阅读说明：本技术 高性能电驱动全氟磺酸ipmc柔性驱动器的制备方法 (Preparation method of high-performance electrically-driven perfluorinated sulfonic acid IPMC flexible driver ) 是由 梁云虹 张�浩 马愫倩 林兆华 任雷 韩志武 任露泉 于 2020-04-26 设计创作，主要内容包括：本发明公开了高性能电驱动全氟磺酸IPMC柔性驱动器的制备方法,本发明以商用Nafion离子交换膜为基体,采用醇辅助化学镀的方法,选用两种不同的金属,在Nafion薄膜表面制备了均匀、致密的钯、铂电极,与传统的电镀相比,本发明极大地降低了制备金属电极的时间成本与经济成本,与传统Nafion人工肌肉的铂电极相比,本发明所提供的钯、铂电极具有更好的性能,大大加快了电驱动人工肌肉的响应速度,本发明在2V～8V、0.1Hz～30Hz的电压驱动下,就可以产生较大的形变和位移,且响应十分迅速,可以同时实现大形变和快速响应,这种高性能电驱动全氟磺酸IPMC柔性驱动器在柔性机器人、人造肌肉、传感器等领域有着广阔的应用前景和使用价值。(The invention discloses a preparation method of a high-performance electrically-driven perfluorinated sulfonic acid IPMC flexible driver, which takes a commercial Nafion ion exchange membrane as a substrate, adopts an alcohol-assisted chemical plating method, selects two different metals, and prepares uniform and compact palladium and platinum electrodes on the surface of a Nafion film The artificial muscle and the sensor have wide application prospect and use value.)

1. The preparation method of the high-performance electrically-driven perfluorinated sulfonic acid IPMC flexible driver is characterized by comprising the following steps of: the method comprises the following steps:

cutting a Nafion film serving as a base material into squares with the side length of 30-50 mm, polishing the upper surface and the lower surface of the Nafion film by using 1000-mesh abrasive paper to roughen the surface, ultrasonically cleaning the Nafion film in deionized water for 10-15 min, soaking the Nafion film in a hydrogen peroxide aqueous solution for 4-6 h, taking out the Nafion film, boiling the Nafion film in deionized water for 0.5-1.5 h, taking out the Nafion film, soaking the Nafion film in a sulfuric acid solution for 4-6 h, and then boiling the Nafion film in deionized water for 0.5-1.5 h;

step two, carrying out chemical plating on the surface of the Nafion film for many times by an alcohol-assisted method, thereby preparing a high-quality, compact and uniform metal electrode;

and step three, drying the Nafion film by using a vacuum drying oven at the temperature of 80-85 ℃ to remove water molecules, then placing the Nafion film in deionized water to fully absorb water and swell, and finally placing the Nafion film in a saturated lithium chloride aqueous solution to soak for 40-48 h to fully replace positive monovalent lithium ions in the solution into the film.

2. The method for preparing high-performance electrically-driven perfluorosulfonic acid IPMC flexible driver according to claim 1, wherein: the method for preparing the high-quality, compact and uniform metal electrode by carrying out chemical plating on the surface of the Nafion film for multiple times through an alcohol-assisted method comprises the following steps:

1) placing the pretreated Nafion film in a tetraammine palladium chloride aqueous solution with the mass fraction of 0.4-0.7% to soak for 1-2 h, so that palladium ammonia ions fully permeate into the Nafion film;

2) transferring the Nafion film after ion adsorption into an isopropanol/water mixed solution with the volume ratio of 1: 3, heating the isopropanol/water mixed solution, maintaining the temperature at 40-45 ℃, dropwise adding a sodium borohydride aqueous solution with the mass fraction of 5m L-7 m L of 4% -7% for reduction reaction, repeatedly dropwise adding for 10-15 times, wherein the interval is 20-30 min each time, the solution needs to be stirred vigorously in the process, the sodium borohydride can reduce palladium ammonia ions on the Nafion film into palladium nano particles and deposit the palladium nano particles on the surface of the film, and the reduction method for a small amount of time can obtain a more compact and uniform metal electrode on the surface of the Nafion film;

3) taking out the Nafion film subjected to primary chemical plating, and soaking the Nafion film in a tetrammine platinum chloride aqueous solution with the mass fraction of 0.4-0.7% for 22-24 h to enable the surface of the Nafion film to adsorb platinum ammonia ions;

4) and (3) repeating the step 2) to reduce platinum ammonia ions into platinum nano particles, and finally obtaining a uniform and dense palladium-platinum double-layer electrode on the surface of the Nafion film.

3. The method for preparing high-performance electrically-driven perfluorosulfonic acid IPMC flexible driver according to claim 1, wherein: the thickness of the Nafion film is 120-200 μm.

4. The method for preparing high-performance electrically-driven perfluorosulfonic acid IPMC flexible driver according to claim 1, wherein: the mass fraction of the aqueous hydrogen peroxide solution is 4-7%.

