KR101603772B1 - Solid electrolyte polymer, Polymer actuator using cross-linking PVDF polymer and Manufacturing Method of the Same - Google Patents

Abstract

A polymer actuator comprising a PVDF based polymer and an electrolytic material is disclosed. The disclosed PVDF-based polymer can be applied to an actuator or the like in a state of being crosslinked by a crosslinking agent.

Description

TECHNICAL FIELD [0001] The present invention relates to a solid polymer electrolyte, a solid electrolyte polymer, a polymer actuator using cross-linked PVDF polymer,

Embodiments of the present invention relate to a solid electrolyte polymer and an actuator using the same, and can be widely used in mobile devices and the like, and can be applied to various fields such as polymer MEMS, bio, and solar cell.

In recent years, polymer polymer actuators using polymer sensors and polymers have been expanding their applications because of their potential applications in various fields. For example, with respect to high performance camera modules for mobile devices, it is expected that actuators can be utilized to implement autofocus and zoom functions.

Conventional electrolyte polymer actuators require the use of a liquid electrolyte to accommodate a chamber capable of holding an electrolyte material, so that a problem of volume increase may arise, and there is a reliability problem of sealing. As an alternative to such an electrolyte polymer actuator, a solid electrolyte polymer actuator using NBR (acrylonitrile butadiene rubber) / polypyrrole is known.

A solid electrolyte polymer and a polymer actuator having excellent thermal stability and chemical resistance and capable of driving at a low voltage, including the polymer electrolyte, are provided.

In an embodiment of the present invention, there is provided a polymer actuator comprising a PVDF polymer and a solid electrolyte layer formed of an electrolytic material.

A first electrode formed on both surfaces of the solid electrolyte layer; And a second electrode.

The PVDF polymer may be crosslinked by a crosslinking agent.

The PVDF-based polymer may be P (vinylidene fluoride) - (trifluoroethylene) - chloro trifluoroethylene (PTFE) or P (vinylidene fluoride) - Trifluoroethylene (PTFE) - CFC (chloro fluoro ethylene).

Wherein the first electrode comprises at least one of PPy (polypyrrole), PEDOT (3,4-Ethylen DiOxy Thiophene), or PPy (polypyrrole), PEDOT Or PANI (Polyaniline).

The crosslinking agent may be selected from the group consisting of dicumyl peroxide (DCP), benzoyl peroxide, bisphenol A, methylenediamine, ethylenediamine (EDA), isopropylethylenediamine (IEDA), 1,3 phenylenediamine (PDA), 1,5-naphthalenediamine -trimethyl-1 or 6-hexanediamine (THDA).

The electrolytic material was prepared from a group consisting of n-butyl-3-methyl imidazolium tetrafluoroborate (BMIBF), n-butyl-3-methyl imidazolium hexafluorophosphate (BMIPF6), and n-butyl-3-methyl imidazolium bis (trifluoromethanesulfonyl) imide It may be one or more selected materials.

In the method of manufacturing a polymer actuator according to the embodiment of the present invention,

Forming a PVDF-based solution as a PVDF-based polymer powder, and then introducing a crosslinking agent into the PVDF-based solution;

Forming the PVDF solution including the crosslinking agent in a film form and then performing heat treatment to form a crosslinked PVDF polymer film;

Coating the crosslinked PVDF polymer film with a conductive polymer solution; And

Injecting an electrolyte into the PVDF polymer film; The present invention also provides a method of manufacturing a polymer actuator.

The conductive polymer may be PPy (polypyrrole), PEDOT (3,4-Ethylen DiOxy Thiophene) or PANI (Polyaniline).

In addition, embodiments of the present invention provide a solid electrolyte polymer formed of a crosslinked PVDF polymer and an electrolytic material.

According to the embodiment of the present invention, by using a crosslinked PVDF polymer as a polymer material for an actuator, it is possible to provide a solid electrolyte polymer and a polymer actuator which can be driven at a low voltage and have excellent thermal stability and chemical resistance.

Hereinafter, the solid electrolyte polymer and the polymer actuator using the crosslinked PVDF polymer will be described in detail with reference to the accompanying drawings. For reference, it should be noted that the thickness and width of each layer or regions shown in the figures are exaggerated for clarity.

FIGS. 1A and 1B are views showing the structure of a solid electrolyte polymer and a polymer actuator including the solid electrolyte polymer using the PVDF polymer according to an embodiment of the present invention.

1A and 1B, a solid electrolyte polymer layer 12 is formed, and an electrode is formed on at least one surface of the solid electrolyte polymer layer 12. For example, the first electrode 10 and the second electrode 14 are formed on the upper surface and / or the lower surface of the solid electrolyte polymer layer 12. The solid electrolyte polymer layer 12 may be formed of a PVDF terpolymer and crosslinked by a cross-linking agent to improve thermal stability and chemical stability. The solid electrolyte polymer layer 12 may contain an electrolytic material inside the crosslinked PVDF-based polymer.

