CN109680270B

CN109680270B - Preparation device and preparation method of array electrode made of IPMC material

Info

Publication number: CN109680270B
Application number: CN201811618290.0A
Authority: CN
Inventors: 王延杰; 杨文�; 王家乐; 张宇霆; 骆敏舟
Original assignee: Changzhou Campus of Hohai University
Current assignee: Changzhou Campus of Hohai University
Priority date: 2018-12-28
Filing date: 2018-12-28
Publication date: 2020-11-24
Anticipated expiration: 2038-12-28
Also published as: CN109680270A

Abstract

The invention relates to a preparation device of an array electrode of an IPMC material, which comprises two oppositely arranged die clamping plates, a plurality of array holes and a plurality of metal-insulator-metal (IPMC) electrodes, wherein the die clamping plates are respectively arranged on two sides of a substrate film; the two liquid storage cavities are respectively communicated with the array holes of the two die clamping plates, the array holes are communicated with the liquid storage cavities and the substrate membrane, and reaction liquid in the liquid storage cavities is guided to the surface of the substrate membrane through the array holes so as to be in point contact with the substrate membrane in an array distribution manner; a first pipeline communicating the two liquid storage cavities; the device is connected with at least one liquid inlet of the liquid storage cavity, and provides a corresponding preparation method, so that the device greatly simplifies the technical process of the preparation of the IPMC array electrode, improves the efficiency and reduces the cost.

Description

Preparation device and preparation method of array electrode made of IPMC material

Technical Field

The invention relates to a preparation device and a preparation method of an electrode, in particular to a preparation device and a preparation method of an array electrode made of an IPMC material.

Background

An Ionic polymer-metal composites (IPMC) belongs to an Electroactive polymer (EAP) material, which can generate a large bending deformation under a low voltage and the deformation disappears after the voltage is removed. If the device is bent under the action of external load, the device can generate measurable electric signals on the upper surface and the lower surface. It also has the characteristics of light weight, good flexibility, flexible movement, easy forming, difficult fatigue after being subjected to large deformation and the like, and is known as an artificial muscle material.

The IPMC material is a sandwich-like structure formed by a layer of ion exchange membrane and two layers of metal electrodes attached to the upper surface and the lower surface of the IPMC material, and metal cations and solvent molecules are arranged in the middle ion exchange membrane. When a voltage is applied to the upper surface and the lower surface of the anode, the metal cations carry the solvent molecules to move towards the cathode side, so that the cathode side expands, the anode contracts and generates bending deformation, and the characteristic can be used for driving. Similarly, if the IPMC material is deformed, the metal cations inside the IPMC material will gather to one side, and the outside shows that there is a potential difference between the upper and lower surfaces of the IPMC material, which is a characteristic of sensing.

The traditional preparation process of the IPMC material needs to put a whole piece of Nafion membrane into a container to perform ion exchange with noble metal salt solution, then the Nafion membrane is taken out to perform chemical reaction with reaction liquid to form a metal electrode, and the process needs to be repeated. Therefore, it is necessary to take out the solution after each reaction with the solution and then put it in another solution, which is very time-consuming. The existing IPMC material array preparation process generally adopts a flexible adhesive tape as a mask plate, and places where electrodes do not need to be plated are covered by the adhesive tape. However, in the repeated preparation process, the Nafion film shrinks and swells, so that the flexible adhesive tape is easy to fall off, and the overall preparation effect is poor.

Disclosure of Invention

The invention provides a preparation device for an arrayed electrode of an IPMC material, aiming at solving the problems of complex preparation process and complex preparation method of the existing IPMC array electrode and aiming at the excellent characteristics of the IPMC material in the aspects of driving and sensing. The device greatly simplifies the process of preparing the IPMC array electrode, improves the efficiency and reduces the cost.

