane in the deionized water for 6h, finally drying the PVDF/PVP/IL.
Example 5 (preparation of IPMC electrode liquid)
Preparation of a common electrode solution: according to the mass ratio of 2: 1, weighing a certain amount of graphite powder and PVDF powder in a beaker, adding 20ml of DMF solvent, heating at 60 ℃ in a heating furnace, mechanically stirring, mixing uniformly, and performing low-pressure suction filtration on bubbles to obtain the IPMC electrode solution.
Preparing a carbon nano tube electrode: weighing 2.0g of original MWCNTs, adding the weighed original MWCNTs into a mixed solution of 150mL of concentrated sulfuric acid and 50mL of concentrated nitric acid, refluxing for 5 hours at 100 ℃, cooling, diluting, performing suction filtration by using a 0.22 mu m polytetrafluoroethylene filter membrane, and washing by using distilled water until the filtrate is neutral; drying for 4h in a vacuum drying oven at 100 ℃. And oxidizing to obtain CNT-COOH, adding dioxane serving as a solvent to ultrasonically disperse the CNT-COOH for 15min, adding EDC/NHS to react for 30min, centrifugally separating to obtain CNT-NHS, adding triethylamine serving as a solvent, adjusting the pH value of the solution to be 6-7, drying the 2-imidazole-1-ethylamine Ionic Liquid (IL) in an oven at 80 ℃, adding the 2-imidazole-1-ethylamine ionic liquid, mixing and stirring uniformly, reacting for 6h to form the carbon nanotube/ionic liquid gel integrated electrode, and finally storing at low temperature for later use.
FIG. 3 is a scanning electron micrograph of the electrode layer, and the sheet resistance of the electrode obtained by the four-probe instrument test is shown in tables 1 and 2.
TABLE 1 Square resistance of common electrode liquid
| 1 | 2 | 3 | 4 | 5 | 6 | Average | |
| Electrode liquid resistance (omega) | 4.60 | 5.95 | 5.14 | 5.12 | 5.19 | 4.94 | 5.16 |
TABLE 2 Square resistance of carbon nanotube electrode solution
| 1 | 2 | 3 | 4 | 5 | 6 | Average | |
| Electrode liquid resistance (omega) | 2.31 | 3.15 | 2.86 | 3.22 | 2.64 | 2.56 | 2.79 |
Example 6 preparation of IPMC
The dried base film in examples 1-4 was soaked in ionic liquid for 5h, dried at 70 ℃, and the prepared carbon nanotube electrode liquid of example 5 was uniformly coated on both side surfaces of the dried base film, and then the upper and lower portions of the film were sandwiched by two clips, and vertically hung in an oven, the temperature was adjusted to 70 ℃, and after drying, cast into an IPMC (sample one) using PVDF/PVP/IL as the base film; IPMC obtained by phase transfer method and using PVDF/PVP/IL as basement membrane (sample two); a through-hole casting type IPMC (sample III) using PVDF/PVP/IL as a base film obtained by removing PVP in a casting film by hypochlorous acid; the PVP in the phase transfer membrane was removed with hypochlorous acid to obtain a through-hole phase transfer type IPMC with PVDF/PVP/IL as the base membrane (sample four).
The IPMC prepared above was observed for the diameter of the fibers of the base film and the thickness of the base film layer by Scanning Electron Microscopy (SEM), wherein SEM pictures of the through-hole phase transfer type IPMC using PVDF/PVP/IL as the base film obtained by removing PVP from the phase transfer film with hypochlorous acid are shown in fig. 4.
Example 7 Electrical signals of IPMC
The experimental device mainly comprises a signal generating unit, a signal amplifying unit and a force sensor (see figure 5). The hardware of the signal generating unit consists of a 6024E multifunctional data acquisition card of NI company; the software is obtained by LabVIEW programming; the signal amplification unit consists of a power amplification chip OPA548 of TI company; the force sensor is a one-dimensional force sensor capable of measuring the micro-Newton level, voltage signals measured by the force sensor are read into a computer through an amplifying circuit and a 6024E multifunctional data acquisition card, and the force signals are obtained after processing.
And (3) testing the electric actuating performance: the IPMC is placed at two poles of a power supply, the control voltage is between 0.5 and 5 volts, the current intensity is between 0.01 and 0.20 ampere, the working frequency is 0.1 to 20 Hz, the displacement of an electric driver and the working time of a material are observed by a high-speed camera (Olympus) and a laser displacement sensor (Keynce), the output force of the electric driver and the working time of the material are measured by a force sensor (the sensitivity is 0.01 milli-Newton), and the force, the displacement and the working time are compared. The results are shown in tables 3 and 4.