Specifically, a material that can be used as a PVDF terpolymer is, for example, P (vinylidene fluoride) -TrFE (trifluoroethylene) -CTFE (chlorofluoroethylene) or P (VDF (vinylidene fluoride) CFE (chloro fluoro ethylene)). The PVDF polymer may be insufficient by itself if the solid electrolyte polymer layer 12 requires high thermal stability and high chemical resistance that is not readily soluble in various solvents. In this case, in order to improve thermal stability and chemical resistance, the PVDF polymer may be used as a solid electrolyte polymer layer 12 in a state of being crosslinked with a crosslinking agent.

Examples of substances that can be used as crosslinking agents include dicumyl peroxide (DCP), benzoyl peroxide, bisphenol A, methylenediamine, ethylenediamine (EDA), isopropylethylenediamine (IEDA) ), 2,4,4-trimethyl-1 or 6-hexanediamine (THDA).

Electrolytic materials that can be included in the crosslinked PVDF polymer include, for example, BMIBF (n-butyl-3-methyl imidazolium tetrafluoroborate), BMIPF6 (n-butyl-3-methyl imidazolium hexafluorophosphate) and BMITFSI -methyl imidazolium bis (trifluoromethanesulfonyl) imide).

The first electrode 10 and the second electrode 14 may be formed of a conductive polymer such as PPy (Polypyrrole), PEDOT (3,4-Ethylene Di-Oxythiophene), or PANI (Polyaniline).

The driving principle of the polymer actuator will be described as follows. When a voltage is applied through the first electrode 10 and / or the second electrode 14, the solid electrolyte polymer layer 12 becomes an oxidized state and becomes positively charged. The negative charge in the solid electrolyte polymer layer 12 is driven to move in the direction of the first electrode 10 or the second electrode 14 while being bent by the swelling phenomenon of the solid electrolyte polymer layer 12. The driving direction of such an actuator can be selectively adjusted according to the applied voltage direction.

2 is a cross-sectional image of a solid electrolyte polymer actuator using a PVDF polymer crosslinked with a THDA crosslinking agent. Here, the first electrode 10 and the second electrode 14 are formed of PPy, which is a conductive polymer, in a thickness of 20 to 25 탆, and the solid electrolyte polymer layer 12 is a P (VDF-TrFE-CTFE) It is made of 30-35μm thick and contains electrolytic material (BMITFSI).

Hereinafter, a method for manufacturing an actuator using a crosslinked PVDF polymer according to an embodiment of the present invention will be described with reference to FIGS. 3A to 3K.

Referring to FIG. 3A, a PVDF polymer powder P is introduced into a container 41 containing a solvent 31 (solvent). P (VDF-TrFE-CTFE) or P (VDF-TrFE-CFE) terpolymer may be used as the PVDF polymer. For example, the PVDF polymer solution is mixed with 5 wt.% PVDF polymer solution at room temperature or heat.

Referring to FIGS. 3B and 3C, a crosslinking agent (CL) is added to the PVDF polymer solution (32). As a cross-linking agent (CL), dicumyl peroxide (DCP), benzoyl peroxide, bisphenol A, methylenediamine, ethylenediamine (EDA), isopropylethylenediamine (IEDA), 1,3phenylenediamine (PDA), 1,5-naphthalenediamine 4-trimethyl-1 or 6-hexanediamine (THDA) may be used. For example, a crosslinking agent (CL) of about 2 wt.% Is put into a container (41) containing a PVDF system solution (32) and then mixed at room temperature or heat while applying a crosslinking agent (CL) (33) of the mixed solution (32).

Referring to FIG. 3D, a mixed solution 33 of a crosslinking agent and a PVDF polymer solution is formed in a film form on a plate 42 using a bar-coater 43, for example, by a solution casting method . Then, the solvent 31 is evaporated.

Referring to FIG. 3E, a PVDF polymer film F1 containing a crosslinking agent is crosslinked by heating in a heating vessel 44, for example, at a temperature of about 160 to 170 degrees centigrade.

Dynamic mechanical analysis (DMA), differential scanning calorimeter (DSC) analysis and solubility test can be performed to confirm the crosslinking of the PVDF polymer by the crosslinking agent. As a result of the DMA analysis of the PVDF polymer film (F1) subjected to the above process, when comparing the glass transition temperature (Tg) of the PVDF polymer in the initial state and the PVDF polymer in the crosslinked state, Tg Rise. Comparing the loss modulus and the storage modulus, the crosslinked PVDF polymer has a higher value than the PVDF in the initial state. In the case of DSC analysis, when the crystallization amount (? H) of the DSC peak of the PVDF polymer in the initial state and the crosslinked PVDF polymer are compared, the value of the crystal amount in the crosslinked state becomes relatively small. This is because when the PVDF polymer is crosslinked by the crosslinking agent, the chains are entangled with each other.

