阅读说明：本技术 一种非对称电极ipmc的制备方法、制得的非对称电极ipmc (Preparation method of asymmetric electrode IPMC and prepared asymmetric electrode IPMC ) 是由 常龙飞 王冬平 宋伟 胡颖 朱子才 王延杰 于 2021-08-10 设计创作，主要内容包括：本发明公开一种非对称电极IPMC的制备方法,涉及非对称型电极离子聚合物-金属复合材料技术领域,本发明包括以下步骤：(1)将基体膜溶液与电极材料混合,分层处理后,得到膜溶液；(2)将膜溶液经过铸膜处理,得到基体膜；(3)基体膜进行还原镀处理后,在膜表面形成电极层,即为非对称电极IPMC。本发明还提供采用上述方法制得的IPMC。本发明的有益效果在于：可以设计非对称型的电极IPMC,包括电极的材料不同和形貌不对称。从而实现具有特定的电极结构,增强电极与基体膜之间的附着力,增加渗入电极的深度以及改善渗入电极的形貌,从而进一步提高IPMC材料的电化学性能和机电性能。(The invention discloses a preparation method of an asymmetric electrode IPMC, which relates to the technical field of asymmetric electrode ionic polymer-metal composite materials, and comprises the following steps: (1) mixing the substrate membrane solution with an electrode material, and carrying out layering treatment to obtain a membrane solution; (2) performing film casting treatment on the film solution to obtain a substrate film; (3) and after the reduction plating treatment is carried out on the substrate film, an electrode layer is formed on the surface of the film, namely the asymmetric electrode IPMC. The invention also provides the IPMC prepared by the method. The invention has the beneficial effects that: asymmetric electrode IPMC can be designed, including different materials and asymmetric morphology of the electrode. Therefore, the specific electrode structure is realized, the adhesion between the electrode and the substrate film is enhanced, the depth of the infiltrated electrode is increased, the appearance of the infiltrated electrode is improved, and the electrochemical performance and the electromechanical performance of the IPMC material are further improved.)

1. A preparation method of an asymmetric electrode IPMC is characterized by comprising the following steps: the method comprises the following steps:

(1) mixing the substrate membrane solution with an electrode material, and carrying out layering treatment to obtain a membrane solution;

(2) performing film casting treatment on the film solution obtained in the step (1) to obtain a substrate film;

(3) and (3) carrying out reduction plating treatment on the substrate film, and forming an electrode layer on the surface of the film, namely the asymmetric electrode IPMC.

2. The method of preparing an asymmetric electrode IPMC according to claim 1, wherein: the electrode material comprises Pd²⁺、Ag⁺、Au⁺、Pt⁺、Ni⁺、Cu²⁺One or more of the complex salts of (a).

3. The method of preparing an asymmetric electrode IPMC according to claim 1, wherein: the base membrane solution includes a Nafion series ion exchange membrane solution of Dupont, an Aciplex series ion exchange membrane solution of Asahi Chemical, a Flemion series ion exchange membrane solution of Asahi Glass, or an Aquivion series ion exchange membrane solution of Solvay Solexis.

4. The method of preparing an asymmetric electrode IPMC according to claim 1, wherein: and (3) roughening the electrode material deposition surface of the base film subjected to the film casting treatment in the step (2).

5. The method of preparing an asymmetric electrode IPMC according to claim 1, wherein: and (4) performing ion exchange treatment after electroplating in the step (3).

6. The method of preparing an asymmetric electrode IPMC according to claim 1, wherein: and printing a layer of conductive silver paste on the non-electrode surface of the electroplated substrate film, and then drying.

7. The method of preparing an asymmetric electrode IPMC according to claim 1, wherein: the reduction treatment in the step (3) comprises the following steps: mixing ultrapure water with ammonia water to prepare a plating solution, and adding NaBH under the oscillation condition₄Reducing the solution, adding the matrix membrane, and adding NaBH again after a period of time₄And (5) treating the reducing liquid.

8. The method of preparing an asymmetric electrode IPMC according to claim 1, wherein: the electroplating in the step (3) comprises the following steps: and placing the reduced substrate film in electrolyte for electroplating treatment.

9. The method of preparing an asymmetric electrode IPMC according to claim 8, wherein: the electrolyte is gold water.

10. An asymmetric electrode IPMC made by the method of any one of claims 1 to 9.

Technical Field

The invention relates to the technical field of asymmetric electrode Ionic Polymer-Metal Composites (IPMC), in particular to a preparation method of an IPMC and the prepared IPMC.