TABLE 3 PVDF/PVP/IL ION-EXCHANGE POLYMER ACTUATOR (SAMPLE III) RELATED PARAMETERS
TABLE 4 PVDF/PVP/IL ION-EXCHANGE POLYMER ACTUATOR (SAMPLE IV) RELATED PARAMETERS
Example 8 Performance testing of IPMC
Ion exchange equivalent test: the ion exchange equivalent (IEC) of the sample from example 6 and a commercial Nafion membrane were tested (table 5). Soaking the prepared dry membrane sample in 2mol/L NaCl solution for 8h to enable sodium ions to exchange hydrogen ions in sulfonic acid groups, and then titrating by using 0.1mol/L standard NaOH solution, wherein the calculation formula of IEC is as follows:
in the formula VNaOHIs the volume of NaOH solution consumed, MNaOHIs the concentration of NaOH and W is the weight of the dry film.
Electromechanical performance testing: the electromechanical performance test platform comprises a signal generator, a force sensor and a multifunctional data acquisition card. The signal generator (SP864, Nanjing) can be at 0-10V, 0.1EConverting sine, square and triangular signals at the frequency of 100 Hz; the measuring range of a force sensor (FEMTO-10000, Switzerland) is 10mN, and the sensitivity is 1 muN; the multifunctional data acquisition card (NI, 6024E) adopts Lapview (v14.0) to support the software. Example 5 sample IPMC sample size 20X 2X 0.33mm3The results of the test under air atmosphere are shown in Table 6.
TABLE 5 IEC, mechanical Property results for each IPMC in example 6
TABLE 6 Electrical actuation Performance and related parameters for each IPMC in EXAMPLE 6
Specific surface area and porosity test: about 100mg of the sample was placed in a sample vial at an adsorber degasser station 250' C and below 6.67X 10-2And (4) degassing the shirt under the vacuum of Pa, transferring the shirt to an analysis station for low-temperature nitrogen adsorption, and obtaining adsorption isothermal money by using a volumetric method. The specific surface area is obtained by linear regression of a BET model; with N2Analyzing the mesopore distribution of the sample by adopting a BJH independent cylinder model with an adsorption isotherm desorption branch as a reference; with N2Analyzing micropores of the sample by HK method based on the adsorption branch of isothermal coin and low pressure to obtain specific surface area and porosity curve (FIG. 5)
Infrared spectrum test:
the model is IRAFFINITY-1S; and (3) testing conditions are as follows: the test resolution is 4cm-1The scanning times are 64 times, and the test range is 400-4500 cm-1. Temperature: at room temperature. Humidity: less than 45% dry environment. Cutting the first, second and fourth samples into 2x2mm shape, oven drying at 70 deg.C, and testing to obtain infrared spectrum (shown in FIG. 8) and integral peak area (shown in Table 7)
Table 7 characteristic peak integrated areas for each sample in example 6
It can be known from tables 5 and 6 that the IPMC of the base film made of PVDF/PVP/IL obtained by the phase transfer method and adding hypochlorous acid to remove PVP of the present invention has a large displacement, and the deflection angle is 2 times of the IPMC deflection angle of the base film made of the general PVDF/PVP/IL cast film and 3 times of the IPMC deflection angle of the base film made of Nafion commercial film at 3V.
The infrared spectrogram of the first sample, the second sample, the third sample and the fourth sample and the integration of characteristic peaks can obtain the membrane by means of phase transfer, and compared with a casting membrane, most of the pore-forming agent PVP can be removed, so that the porosity of the membrane is greatly improved, and the measurement result of the porosity can be seen. The PVP feature profile of the sample is reduced in intensity by the action of hypochlorous acid, so that the remaining PVP can be further removed, which is beneficial for improving the braking performance of the actuator and prolonging the actuation time of the actuator.
The IPMC using PVDF/PVP/IL obtained by a phase transfer method and adding hypochlorous acid to remove PVP as a basement membrane has the characteristic of long-time stable operation, the IPMC is driven under ionic liquid, the ionic liquid drive enables the motion state of the IPMC to be more stable, meanwhile, as the ionic liquid is not volatilized and consumed in the motion process, the phase transfer mode and the hypochlorous acid remove the residual PVP to obtain a highly porous structure, so that the IPMC can store and absorb more ionic liquid, and the ionic liquid drive time is longer. The stable movement time of the IPMC taking the PVDF/PVP/IL casting film obtained by the phase transfer method as the base film is 1.9h under the conditions of 3V voltage and 0.5HZ frequency, and the stable movement time of the IPMC taking the PVDF/PVP obtained by the phase transfer method and adding hypochlorous acid to remove PVP as the base film is 2.2h under the conditions of 3V voltage and 0.5HZ frequency.
The IPMC using PVDF/PVP/IL obtained by the phase transfer method and adding hypochlorous acid to remove PVP as the basement membrane has higher ion exchange equivalent which is 2 times of Nafion commercial membrane and 3 times of Nafion casting membrane.
The IPMC (sample four) obtained by the invention is driven by Ionic Liquid (IL), compared with water driving, the ionic liquid driving can enable the motion state of the IPMC to be more stable, and the working time is greatly improved, and the IPMC can stably work for 2.2h in the ionic liquid, which is 2 times of the time under the water driving.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A through-hole phase transfer type IPMC with PVDF/PVP/IL as a basement membrane is characterized in that: the carbon nanotube membrane electrode is prepared by dispersing carbon nanotubes through 2-imidazole-1-base ethylamine ionic liquid, is firstly oxidized, then activated by EDC/NHS, and then coupled with the 2-imidazole-1-base ethylamine ionic liquid to form gel; the electric signal input into the system is 0.1-10Hz and 0.5-5V sine wave, square wave or triangular wave.