In order to solve the problems, the invention adopts the technical scheme that: a device for preparing an array electrode of IPMC material comprises

The two oppositely arranged die clamping plates are respectively arranged on two sides of the substrate film, and a plurality of array holes distributed in an array manner are arranged on the die clamping plates;

the two liquid storage cavities are respectively communicated with the array holes of the two die clamping plates, the array holes are communicated with the liquid storage cavities and the substrate membrane, and reaction liquid in the liquid storage cavities is guided to the surface of the substrate membrane through the array holes so as to be in point contact with the substrate membrane in an array distribution manner;

a first pipeline communicating the two liquid storage cavities;

a liquid inlet connected with at least one liquid storage cavity.

Further, the liquid storage cavity is arranged in the cavity plate, and the liquid storage cavity is formed by digging the cavity from one side of the cavity plate to the other side of the cavity plate.

Furthermore, the two ends of the first pipeline are detachably arranged on the side wall of the liquid storage cavity.

Further, the first pipeline is connected with the liquid storage cavity through a second pipeline, the second pipeline is arranged in the cavity plate and communicated with the liquid storage cavity, and the second pipeline is communicated with the outside of the cavity plate.

Further, the second pipeline is perpendicular to the side wall of the liquid storage cavity.

Further, the liquid storage cavity is arranged on the cavity plate, the cavity plate is dug to form the liquid storage cavity, an opening at one end of the liquid storage cavity is opposite to the array holes distributed on the die clamping plate in an array mode, and an opening at the other end of the liquid storage cavity is sealed through the cover plate.

Further, be provided with first inlet on the apron be equipped with the second inlet in intercommunication stock solution chamber on the cavity board, first inlet intercommunication second inlet and stock solution chamber.

Furthermore, a second pipeline which is communicated with the liquid storage cavity outside the cavity plate is arranged in the cavity plate, the second liquid inlet is connected with the side wall of the second pipeline, and reaction liquid injected into the first liquid inlet enters the liquid storage cavity through the second liquid inlet and the second pipeline.

Furthermore, the cover plate, the cavity plate and the mold clamping plate are provided with fixing holes penetrating through the cover plate, the cavity plate and the mold clamping plate, the cover plate, the cavity plate and the mold clamping plate are fixedly connected through bolts penetrating through the fixing holes, and one side of the cover plate, which is back to the cavity plate, is provided with a pressing strip for pressing the cover plate.

The invention also provides a preparation method of the array electrode of the IPMC material based on the preparation device, which comprises the following steps

Step 1, sand blasting is carried out on a substrate film;

step 2, carrying out ultrasonic cleaning on the substrate film subjected to sand blasting;

step 3, sequentially carrying out acid boiling and water boiling to wash the substrate film;

step 4, putting the substrate film between two clamping plates to enable the clamping plates to clamp the substrate film;

and 5, injecting the prepared Pd solution into at least one liquid storage cavity from a liquid inlet by using an injector, filling the two liquid storage cavities through the first pipeline, and then putting the device for preparing the array electrode of the IPMC material into an oscillator for oscillation so as to ensure that the metal Pd solution is fully contacted with the substrate membrane.

The beneficial effects produced by the invention comprise: the device can clamp the pretreated Nafion membrane in the mold clamping plate, sequentially assemble the two cavity plates, the cover plate and the pressing strip, and screw the bolt to a proper position, so that the reaction liquid can not leak between the mold clamping plate and the Nafion membrane. Then, the two liquid storage cavities are connected by two hoses, so that the reaction liquids in the liquid storage cavities are communicated. The reaction liquid is injected into the liquid storage cavity from the first liquid inlet of the cover plate by the injector, after the liquid storage cavity is filled with the reaction liquid, the opening is sealed by the plug, and then the whole device is placed into the oscillator for oscillation. After the reaction was completed, the hose was disassembled, and the reaction solution was discharged.

In the whole preparation process of the material, only different solutions are required to be sequentially injected into the device, and the Nafion membrane is not required to be disassembled and replaced, so that the process is simplified, and the damage to the substrate membrane in the process of moving the Nafion membrane is avoided. Meanwhile, because the invention carries out fixed-point preparation in the device, the solution consumption is greatly reduced.