5. The method for preparing high-performance electrically-driven perfluorosulfonic acid IPMC flexible driver according to claim 1, wherein: the mass fraction of the sulfuric acid solution is 4-7%.

Technical Field

The invention relates to the technical field of novel intelligent materials, in particular to a preparation method of a high-performance electrically-driven perfluorinated sulfonic acid IPMC flexible driver.

Background

Electroactive polymers (EAPs) are novel intelligent high molecular materials with driving properties, and under the action of an external electric field, the electroactive polymers can perform bending, stretching, contracting, twisting and other actions, and are also called as artificial muscles because the actuation properties of the electroactive polymers are very similar to those of biological muscles and the electroactive polymers have good biocompatibility. According to the working principle, electroactive polymers can be classified into two major types, namely, an electron type EAP which generates a driving force by applying a high voltage of kilovolts, and an ion type EAP which generates a driving force by diffusion and migration of ions in the polymer under a low voltage electric field. An ionic polymer-metal composite material (IPMC) is one of ionic electroactive polymers, can generate larger displacement and deformation under the condition of lower driving voltage, has the advantages of high driving energy density, good flexibility, light weight, no noise, strong operability and the like, can well meet the requirement of artificial muscles, is one of the most widely applied ionic electroactive polymer matrixes, and is characterized in that a perfluorosulfonic acid (Nafion) ion exchange membrane is one of the most widely applied ionic electroactive polymer matrixes, hydrated cations in the membrane migrate to a cathode under the action of an external electric field, and the membrane is bent towards an anode due to shrinkage of the anode caused by swelling of the cathode. At present, the development of artificial muscles based on Nafion films is not complete, if large deformation and quick response are difficult to realize simultaneously, the development and the application of the Nafion artificial muscles are limited to a great extent, in order to improve the performance of the Nafion artificial muscles, the invention selects two different metals of palladium and platinum, and alcohol-assisted chemical plating is carried out twice to form a composite electrode, so that the high-performance electrically-driven perfluorosulfonic acid IPMC flexible driver with quick response, large deformation is prepared.

Disclosure of Invention

The invention aims to solve the defect that the traditional Nafion IPMC flexible driver is difficult to realize large deformation and quick response at the same time, and provides a preparation method of a high-performance electrically-driven perfluorosulfonic acid IPMC flexible driver.

The preparation method of the high-performance electrically-driven perfluorinated sulfonic acid IPMC flexible driver comprises the following steps:

cutting a Nafion film serving as a base material into squares with the side length of 30-50 mm, polishing the upper surface and the lower surface of the Nafion film by using 1000-mesh sand paper to coarsen the surface, ultrasonically cleaning the Nafion film in deionized water for 10-15 min, soaking the Nafion film in a hydrogen peroxide aqueous solution for 4-6 h, taking out the Nafion film, boiling the Nafion film in deionized water for 0.5-1.5 h, taking out the Nafion film, soaking the Nafion film in a sulfuric acid solution for 4-6 h, and then boiling the Nafion film in deionized water for 0.5-1.5 h;

step two, carrying out chemical plating on the surface of the Nafion film for many times by an alcohol-assisted method, thereby preparing a high-quality, compact and uniform metal electrode;

and step three, drying the Nafion film by using a vacuum drying oven at the temperature of 80-85 ℃ to remove water molecules, then placing the Nafion film in deionized water to fully absorb water and swell, and finally placing the Nafion film in a saturated lithium chloride aqueous solution to soak for 40-48 h to fully replace positive monovalent lithium ions in the solution into the film.

The method for preparing the high-quality, compact and uniform metal electrode by carrying out chemical plating on the surface of the Nafion film for multiple times through an alcohol-assisted method comprises the following steps:

1) placing the pretreated Nafion film in a tetraammine palladium chloride aqueous solution with the mass fraction of 0.4-0.7% to soak for 1-2 h, so that palladium ammonia ions fully permeate into the Nafion film;

2) transferring the Nafion film after ion adsorption into an isopropanol/water mixed solution with the volume ratio of 1: 3, heating the isopropanol/water mixed solution, maintaining the temperature at 40-45 ℃, dropwise adding a sodium borohydride aqueous solution with the mass fraction of 5m L-7 m L of 4% -7% for reduction reaction, repeatedly dropwise adding for 10-15 times, wherein the interval is 20-30 min each time, the solution needs to be stirred vigorously in the process, the sodium borohydride can reduce palladium ammonia ions on the Nafion film into palladium nano particles and deposit the palladium nano particles on the surface of the film, and the reduction method for a small amount of time can obtain a more compact and uniform metal electrode on the surface of the Nafion film;

3) taking out the Nafion film subjected to primary chemical plating, and soaking the Nafion film in a tetrammine platinum chloride aqueous solution with the mass fraction of 0.4-0.7% for 22-24 h to enable the surface of the Nafion film to adsorb platinum ammonia ions;

4) repeating the step 2), so that platinum ammonia ions are reduced into platinum nano particles, and finally, obtaining a uniform and dense palladium-platinum double-layer electrode on the surface of the Nafion film;

the thickness of the Nafion film is 120-200 μm;

the mass fraction of the aqueous hydrogen peroxide solution is 4-7 percent;

the mass fraction of the sulfuric acid solution is 4-7%.

