TWI796012B - Stretchable electroconductive material, method for manufacturing the same, and stretchable device using the stretchable electroconductive material - Google Patents

Abstract

A stretchable electroconductive material includes 100 parts by weight of PEDOT-PSS, 200 parts to 1000 parts by weight of a repair linking agent, 15 parts to 300 parts by weight of an ionic liquid plasticizer, and 15 parts to 200 parts by weight of carbon material particles. The repair linking agent is selected from a group consisting of polyethylene glycol and polyethylene oxide, and any combination thereof. The repair linking agent, the ionic liquid plasticizer, and the carbon material particles are doped in the PEDOT-PSS. A method for manufacturing the stretchable electroconductive material and a device using the stretchable electroconductive material are also provided.

Description

Stretchable conductive material and preparation method thereof, device with stretchable performance

The invention relates to a deformable material, in particular to a stretchable conductive material and its preparation, and a device with stretchable performance using the stretchable conductive material.

Stretchable conductive materials are widely used in various electronic fields, such as: soft (stretchable) electronics, wearable devices, implanted components, artificial limbs, intelligent robots and various irregular surfaces that require conductive properties. Considerable emphasis is placed on academic research. However, how to endow stretchable conductive materials with self-healing properties is the focus of current research.

In view of this, it is necessary to provide a method for preparing stretchable conductive materials with self-healing ability.

In addition, it is also necessary to provide a stretchable conductive material and a stretchable device using the stretchable conductive material.

A method for preparing a stretchable conductive material, comprising the following steps: dissolving 100 parts by weight of poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid in water, and then sequentially adding 200 to 1000 parts by weight of repairing Connecting agent and ionic liquid plasticizer of 15～300 weight parts, mix and make mixed solution, wherein, described repair connecting agent is selected from at least one in polyethylene glycol and polyethylene oxide; Dispersing the carbon material particles in isopropanol to prepare a dispersion liquid; mixing the mixed solution with the dispersion liquid to form a conductive paste, in the conductive paste, the carbon material particles and the poly( The weight ratio of 3,4-ethylenedioxythiophene)-polystyrenesulfonic acid is 3:20~2:1; and the conductive paste is coated and dried to form a stretchable conductive material.

A stretchable conductive material, comprising: 100 parts by weight of poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid; 200-1000 parts by weight of repairing linker; 15-300 parts by weight of ionic liquid plasticizer agent; and 15 to 200 parts by weight of carbon material particles; wherein, the repair linking agent is selected from at least one of polyethylene glycol and polyethylene oxide, the repair linking agent, the ionic liquid plasticizer And the carbon material particles are doped in the poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid.

A device with stretchability, comprising the stretchable conductive material as described above.

In the above preparation method of the stretchable conductive material, the poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid is used as the main conductive medium of the stretchable conductive material to conduct electricity. The ionic liquid plasticizer doped in poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid can improve the conductivity of poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid , while changing the arrangement of poly(3,4-ethylenedioxythiophene) to achieve a toughening effect, thereby improving the tensile properties of the stretchable conductive material. The repair linking agent can further improve the conductivity and mechanical properties of the stretchable conductive material, and at the same time, the repair linker is introduced into poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid to make the stretchable conductive material Realize reversible dynamic bonding, so that stretchable conductive materials have self-healing properties. Firstly, poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid and the like are dispersed in water to obtain the mixed solution, and the carbon material particles are dispersed in isopropanol to obtain the dispersion liquid, Then the mixed solution is mixed with the dispersion liquid, so that the poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid can be intermixed and dispersed with the carbon material particles to achieve the effect of uniform dispersion.

The following clearly and completely describes the technical solutions in the embodiments of the present application. Apparently, the described embodiments are only some of the embodiments of the present application, but not all of them.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field of the application. The terms used herein in the description of the application are for the purpose of describing specific embodiments only, and are not intended to limit the application.

In the case of no conflict, the following embodiments and features in the embodiments can be combined with each other.

A method for preparing a stretchable conductive material according to an embodiment of the present invention comprises the following steps:

Step S1, dissolving poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT-PSS) in water, then sequentially adding a repairing linker and an ionic liquid plasticizer, and mixing to obtain a mixed solution. Wherein, the repair linking agent is selected from at least one of polyethylene glycol (PEG) and polyethylene oxide (PEO).

In the mixed solution, poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid is 100 parts by weight, the repair linking agent is 200~1000 parts by weight, and the ionic liquid plasticizer is 15 parts by weight. ~300 parts by weight.