Drawings

FIG. 1 is a view showing an appearance structure of the whole apparatus;

FIG. 2 is a perspective view of the three-dimensional structure of the upper cover plate;

FIG. 3 is a perspective of the three-dimensional structure of the lower cover plate;

FIG. 4 is a perspective view of a three-dimensional structure of a first cavity plate;

FIG. 5 is a cross-sectional view of a cavity plate

FIG. 6 is a perspective view of a three-dimensional structure of a mold clamp plate

FIG. 7 is a perspective view of a three-dimensional structure of a single compression strip

FIG. 8 is a sample schematic of IPMC with arrayed electrodes

Reference numbers in the figures: 1. the cover plate, 101, first inlet, 102, third fixed orifices, 2, cavity board, 201, stock solution chamber, 202, second inlet, 203, second fixed orifices, 204, second pipeline, 3, mould splint, 301, array hole, 302, first fixed orifices, 4, first pipeline, 5, bolt, 6, compress tightly the strip, 601, fourth fixed orifices, 602, breach.

Detailed Description

The present invention is explained in further detail below with reference to the drawings and the detailed description, but it should be understood that the scope of the present invention is not limited by the detailed description.

As shown in fig. 1 to 8, the apparatus for preparing an arrayed electrode of an IPMC material in the present invention includes two cover plates 1, two cavity plates 2, and two mold clamping plates 3, the mold clamping plates 3 are disposed on two sides of a substrate film, the mold clamping plates 3 are provided with array holes 301 distributed in an array manner, the distribution shape of the array holes 301 is the distribution shape of electrodes on the substrate film, the array holes 301 may be square, circular, or other shapes, the mold clamping plates 3 are square structures, and four corners of the square mold clamping plates 3 are provided with first fixing holes 302 penetrating through the mold clamping plates 3 for fixing the two mold clamping plates 3 by mounting bolts 5.

The center of the cavity plate 2 is provided with a through cavity penetrating through the upper side and the lower side of the cavity plate 2, the through cavity is a liquid storage cavity 201, one end of the liquid storage cavity 201 is connected with the mold clamping plate 3 and is opposite to the array holes 301 distributed in an array manner on the mold clamping plate 3, and the other end of the liquid storage cavity 201 is connected with the cover plate 1, so that the opening width of the liquid storage cavity 201 is not less than the distribution range of the array holes 301; the appearance of cavity board 2 is square, circular or other shapes to keep unanimous with apron 1 appearance, its inside stock solution chamber 201 cross-sectional shape can be square, circular or other shapes, still opened a pair of horizontal through-hole on the cavity board 2, second pipeline 204 promptly, the perpendicular stock solution chamber 201 lateral wall setting of second pipeline 204, and run through the left and right sides of cavity board 2, second pipeline 204 leads to the cavity board 2 outside by stock solution chamber 201, the opening symmetric distribution is in the left and right sides of cavity board 2. The cavity plate 2 is provided with a second fixing hole 203 corresponding to the first fixing hole 302 of the mold clamping plate 3, and the second fixing hole is used for fixedly connecting the two cavity plates 2.

The cavity plate 2 is provided with two first cavity plates and two second cavity plates which are respectively connected with two mold clamping plates 3, the liquid storage cavity 201 of the first cavity plate is connected with the liquid storage cavity 201 of the second cavity plate through a first pipeline 4, and two ends of the first pipeline 4 are respectively connected with an opening of a second pipeline 204 on the first cavity plate, which leads to the outer side of the cavity plate 2, and an opening of the second pipeline 204 on the second cavity plate, which leads to the outer side of the cavity plate 2. The first pipelines 4 are arranged in two and are respectively arranged at the left side and the right side of the cavity plate 2.