The working principle and the process of the invention are as follows:

the invention relates to a high-performance electrically-driven perfluorinated sulfonic acid IPMC flexible driver, which is obtained by adopting an alcohol-assisted chemical plating method, sequentially preparing a palladium electrode layer and a platinum electrode layer on the surface of a Nafion ion exchange membrane substrate, and finally carrying out sufficient ion exchange to ensure that cations are replaced into the membrane⁺Will diffuse to the cathode while L i⁺Will drive the water molecules in the film to migrate to the cathode side together, so that the cathode of the Nafion filmThe expansion is caused by the increase of water, and the anode is shrunk by the loss of water, so that the entire Nafion film is bent toward the anode side, thereby generating a driving force for deformation.

The invention has the beneficial effects that:

the electrically-driven perfluorinated sulfonic acid IPMC flexible driver material provided by the invention takes a commercial Nafion ion exchange membrane as a substrate, adopts an alcohol-assisted chemical plating method, selects two different metals, the method prepares uniform and compact palladium and platinum electrodes on the surface of the Nafion film, greatly reduces the time cost and economic cost for preparing the metal electrode compared with the traditional electroplating, compared with the platinum electrode of the traditional Nafion artificial muscle, the palladium and platinum electrodes provided by the invention have better performance, greatly accelerate the response speed of the electrically driven artificial muscle, can generate larger deformation and displacement under the drive of voltages of 2V-8V and 0.1 Hz-30 Hz, have very quick response, the high-performance electrically-driven perfluorinated sulfonic acid IPMC flexible driver can simultaneously realize large deformation and quick response, and has wide application prospect and use value in the fields of flexible robots, artificial muscles, sensors and the like.

Drawings

FIG. 1 is a schematic diagram of the operation of the present invention;

FIG. 2 is a flow chart of the preparation of the present invention;

FIG. 3 is a graph of tip displacement over time with a voltage drive at a frequency of 0.1Hz in accordance with the present invention;

fig. 4 is a graph of the maximum displacement of the present invention as a function of drive voltage.

Detailed Description

Referring to fig. 1 to 4, a method for manufacturing a high-performance electrically-driven perfluorosulfonic acid IPMC flexible driver includes the following steps:

step one, cutting a Nafion 117 film produced by DuPont company with the thickness of 180 microns into square small pieces with the side length of 30mm, polishing the upper surface and the lower surface of the Nafion film by using 1000-mesh sand paper to coarsen the surface of the film, then ultrasonically cleaning the film in deionized water for 10min, soaking the Nafion film in a 5% hydrogen peroxide water solution for 4h, taking out the Nafion film, boiling the Nafion film in the deionized water for 1h, taking out the Nafion film, soaking the Nafion film in a 5% sulfuric acid solution for 4h, then boiling the Nafion film in the deionized water for 1h, and increasing the surface roughness of the Nafion film after the pretreatment, swelling the Nafion film by absorbing water, and becoming soft and transparent;

step two, carrying out chemical plating on the surface of the Nafion film for many times by an alcohol-assisted method, thereby preparing a high-quality, compact and uniform metal electrode;

1) placing the pretreated Nafion film in 0.5% by mass of tetraammine palladium chloride aqueous solution to soak for 2h, so that palladium ammonia ions fully permeate into the Nafion film;

2) placing a Nafion film in a mixed solution of isopropanol and water in a volume ratio of 1: 3, soaking to enable the Nafion film to fully absorb water and swell, heating the mixed solution of isopropanol and water to 40 ℃, keeping the temperature, dropwise adding 5m sodium borohydride aqueous solution with the mass fraction of 5% of L as a reducing agent under vigorous stirring, repeating for ten times at intervals of 30min each time, and reducing palladium ammonia ions adsorbed on the surface of the Nafion film into simple substance palladium under the action of the reducing agent, wherein the method for a few times can enable metal palladium on the surface of the Nafion film to be more uniform and compact;

3) taking out the Nafion film subjected to the primary chemical plating, and soaking the Nafion film in 0.5% tetramine platinum chloride aqueous solution for 24 hours to enable the surface of the Nafion film to adsorb platinum ammonia ions;

4) repeating the step 2) to reduce platinum ammonia ions, and finally obtaining a uniform and dense palladium-platinum double-layer electrode on the surface of the Nafion film;

and step three, drying the Nafion film at the temperature of 80 ℃ by using a vacuum drying oven to remove water molecules, then placing the Nafion film in deionized water to fully absorb water and swell, and finally placing the Nafion film in a saturated lithium chloride aqueous solution to soak for 46 hours to fully displace positive monovalent lithium ions in the solution into the film.