Background

The core technology of the IPMC fabrication process is to achieve efficient bonding of the electrode and the substrate film. Research has shown that: the IPMC can exhibit an excellent transduction function only if electrode particles penetrate into an ion membrane substrate to form a certain interface layer.

The method of making the IPMC material disclosed in the application No. 201811220201.7 includes the steps of: the base film roughening treatment occurs after the base film is subjected to the first ion exchange treatment and before the base film is subjected to the first reduction treatment. Also discloses a preparation method of the intermediate of the IPMC material and the IPMC material prepared by the preparation method of the IPMC material. The method has the advantages of enhancing the adhesion between the electrode and the matrix film, increasing the depth of the infiltrated electrode and improving the appearance of the infiltrated electrode, thereby further improving the electrochemical performance and the electromechanical performance of the IPMC material.

In the preparation of the IPMC material in the prior art, in the soaking reduction method and the autocatalytic reduction method, firstly, an ionic polymer matrix membrane is soaked in an ionic complex solution (such as platinum, gold, palladium, silver and other ionic complexes), ion exchange is performed, and then chemical reduction is performed to deposit and permeate a layer of electrode on the upper and lower surfaces of the matrix membrane, thereby forming a composite material with a sandwich structure.

However, with the widening of the application field, the electrode requirements of the IPMC are not limited to the double-layer electrode, and as disclosed in the patent with the application number of 201710058364.9, a single-layer electrode type IPMC structure and a preparation process thereof are characterized in that: one side of a substrate film layer is coated with a packaging layer, and the other side is provided with an electrode layer, and the preparation process comprises the following steps: after one surface of the base film layer is covered with a mask material, an electrode material is plated on the other surface of the base film layer, and the like. In addition, as the paper wanocenling, sensitive, which is pine, and the like, IPMC unidirectional bending [ J ] manned aerospace is realized through an asymmetric electrode, 2017,23(004): 541-.

However, the above prior art preparation method mainly combines a mask method or a laser ablation electrode method to realize a patterned electrode on both sides, and the electrode plating method used in the prior art is still the conventional IPMC immersion reduction plating method. Thus, the interface of the two layers of electrodes with the membrane is still symmetrical. The invention provides a novel IPMC preparation method aiming at the application requirements of a curled IPMC driver, the ion exchange process in the traditional process is replaced by a direct fusion method, and the asymmetry of the electrode interfaces at two sides is realized by utilizing the density difference of electrode complex salt and matrix membrane solution. The IPMC material prepared by the method has excellent performance and simple preparation method, the interface between the prepared IPMC electrode and the matrix film has obvious gradient distribution, and the asymmetric electrode can be realized.

Disclosure of Invention

The technical problem to be solved by the invention is that the electrode layers are usually coated on the two sides of the membrane which cannot be avoided by the method in the prior art, only one side of the membrane can be covered according to needs to prepare the electrode layer with a single side, and the operation is complicated, so that the preparation method of the asymmetric electrode IPMC and the prepared asymmetric electrode IPMC are provided.

The invention solves the technical problems through the following technical means:

a preparation method of an asymmetric electrode IPMC comprises the following steps:

(1) mixing the substrate membrane solution with an electrode material, and carrying out layering treatment to obtain a membrane solution;

(2) performing film casting treatment on the film solution obtained in the step (1) to obtain a substrate film;

(3) and (3) carrying out reduction plating treatment on the substrate film, and forming an electrode layer on the surface of the film, namely the asymmetric electrode IPMC.

Has the advantages that: electrode materials required by IPMC are doped into a matrix film solution to form a film, and the film is chemically reduced and plated on the surface of the film to form an electrode, so that an asymmetric electrode IPMC can be designed, wherein the electrode comprises different materials and asymmetric appearance. Therefore, the specific electrode structure is realized, the adhesion between the electrode and the substrate film is enhanced, the depth of the infiltrated electrode is increased, the appearance of the infiltrated electrode is improved, and the electrochemical performance and the electromechanical performance of the IPMC material are further improved.

The invention can directly generate a single-side electrode on one side of the substrate film without mask design on one side of the film, and thus, the electrode design can be carried out on the other side of the film according to the requirement. Compared with the prior art, the preparation process has obvious innovation and effect improvement.

Preferably, the electrode material is selected from, but not limited to: pd²⁺、Ag⁺、Au⁺、Pt⁺、Ni⁺、Cu²⁺One or more of the complex salts of (a).