An interface device is arranged at the opening of the second duct 204 to the outside of the cavity plate 2, through which interface device the second duct 204 is connected to said first duct 4. The first conduit 4 in the present invention is a universal hose having a size corresponding to the opening of the second conduit 204 in the cavity plate 2.

The cover plate 1 is provided with two cover plates, and the two cover plates are respectively used for connecting the first cavity plate and the second cavity plate and are used for sealing the liquid storage cavity 201. The cover plate 1 is a thin plate structure, the shape of the cover plate is square, round or other shapes, a third fixing hole 102 which is consistent with the position of a second fixing hole 203 is arranged near the edge and is used for fixing the cover plate 1 on a cavity plate 2, the cover plate 1 comprises a first cover plate which is respectively corresponding to a first cavity plate and a second cover plate which is corresponding to a second cavity plate, the cover plate 1, the cavity plate 2 and a mould clamping plate 3 are arranged in an up-and-down row, the first cover plate is arranged on the upper part of the first cavity plate, a first liquid inlet 101 which is used for injecting reaction liquid into a liquid storage cavity 201 is arranged on the first cover plate, two first liquid inlets 101 are arranged on the first cavity plate which is arranged on the upper part, the first liquid inlet 101 is opposite to the second liquid inlet 202, the second liquid inlet 202 leads to a second channel, the reaction liquid enters the second liquid inlet 202 and the second channel after being injected through the first liquid inlet 101, and then partially enters the liquid storage cavity 201, and partly through the first conduit 4 into the reservoir 201 on the second chamber plate.

Still be equipped with in the outside of two apron 1 and be used for compressing tightly apron 1, cavity board 2 and mould splint 3 compress tightly strip 6, it is equipped with two to compress tightly strip 6, cross arrangement, both ends at the gold bar of escorting are equipped with fourth fixed orifices 601, first fixed orifices 302, second fixed orifices 203, third fixed orifices 102 and fourth fixed orifices 601 are linked together, run through four fixed orifices through bolt 5 and compress tightly each plate reciprocal anchorage together, the setting that compresses tightly strip 6 can prevent when bolt 5 at four angles is screwed up, the clearance appears in the central part of device, influence sealed effect. The two pressing strips 6 in the invention adopt an interlocking structure, a single pressing strip 6 is in a cuboid strip shape, and a part of the middle pressing strip 6 is removed to form a notch 602, so that the two lock catches can be assembled into a whole to form the interlocking structure.

The preparation device of the invention is as follows: the size, number and spacing of the array holes 301 of the mold splint 3 are designed according to requirements. A Nafion membrane of a specific size is placed between two identical mold jaws 3, aligning the array holes 301 and the fixation holes. Fixing the cavity plate 2 outside the mold clamping plate 3, fixing the cover plate 1 outside the cavity plate 2, fixing the lock catch outside the cover plate 1, and integrally fixing and fastening the structure according to the fixing hole by using a bolt 5 and a nut. The cavity of the upper and lower cavity plates 2 is communicated by a hose.

The preparation device is structurally characterized in that a first solution inlet 101 for solution is formed in the upper cover plate 1, and reaction solution enters and exits the device from the first solution inlet. The cavity plate 2 is provided with a second liquid inlet 202 corresponding to the upper cover plate 1, from which the solution can flow into the liquid storage cavity 201, so that the positions of the first liquid inlet 101 and the second liquid inlet 202 are identical, and the sizes and the dimensions are also identical. The middle part of the cavity plate 2 is provided with a liquid storage cavity 201 for storing reaction liquid, in order to enable the liquid in the cavities of the upper cavity plate and the lower cavity plate 2 to be communicated, the middle part of the cavity plate 2 is provided with a second pipeline 204, and the second pipeline is connected to the liquid storage cavity 201 of the lower cavity plate 2 through a first pipeline 4, and the cover plate 1 is used for preventing the solution from leaking out of the liquid storage cavity 201 during the reaction. Meanwhile, in order to ensure that the position of the reservoir 201 does not interfere with the positions of the solution inlet and outlet (i.e., the inlet of the liquid into the reservoir 201 and the outlet of the liquid out of the reservoir 201), the positions of the solution inlet and outlet should be outside the position of the cavity. The mold holder 3 is designed so that the reaction solution can react on the Nafion membrane and form the array-type electrodes. The mold clamping plate 3 is provided with an array of small holes, and liquid in the cavity can reach the surface of the Nafion membrane from the small holes and generate chemical reaction. In position, the apertures in the clamping plate should be located within the cavity to ensure a smooth inflow of fluid. The cover plate 1, the cavity plate 2 and four corners of the clamping plate are provided with fixing holes, and the size and the position of the fixing holes are completely the same and are used for connecting the bolts 5.