A method of forming a polymer actuator using a PVDF polymer in which crosslinking by a crosslinking agent is confirmed will be described.

Referring to FIG. 3F, a PVDF polymer membrane is immersed in a container 45 containing a conductive polymer solution 34 to coat a crosslinked PVDF polymer membrane with a conductive polymer layer to be used as an electrode. As the conductive polymer, PPy (polypyrrole), PEDOT (3,4-Ethylen DiOxy Thiophene), PANI (Polyaniline) and the like can be used. For example, the crosslinked PVDF polymer membrane is immersed in the pyrrole stock solution for several minutes to several tens of minutes by using pyrrole as the conductive polymer solution 34. [ Then, the PVDF polymer film F2 is impregnated with pyrrole, and then the PVDF polymer film F2 impregnated with the pyrrole is taken out. Then, the pyrrole buried on the surface of the PVDF polymer film F2 is wiped with a filter paper or the like. In order to polymerize pyrrole, which is a monomer, to form PPy, a PVDF polymer film impregnated with pyrrole is immersed in a container 45 containing an oxidizing agent 35, as shown in Fig. 3G. As the oxidizing agent (35), a metal compound, iron toluene sulfonate (FTS), FeCl ₃ or AuCl ₃ can be used. For example, a 2M FeCl ₃ solution can be impregnated with a PVDF polymer membrane. As a result, a conductive polymer-coated PVDF polymer film (F3) can be formed.

3H, the slope of the PVDF polymer film F4 coated with the conductive polymer taken out from the container 45 is cut along the line c, and then washed with methanol, for example, to remove the pyrrole monomer . Then, a polymer film (F5) of a conductive polymer / PVDF polymer film / conductive polymer structure, for example, a PPy / PVDF polymer film / PPy film can be formed by drying at room temperature in a vacuum oven 46 as shown in Fig. 3i .

3J, in order to inject an electrolytic substance into the PVDF polymer film, a conductive polymer / PVDF polymer film having a certain size prepared in the above-described manner in the container 45 containing the liquid electrolyte 36 in which the electrolytic substance is dissolved in the solvent / Immerses the membrane of the conductive polymer structure. As the electrolytic material, n-butyl-3-metyl imidazolium tetrafluoroborate (BMIBF), n-butyl-3-metyl imidazolium hexafluorophosphate (BMIPF6) or n-butyl-3-methyl imidazolium bis (trifluoromethanesulfonyl) imide have. As the solvent, PC (propylene carbonate), acetonitile, methyl benzoate or EC (methyl benzoate ethylene carbonate) may be used. Heat or pressure may be applied during the impregnation process to ensure that the liquid electrolyte 36 is sufficiently impregnated within the PVDF polymer membrane. As a result, the PVDF polymer film F6 impregnated with the liquid electrolyte 36 can be obtained. Referring to FIG. 3K, the solvent used in impregnating the liquid electrolyte may be evaporated to leave only the electrolytic material inside the PVDF polymer, thereby forming the PVDF polymer actuator F7 containing the electrolytic material.

In order to confirm the movement of the actuator manufactured as described above, a 5 x 30 mm ² actuator was manufactured. Here, the actuator includes a BMITFSI electrolytic material in a PVDF polymer film formed of P (VDF (vinylidene fluoride) -TrFE (trifluoroethylene) -CTFE (chloro trifluoro ethylene)) using DCP as a crosslinking agent, will be. The actuator was subjected to cyclic voltammetry using a Potentiostat instrument (PARSTAT 2263) at a rate of 500 mV / sec in the range of -5 V to 5 V. To measure the actuator displacement (mm) at this time, a laser beam (KEYENCE LK-081, KEYENCE Co., Japan) was installed and the drive displacement was measured. As a result of the measurement, the driving displacement of 5 mm or more was confirmed, and the driving displacement of about 10 mm and 15 mm was also confirmed.

While a great many have been described in the foregoing description, they should not be construed as limiting the scope of the invention, but rather as examples of embodiments. Accordingly, the scope of the present invention should not be limited by the illustrated embodiments but should be determined by the technical idea described in the claims.

FIGS. 1A and 1B are diagrams illustrating the structure of a solid electrolyte polymer and a polymer actuator including the same according to an embodiment of the present invention using a crosslinked PVDF polymer.

2 is a cross-sectional image of a solid electrolyte polymer actuator using a crosslinked PVDF polymer.

3A to 3K are views showing a method of manufacturing an actuator using a crosslinked PVDF polymer according to an embodiment of the present invention.