Preferably, the matrix film solution is selected from, but not limited to: a Nafion series ion exchange membrane solution from Dupont, an Aciplex series ion exchange membrane solution from Asahi Chemical, a Flemion series ion exchange membrane solution from Asahi Glass, or an Aquivion series ion exchange membrane solution from Solvay Solexis.

Preferably, the step (3) is performed by ion exchange treatment after electroplating.

Has the advantages that: through ion exchange sitesThe driving ions in the membrane are changed into Na⁺Or other types of ions, causing hydrated cations in the membrane to move under the action of an electric field, resulting in deformation of the IPMC.

Preferably, the electrode material deposition surface of the base film after the film casting treatment in the step (2) is subjected to a roughening treatment.

Has the advantages that: the performance of the electrode is enhanced by forming a transition layer between the substrate film and the electrode by roughening treatment.

Preferably, the roughening treatment comprises one of sand blasting, sanding, micro needle roughening, plasma etching.

Preferably, a layer of conductive silver paste is printed on the electroless surface of the substrate film after electroplating, and then dried.

Has the advantages that: the asymmetric electrode IPMC of the present invention has an electrode layer on one side, and a different electrode layer may be provided on the other side of the film as needed.

Preferably, DMAC is added into the matrix film solution, and the mass ratio of the matrix film solution to the DMAC is 3: 1.

Preferably, the cast film treatment is carried out under a vacuum condition, the treatment temperature is 90-120 ℃, and the treatment time is 15-30 h.

Preferably, the reduction treatment in the step (3) comprises the following steps: mixing ultrapure water with ammonia water to prepare a plating solution, and adding NaBH under the oscillation condition₄Reducing the solution, adding the matrix membrane, and adding NaBH again after a period of time₄And (5) treating the reducing liquid.

Preferably, ultrapure water and ammonia water are mixed according to the volume ratio of 300:1, and 5 wt% of NaBH is added under the oscillating condition at the temperature of 40-60 DEG C₄Reducing the solution, putting the solution into a substrate film, and adding 5 wt% NaBH once every 5-30 min₄Reducing the solution in NaBH₄The reduction reaction is carried out in the environment with the concentration of 0.05 g/L-1 g/L, and the total time is 2-4 h; the mass concentration of the ammonia water is 25-28%.

Preferably, the electroplating in the step (3) comprises the following steps: and placing the reduced substrate film in electrolyte for electroplating treatment.

Preferably, the cathode adopted by the electroplating is an array needle, the anode is a titanium mesh, and the current is 0.1-0.3A.

Preferably, the electrolyte is gold water.

Preferably, the mass ratio of the base film solution to the electrode material is 36-144: 1.

An asymmetric electrode IPMC prepared by the method.

Has the advantages that: the asymmetric electrode IPMC prepared by the invention has excellent electrochemical performance and electromechanical performance.

The invention has the advantages that: electrode materials required by IPMC are doped into a matrix film solution to form a film, and the film is chemically reduced and plated on the surface of the film to form an electrode, so that an asymmetric electrode IPMC can be designed, wherein the electrode comprises different materials and asymmetric appearance. Therefore, the specific electrode structure is realized, the adhesion between the electrode and the substrate film is enhanced, the depth of the infiltrated electrode is increased, the appearance of the infiltrated electrode is improved, and the electrochemical performance and the electromechanical performance of the IPMC material are further improved.

Drawings

FIG. 1 is a schematic view of the IPMC material of the present invention.

FIG. 2 is a structural view of IPMC in embodiment 1 of the present invention;

FIG. 3 is a structural view of IPMC in embodiment 3 of the present invention;

FIG. 4 is a graph of displacement performance under DC 5V excitation in example 1 of the present invention;

FIG. 5 is a graph showing displacement behavior under DC 5V excitation in example 2 of the present invention;

in the figure: 1 is a first electrode layer; 2 is a matrix film layer; 3a second electrode layer.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.

The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.

Example 1

The embodiment discloses a preparation process of a single-sided electrode Pd-Au-IPMC material, which comprises the following steps of (1) preparing a first electrode layer 1 on one side of a substrate film layer 2, wherein the first electrode layer 1 contains metal electrodes Pd and Au, and the inner layer is a Pd electrode; the outer layer is an Au electrode, as shown in FIG. 2. The method specifically comprises the following steps:

(1) mixing material treatment: 24.48g of Nafion D520 solution, 8.16g of DMAC organic solvent and 169.95mg of Pd (NH)₃)₄Cl₂Adding the complex salt of palladium into a beaker, and fully stirring and mixing the complex salt of palladium at 50 ℃ under the condition of 600r/min for 5 hours. The Nafion solution has certain consistency, and can be better formed into a required shape in a mould by adding DMAC organic solvent for mixing and diluting.