The method for preparing the array electrode of the IPMC material by adopting the device comprises the following steps:

a Nafion film was used as a base film, and the film was cut to a size of 30 mm. times.30 mm. The sand blasting is carried out by a sand blasting machine, the matrix film is enabled to do Z-shaped uniform motion along the nozzle in the sand blasting process, the purpose is that the sand blasting of the whole matrix film is uniform, the pressure in the sand blasting process is 0.4MPa, and the two surfaces are respectively blasted for 30s, so that the surfaces of the matrix film are roughened.

And (3) putting the Nafion membrane subjected to sand blasting into a beaker filled with 200ml of deionized water, and cleaning by ultrasonic waves, wherein the purpose of ultrasonic cleaning is to remove impurities remained on the surface of the substrate membrane after sand blasting, and the cleaning temperature is 60 ℃ and the cleaning time is 30 min.

And (3) boiling and washing the Nafion membrane subjected to ultrasonic cleaning by using 2mol/L of hydrochloric acid with the dosage of 200ml, at the boiling and washing temperature of 100 ℃ for 30min, so as to remove impurities in the matrix membrane.

Then, the IPMC material is boiled and washed by 200ml of deionized water for 30min at 100 ℃, so as to increase the water storage capacity of the IPMC material.

The Nafion membrane after the above treatment is put in place in the mold cramp 3, and the desired electrode position can be obtained by adjusting the position of the Nafion membrane in the mold cramp 3. Then, the cavity plate 2 is partially placed on both sides of the mold clamping plate 3, the fixing holes at the four corners are required to be aligned, the cover plate 1 is covered, the first liquid inlet 101 on the cover plate 1 is required to be aligned with the second liquid inlet 202 on the cavity plate 2, and after the lock catch is installed, the bolts 5 and nuts of M4 are screwed at the four corners and screwed to proper positions, so that proper pressure is generated in the clamping plate. Then, the upper and lower cavity plates 2 are partially communicated by connecting the upper and lower cavity plates 2 through a hose, and after the connection, the tightness of the whole device is required to be noticed, so that liquid leakage cannot occur after liquid is injected.

Preparing metal Pd salt solution, weighing Pd (NH) by an electronic balance₄)₃Cl₂84.978mg was put into a beaker, and 4.61ml of aqueous ammonia was added thereto, followed by addition of 34.6 ml of deionized water to dissolve the mixture.

Injecting the prepared Pd solution from the first liquid inlet 101 of the cover plate 1 of the device by using a syringe, enabling the solution to reach the liquid storage cavities 201 of the upper and lower cavity plates 2, stopping injecting after the upper and lower liquid storage cavities 201 are filled with the solution, plugging a plug at the injection inlet for sealing to ensure that the reaction liquid cannot leak, and then putting the whole device into an oscillator for oscillation for 1h to enable the metal Pd solution to be in full contact with the Nafion membrane.

Preparing a reducing solution: 80.6ml of deionized water is measured by a measuring cylinder, 434 mu l of ammonia water is measured by a pipette, and NaBH is weighed by an electronic balance₄3.2mg of the resulting mixture was mixed in a beaker to prepare a reducing solution.