2. The through-hole phase transfer IPMC with PVDF/PVP/IL as basement membrane according to claim 1, characterized by: the thickness of the basement membrane is 100-800 microns, and the thickness of the carbon nanotube electrode is 10-60 microns.
3. The through-hole phase transfer IPMC with PVDF/PVP/IL as basement membrane according to claim 1, characterized by: the surface resistance of the carbon nano tube membrane electrode is 0.5-300 omega.
4. The method for preparing the through-hole phase transfer type IPMC with PVDF/PVP/IL as the basement membrane according to any of claims 1-3, characterized by the following steps:
(1) preparation of PVDF/PVP/IL basement membrane solution: adding a DMF solvent into a mixture of PVDF and PVP, heating, stirring and mixing, then adding 1-ethyl-3-methylimidazole tetrafluoroborate ionic liquid, uniformly mixing, standing, vacuumizing and removing air bubbles in the solution to obtain a PVDF/PVP/IL membrane solution;
(2) preparation of PVDF/PVP/IL basement membrane: quantitatively dripping the PVDF/PVP/IL membrane solution prepared in the step (1) on a glass plate, then flatly spreading the PVDF/PVP/IL membrane solution on a spin coater, standing the PVDF/PVP/IL membrane solution for 80s, then putting the PVDF/PVP/IL membrane solution in 20% ethanol solidification liquid, completing the phase inversion process, precipitating and forming a membrane, putting the membrane in deionized water, changing water every 5-8h, removing the residual solvent on the membrane, and finally drying the membrane in a 70 ℃ drying oven to obtain a PVDF/PVP/IL basement membrane;
(3) removal of PVP from PVDF/PVP/IL basement membrane: putting the PVDF/PVP/IL basement membrane prepared in the step (2) into a hypochlorous acid solution with the mass concentration of 0.5%, adjusting the pH =5-7, heating in a water bath at 50 ℃, and heating at a constant temperature for 48 hours;
(4) PVDF/PVP/IL basement membrane chimerism preparation of IPMC: and uniformly coating the prepared carbon nano tube/ionic liquid gel integrated electrode liquid on two sides of the surface of the dried base film, then putting the base film into an oven, adjusting the temperature to 70 ℃, and drying to obtain the IPMC taking PVDF/PVP/IL as the base film.
5. The method for preparing the through-hole phase transfer IPMC with PVDF/PVP/IL as the basement membrane according to claim 4, wherein: in the PVDF/PVP/IL membrane solution in the step (1), the mass fraction of PVDF is 14%, the mass fraction of 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid is 5%, and the mass of PVP accounts for 15% of the mass of PVDF.
6. The method for preparing the through-hole phase transfer IPMC with PVDF/PVP/IL as the basement membrane according to claim 4, wherein: in the step (2), 2-7mL of PVDF/PVP/IL membrane solution is dripped on a glass plate, and the rotating speed of a spin coater is 40-80 r/min.
7. The method for preparing the through-hole phase transfer IPMC with PVDF/PVP/IL as the basement membrane according to claim 4, wherein: and (3) removing the residual pore-foaming agent PVP through hypochlorous acid so that the total pore volume of the membrane is 0.5-0.85.
8. The method for preparing the through-hole phase transfer IPMC with PVDF/PVP/IL as the basement membrane according to claim 4, wherein: the preparation method of the carbon nanotube/ionic liquid gel integrated electrode liquid in the step (4) comprises the following steps: weighing original MWCNTs by adopting a carbon nano tube oxidation grafting method, adding the weighed original MWCNTs into a mixed solution of concentrated sulfuric acid and concentrated nitric acid, refluxing for 5 hours at the temperature of 100 ℃, cooling, diluting, performing suction filtration by using a polytetrafluoroethylene filter membrane, and washing by using distilled water until filtrate is neutral; drying in a vacuum drying oven at 100 ℃ for 4h, oxidizing to obtain CNT-COOH, adding dioxane as a solvent to ultrasonically disperse the CNT-COOH for 15min, adding EDC/NHS to react for 30min, centrifugally separating to obtain CNT-NHS, adding triethylamine as a solvent, adjusting the pH of the solution to be =6-7, adding dried 2-imidazole-1-ethylamine ionic liquid, mixing and stirring uniformly, reacting for 6h to form a carbon nanotube/ionic liquid gel integrated electrode liquid, and finally storing at low temperature for later use.
9. The method for preparing the through-hole phase transfer type IPMC using PVDF/PVP/IL as the basement membrane according to claim 8, wherein: the mass ratio of the CNT-NHS to the 2-imidazole-1-yl ethylamine ionic liquid is 13: 54.
10. The use of the PVDF/PVP/IL base film through-hole phase transfer IPMC as claimed in any one of claims 1 to 3 for electric actuator.
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