(2) Standing the solution: pouring the mixed solution into a die with the size of 61mm x 61mm x 40mm, keeping the mixed solution under vacuum for 15min, removing gas included in the solution, and simultaneously realizing layering and precipitation or floating of the ion complex. In order to make the electrode material fully dispersed in the diluted solution, the electrode material is uniformly distributed on the bottom or the surface of the solution under a standing condition.

(3) And (3) casting film treatment: and (3) putting the mould containing the mixed solution into a vacuum drying oven, setting the temperature to be 90 ℃, keeping the temperature for about 20 hours, and carrying out annealing treatment when the film is observed to be basically solidified, setting the temperature to be 120 ℃, and setting the annealing time to be 2 hours.

(4) Ion reduction: weighing 186mL of DI water and 0.62mL of ammonia water (the content is 25-28%) to prepare a plating solution in a beaker, and firstly adding 5 wt% of NaBH under the conditions of 50 ℃ and a water bath constant temperature oscillator at 300r/min₄0.6mL of reducing solution is added into the membrane cast in the step (3), and then the membrane is added every 5min5 wt% NaBH at a time₄0.6mL of reducing solution is used for 24 times in total, and the total time is 2 h.

(5) Electroplating: and (3) performing edge cutting treatment on the membrane treated in the step (4), and performing gold plating treatment on the surface of the sample wafer under the action of current of 0.2A in 1.6g/L of gold water (100mL) as electrolyte, an array needle as a sound pole and a titanium net as an anode.

(6) Ion exchange: putting the membrane electroplated in the step (5) into 0.2mol/L NaOH solution, exchanging for 2h in a magnetic stirrer at 50 ℃ and 300r/min to convert the driving ions in the membrane into Na⁺。

FIG. 4 is a displacement curve of example 1 at DC voltage of 5V. The electromechanical properties of the sample were analyzed mainly by measuring the tip displacement of the sample having the cantilever beam structure. The sample is cut into strips with the size of 35mm x 5mm, a copper clamp is used for clamping the position 5mm away from the tail end of the sample wafer, one side of an electrode layer is connected with the anode, and the length of the other free end is 30 mm. Direct current 5V excitation voltage is output through a digital source meter, the IPMC material generates deformation of different degrees after receiving corresponding electric signals, the laser displacement sensor can accurately detect the deformation displacement value of the sample wafer, displacement signals are collected through matched software, and finally collected displacement information is processed and analyzed.

The measurement results show that the sample wafer generates displacement deformation of 1.103mm at the maximum under the DC voltage of 5V.

Example 2

The embodiment discloses a preparation process of a single-sided electrode Pd-Au-IPMC material, which specifically comprises the following steps:

(1) mixing material treatment: 24.48g of Nafion D520 solution, 8.16g of DMAC organic solvent and 169.95mg of Pd (NH)₃)₄Cl₂Adding the complex salt of palladium into a beaker, and fully stirring and mixing the complex salt of palladium at 50 ℃ under the condition of 600r/min for 5 hours.

(2) Standing the solution: pouring the mixed solution into a mold with a size of 61mm x 61mm x 40mm, maintaining the mold under vacuum for 15min, removing gas in the solution, and standing the mold in a horizontal position for 6h to allow Pd (NH)₃)₄Cl₂The complex salt of palladium precipitates well to the bottom of the solution.

(3) And (3) casting film treatment: and (3) putting the mould containing the mixed solution into a vacuum drying oven, setting the temperature to be 90 ℃, keeping the temperature for about 20 hours, and carrying out annealing treatment when the film is observed to be basically solidified, setting the temperature to be 120 ℃, and setting the annealing time to be 2 hours.

(4) Roughening treatment: pd (NH) of the membrane₃)₄Cl₂The deposition surface of the complex salt of palladium is roughened by a microneedle roller, the rest positions of four edges of the matrix film are fixed by an adhesive tape, and the surface of the matrix film is roughened back and forth for 100 cycles.

(5) Ion reduction: weighing 186mL of DI water and 0.62mL of ammonia water (the content is 25-28%) to prepare a plating solution in a beaker, and firstly adding 5 wt% of NaBH under the conditions of 50 ℃ and a water bath constant temperature oscillator at 300r/min₄1.2mL of reducing solution is put into the membrane cast in the step (3), and 5 wt% NaBH is added every 10min₄1.2mL of reducing solution, 12 times in total, and the total time is 2 h.