And inflating the device from an injection port of the device by using a device such as an air pump and the like so as to discharge the Pd solution in the device, then injecting the prepared reducing solution into the device, stopping injecting after the reducing solution fills the cavity, plugging a plug, putting the whole device into an oscillator, and oscillating and reducing for 0.5h so that palladium ions on the surface of the Nafion membrane are reduced into metal palladium attached to the surface of the Nafion membrane.

The above process of palladium plating and reduction was repeated 2 times.

The apparatus was disassembled, and the substrate film was taken out of the apparatus, and electroplating was carried out using gold water containing gold ions as an electroplating solution, a titanium mesh as an anode, and a metal probe as a cathode. The voltage during electroplating was 5V, the current was 0.05A, and the time was 30s, and after completion of electroplating, the operation was repeated to perform electroplating on the other side. After electroplating, the IPMC material with array electrodes as shown in FIG. 6 can be obtained.

The above description is only a preferred embodiment of the present invention, and the present invention is not limited to the content of the embodiment. It will be apparent to those skilled in the art that various changes and modifications can be made within the technical scope of the present invention, and any changes and modifications made are within the protective scope of the present invention.

Claims

1. A preparation device of an array electrode of an IPMC material is characterized in that: comprises that

a first pipeline communicating the two liquid storage cavities;

a liquid inlet connected with at least one liquid storage cavity.

2. The apparatus of claim 1, wherein the IPMC material array electrode comprises: the liquid storage cavity is arranged in the cavity plate, and the liquid storage cavity is formed by digging the cavity from one side of the cavity plate to the other side of the cavity plate.

3. The apparatus of claim 1, wherein the IPMC material array electrode comprises: the two ends of the first pipeline are detachably arranged on the side wall of the liquid storage cavity.

4. The apparatus of claim 2, wherein the IPMC material array electrode comprises: the first pipeline is connected with the liquid storage cavity through a second pipeline, the second pipeline is arranged in the cavity plate and communicated with the liquid storage cavity, and the second pipeline is communicated to the outside of the cavity plate.

5. The apparatus of claim 4, wherein the IPMC material array electrode comprises: the second pipeline is perpendicular to the side wall of the liquid storage cavity.

6. The apparatus of claim 1, wherein the IPMC material array electrode comprises: the liquid storage cavity is arranged on the cavity plate, the cavity plate is provided with through cavities penetrating through two sides of the cavity plate to form the liquid storage cavity, an opening at one end of the liquid storage cavity is right opposite to a plurality of array holes distributed in an array mode on the mold clamping plate, and an opening at the other end of the liquid storage cavity is sealed through the cover plate.

7. The apparatus of claim 6, wherein the IPMC material array electrode comprises: at least one cover plate is provided with a first liquid inlet, the cavity plate connected with the cover plate is provided with a second liquid inlet communicated with the liquid storage cavity, and the first liquid inlet is communicated with the second liquid inlet and the liquid storage cavity.

8. The apparatus of claim 7, wherein the IPMC material array electrode comprises: and a second pipeline leading from the liquid storage cavity to the outside of the cavity plate is arranged in the cavity plate, the second liquid inlet is connected with the side wall of the second pipeline, and liquid injected into the first liquid inlet enters the liquid storage cavity through the second liquid inlet and the second pipeline.

9. The apparatus of claim 6, wherein the IPMC material array electrode comprises: the cover plate, the cavity plate and the mold clamping plate are provided with fixing holes penetrating through the cover plate, the cavity plate and the mold clamping plate, the cover plate, the cavity plate and the mold clamping plate are fixedly connected through bolts penetrating through the fixing holes, and one side, back to the cavity plate, of the cover plate is provided with a pressing strip for pressing the cover plate.

10. A method for preparing an array electrode of IPMC material based on the apparatus of claim 1, wherein: comprises the following steps

Step 1, sand blasting is carried out on a substrate film;