In this embodiment, the content of water only needs to dissolve poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid, the repair linking agent and the ionic liquid plasticizer, and it is not necessary to Limit.

Preferably, the polyethylene glycol has a molecular weight of 100-500, and the polyethylene oxide has a molecular weight of 50,000-150,000. More preferably, the polyethylene glycol has a molecular weight of 100-400, and the polyethylene oxide has a molecular weight of 80,000-120,000, so as to further improve the self-healing ability of the stretchable conductive material.

The ionic liquid plasticizer can be selected from but not limited to 1-ethyl-3-methylimidazolium tetracyanoborate, lithium bistrifluoromethanesulfonyl imide, 1-butyl-3-methylimidazolium At least one of sulfate, sodium dioctyl lipoate, sodium dodecylbenzenesulfonate, and the like.

In this embodiment, the poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid, the repairing agent and the ionic liquid plasticizer are mixed by stirring. Wherein, the stirring rate is 600rpm~1500rpm, and the stirring time is 10hr~14hr.

Step S2, dispersing the carbon material particles in isopropanol to prepare a dispersion liquid.

The carbon material particles may include at least one or both of carbon nanotubes and graphene. Preferably, the aspect ratio of the carbon nanotubes may be 100:1-1000:1. More preferably, the aspect ratio of the carbon nanotubes may be 500:1-700:1.

Specifically, the diameter of the carbon nanotubes is preferably 45 nm to 55 nm, and the length of the carbon nanotubes is preferably 27 microns to 33 microns.

The number of layers of the graphene is preferably 5-15 layers, the thickness of the graphene is preferably 2nm-5nm, and the specific surface area is preferably 80m ² /g-150m ² /g.

In this embodiment, the mass percentage of the carbon material particles in the dispersion liquid may be 0.5%-5%.

In this embodiment, the carbon material particles may be placed in isopropanol for stirring and then ultrasonic vibration to obtain the dispersion. Wherein, the stirring rate may be 600rpm~1500rpm, and the stirring time is 2hr~4hr. The frequency of the ultrasonic vibration is 10kHz-50kHz, and the time is 30min-90min.

Step S3, mixing the mixed solution with the dispersion liquid to form a conductive paste. In the conductive paste, the weight ratio of the carbon material particles to the poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid is 3:20-2:1.

In this embodiment, the conductive paste can be formed by first stirring and then ultrasonically vibrating. Wherein, the stirring rate may be 600rpm~1500rpm, and the stirring time is 2hr~4hr. The frequency of the ultrasonic vibration is 10kHz-50kHz, and the time is 30min-90min.

In some embodiments, the viscosity of the conductive paste may be 50cps˜1000cps.

Step S4, coating and drying the conductive paste to form a stretchable conductive material.

The drying temperature may be 60°C-140°C. The drying time may be 90 minutes to 120 minutes. In some embodiments, the drying time can also be adjusted according to the thickness of the coated conductive paste.

In some embodiments, preferably, the coated conductive paste is dried by stepwise temperature rise. More preferably, it can be kept at a temperature of 60°C for 30 minutes to slowly volatilize the isopropanol and water in the conductive paste, and then be kept at a temperature of 90°C for 30 minutes to completely remove the isopropanol and water in the conductive paste. Remove, and finally keep warm for 30min~60min at a temperature of 140°C, so that the polymers in the conductive paste react to form a thin film with a stable structure, and obtain a stretchable conductive material.

In the above preparation method of the stretchable conductive material, the poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid is used as the main conductive medium of the stretchable conductive material to conduct electricity. The ionic liquid plasticizer doped in poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid can improve the conductivity of poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid , while changing the arrangement of poly(3,4-ethylenedioxythiophene) to achieve a toughening effect, thereby improving the tensile properties of the stretchable conductive material. The repair linking agent can further improve the conductivity and mechanical properties of the stretchable conductive material, and at the same time, the repair linker is introduced into poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid to make the stretchable conductive material Realize reversible dynamic bonding, so that stretchable conductive materials have self-healing properties. Firstly, poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid and the like are dispersed in water to obtain the mixed solution, and the carbon material particles are dispersed in isopropanol to obtain the dispersion liquid, Then the mixed solution is mixed with the dispersion liquid, so that the poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid can be intermixed and dispersed with the carbon material particles to achieve the effect of uniform dispersion.