(6) Electroplating: and (3) performing edge cutting treatment on the membrane treated in the step (4), and performing gold plating treatment on the surface of the sample wafer under the action of current of 0.2A in 1.6g/L of gold water (100mL) as electrolyte, an array needle as a sound pole and a titanium net as an anode.

(7) Ion exchange: putting the membrane electroplated in the step (5) into 0.2mol/L NaOH solution, exchanging for 2h in a magnetic stirrer at 50 ℃ and 300r/min to convert the driving ions in the membrane into Na⁺。

FIG. 5 is a displacement curve of example 2 at DC voltage of 5V. The electromechanical properties of the sample were analyzed mainly by measuring the tip displacement of the sample having the cantilever beam structure. The sample is cut into strips with the size of 35mm x 5mm, a copper clamp is used for clamping the position 5mm away from the tail end of the sample wafer, one side of an electrode layer is connected with the anode, and the length of the other free end is 30 mm. Direct current 5V excitation voltage is output through a digital source meter, the IPMC material generates deformation of different degrees after receiving corresponding electric signals, the laser displacement sensor can accurately detect the deformation displacement value of the sample wafer, displacement signals are collected through matched software, and finally collected displacement information is processed and analyzed.

The measurement result shows that the sample wafer generates displacement deformation of 2.034mm at the maximum under the direct current voltage of 5V.

Example 3

The embodiment discloses a preparation process of an asymmetric electrode Pd-Au-Ag-IPMC material, as shown in FIG. 3, one surface of a substrate film layer 2 is a first electrode layer 1 containing metal electrodes Pd and Au, wherein an inner layer (close to the substrate film layer 2) is a Pd electrode; the outer layer is an Au electrode; the other side of the substrate film layer 2 is a second electrode layer 3 containing a metal electrode Ag. The method specifically comprises the following steps:

(1) mixing material treatment: 24.48g of Nafion D520 solution, 8.16g of DMAC organic solvent and 169.95mg of Pd (NH)₃)₄Cl₂Adding the complex salt of palladium into a beaker, and fully stirring and mixing the complex salt of palladium at 50 ℃ under the condition of 600r/min for 5 hours.

(2) Standing the solution: the mixed solution was poured into a 61mm x 61mm x 40mm mold and kept under vacuum for 15min to remove air entrapped in the solution.

(3) And (3) casting film treatment: and (3) putting the mould containing the mixed solution into a vacuum drying oven, setting the temperature to be 90 ℃, keeping the temperature for about 20 hours, and carrying out annealing treatment when the film is observed to be basically solidified, setting the temperature to be 120 ℃, and setting the annealing time to be 2 hours.

(4) Ion reduction: weighing 186mL of DI water and 0.62mL of ammonia water (the content is 25-28%) to prepare a plating solution in a beaker, and firstly adding 5 wt% of NaBH under the conditions of 50 ℃ and a water bath constant temperature oscillator at 300r/min₄0.6mL of reducing solution is put into the membrane cast in the step (3), and 5 wt% NaBH is added every 5min₄0.6mL of reducing solution is used for 24 times in total, and the total time is 2 h.

(5) Electroplating: and (3) performing edge cutting treatment on the membrane treated in the step (4), and performing gold plating treatment on the surface of the sample wafer under the action of current of 0.2A in 1.6g/L of gold water (100mL) as electrolyte, an array needle as a sound pole and a titanium net as an anode.

(6) Electrode coating: printing a layer of conductive silver paste on the electrodeless surface of the film, and drying for 4 hours on a drying heating table at 40 ℃.

(7) Ion exchange: putting the membrane electroplated in the step (5) into 0.2mol/L NaOH solution, and exchanging for 2h in a magnetic stirrer at 50 ℃ and 300r/minTo convert the driving ions in the membrane into Na⁺。

The technical core of the invention is to firstly provide that electrode materials required by IPMC are doped into a matrix film solution to form a film, and then the film is chemically reduced and plated on the surface of the film to form an electrode, so that an asymmetric electrode IPMC can be designed, wherein the electrode comprises different materials and asymmetric appearance. Therefore, the specific electrode structure is realized, the adhesion between the electrode and the substrate film is enhanced, the depth of the infiltrated electrode is increased, the appearance of the infiltrated electrode is improved, and the electrochemical performance and the electromechanical performance of the IPMC material are further improved.

The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.