Description of the Related Art

10 ... first electrode 12 ... solid electrolyte polymer layer

14 ... second electrode 31 ... solvent

32 ... PVDF system solution 33 ... mixed solution

34 ... conductive polymer solution 35 ... oxidizing agent

36 ... liquid electrolyte 41, 45 ... container

42 ... plate 43 ... bar-coater

44 ... heating vessel 46 ... oven

Claims (18)

Wherein the PVDF polymer is crosslinked by a crosslinking agent and the crosslinking agent is selected from the group consisting of dicumyl peroxide (DCP), benzoyl peroxide, bisphenol A, methylenediamine, ethylenediamine (EDA) polymer actuators such as isopropylethylenediamine (IEDA), 1,3-phenylenediamine (PDA), 1,5-naphthalenediamine (NDA), 2,4,4-trimethyl-1 or 6-hexanediamine (THDA). The method according to claim 1, A first electrode formed on both surfaces of the solid electrolyte layer; And a second electrode. delete The method according to claim 1, The PVDF-based polymer is a polymer actuator wherein P (vinylidene fluoride) -TrFE (trifluoroethylene) -CTFE (chloro trifluoroethylene) or P (VDF (vinylidene fluoride) -TrFE (trifluoroethylene) -CFluoroethylene). 3. The method of claim 2, Wherein the first electrode comprises polypyrolene (PPy), 3,4-ethylenedioxythiophene (PEDOT), or PANI (Polyaniline). 3. The method of claim 2, Wherein the second electrode comprises polypyrolene (PPy), 3,4-ethylenedioxythiophene (PEDOT), or PANI (Polyaniline). delete The method according to claim 1, The electrolytic material was prepared from a group consisting of n-butyl-3-methyl imidazolium tetrafluoroborate (BMIBF), n-butyl-3-methyl imidazolium hexafluorophosphate (BMIPF6), and n-butyl-3-methyl imidazolium bis (trifluoromethanesulfonyl) imide Polymer actuators that are one or more selected materials. A method of manufacturing a polymer actuator, Forming a PVDF-based solution as a PVDF-based polymer powder, and then introducing a crosslinking agent into the PVDF-based solution; Forming the PVDF-based solution containing the crosslinking agent in a film form and then performing heat treatment to form a crosslinked PVDF polymer film; Coating the crosslinked PVDF polymer film with a conductive polymer solution; And Injecting an electrolyte into the PVDF polymer film; / RTI > The crosslinking agent may be selected from the group consisting of dicumyl peroxide (DCP), benzoyl peroxide, bisphenol A, methylenediamine, ethylenediamine (EDA), isopropylethylenediamine (IEDA), 1,3 phenylenediamine (PDA), 1,5-naphthalenediamine -trimethyl-1 or 6-hexanediamine (THDA). 10. The method of claim 9, The PVDF polymer may be a polymer actuator such as P (VDF (vinylidene fluoride) -TrFE (trifluoroethylene) -CTFE (chloro trifluoroethylene)) or P (VDF (vinylidene fluoride) -TrFE Gt; 10. The method of claim 9, Wherein the conductive polymer is PPy (polypyrrole), PEDOT (3,4-Ethylen DiOxythiopene), or PANI (Polyaniline). delete 10. The method of claim 9, Wherein the electrolytic solution comprises an electrolytic material dissolved in a solvent. 14. The method of claim 13, The electrolytic material was prepared from a group consisting of n-butyl-3-methyl imidazolium tetrafluoroborate (BMIBF), n-butyl-3-methyl imidazolium hexafluorophosphate (BMIPF6), and n-butyl-3-methyl imidazolium bis (trifluoromethanesulfonyl) imide ≪ / RTI > wherein the polymeric material is at least one selected material. Wherein the PVDF polymer is crosslinked by a crosslinking agent and the crosslinking agent is selected from the group consisting of dicumyl peroxide (DCP), benzoyl peroxide, bisphenol A, methylenediamine, ethylenediamine (EDA), isopropylethylenediamine ), 1,3-Phenylenediamine (PDA), 1,5-Naphthalenediamine (NDA), 2,4,4-trimethyl-1 or 6-hexanediamine (THDA) 16. The method of claim 15, The PVDF polymer is a solid electrolyte polymer that is P (vinylidene fluoride) -TrFE (trifluoroethylene) -CTFE (chloro trifluoroethylene) or P (VDF (vinylidene fluoride) -TrFE . delete 16. The method of claim 15, The electrolytic material was prepared from a group consisting of n-butyl-3-methyl imidazolium tetrafluoroborate (BMIBF), n-butyl-3-methyl imidazolium hexafluorophosphate (BMIPF6), and n-butyl-3-methyl imidazolium bis (trifluoromethanesulfonyl) imide A solid electrolyte polymer that is one or more selected materials.

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