An embodiment of the present application also provides a stretchable conductive material, including 100 parts by weight of poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid, 200-1000 parts by weight of repairing agent, 15-300 parts by weight Parts of ionic liquid plasticizer and 15-200 parts by weight of carbon material particles. The repair linking agent, the ionic liquid plasticizer and the carbon material particles are doped in the poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid.

The repair linking agent is selected from at least one of polyethylene glycol (PEG) and polyethylene oxide (PEO). Preferably, the polyethylene glycol has a molecular weight of 100-500, and the polyethylene oxide has a molecular weight of 50,000-150,000. More preferably, the polyethylene glycol has a molecular weight of 100-400, and the polyethylene oxide has a molecular weight of 80,000-120,000.

The ionic liquid plasticizer can be selected from but not limited to 1-ethyl-3-methylimidazolium tetracyanoborate, lithium bistrifluoromethanesulfonyl imide, 1-butyl-3-methylimidazolium At least one of sulfate, sodium dioctyl lipoate, sodium dodecylbenzenesulfonate, and the like.

The carbon material particles may include at least one or both of carbon nanotubes and graphene. Preferably, the aspect ratio of the carbon nanotubes may be 100:1-1000:1. More preferably, the aspect ratio of the carbon nanotubes may be 500:1-700:1.

Specifically, the diameter of the carbon nanotubes is preferably 45 nm to 55 nm, and the length of the carbon nanotubes is preferably 27 microns to 33 microns.

The number of layers of the graphene is preferably 5-15 layers, the thickness of the graphene is preferably 2nm-5nm, and the specific surface area is preferably 80m ² /g-150m ² /g.

The above-mentioned stretchable conductive material can be applied in devices (not shown in the figure), which can be but not limited to wearable devices, artificial limbs, intelligent robots and the like.

The present invention will be described in detail below with examples and comparative examples.

Example 1

Dissolve 100g of poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid in 9300g of water, then add 600g of polyethylene glycol and 150g of 1-ethyl-3-methylimidazolium tetracyanide in sequence Base borate was stirred at a rate of 800rmp for 12 hours to obtain a mixed solution.

50 g of carbon nanotubes were dispersed in 5000 g of isopropanol, stirred at a rate of 800 rpm for 3 hours, and then ultrasonically oscillated at a frequency of 20 kHz for 1 hour to obtain a dispersion.

The above-mentioned mixed solution and the above-mentioned dispersion liquid were mixed, stirred at a rate of 800 rpm for 3 hours, and then ultrasonically oscillated at a frequency of 20 kHz for 1 hour to prepare a conductive paste.

The above-mentioned conductive paste was coated on a base material and kept at a temperature of 60° C. for 30 minutes, then at a temperature of 90° C. for 30 minutes, and finally at a temperature of 140° C. for 60 minutes to form a conductive film. Wherein, the thickness of the conductive film is 20um.

Example 2

The difference from Example 1 is that the added 1-ethyl-3-methylimidazolium tetracyanoborate has a mass of 15 g.

Example 3

The difference from Example 1 is that the added carbon nanotubes have a mass of 15 g.

Example 4

The difference from Example 1 is that the added carbon nanotubes have a mass of 150 g.

Comparative example 1

The difference with Example 1 is: the quality of the polyethylene glycol added is 150g.

Comparative example 2

Dissolve 100g of poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid in 9300g of water to prepare a slurry, apply the above slurry on a substrate and keep it warm at 60°C for 30min, Then keep it at a temperature of 90° C. for 30 minutes, and finally keep it at a temperature of 140° C. for 60 minutes to form a conductive film. Wherein, the thickness of the conductive film is 20um.

Comparative example 3

Dissolve 100g of poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid in 9300g of water, then add 600g of polyethylene glycol and 150g of 1-ethyl-3-methylimidazolium tetracyanide in sequence Base borate was stirred at a rate of 800rmp for 12 hours to obtain a mixed solution.

The above mixed solution was coated on a substrate and kept at a temperature of 60°C for 30 minutes, then at a temperature of 90°C for 30 minutes, and finally at a temperature of 140°C for 60 minutes to form a conductive film. Wherein, the thickness of the conductive film is 20um.

The initial circuit resistance values of the four conductive films prepared in Examples 1-4 and the three conductive films prepared in Comparative Examples 1-3 were measured respectively, and are recorded in Table 1 below. Then pull the above-mentioned 7 kinds of conductive films Stretch, stretch 10% each time, test the resistance value of the stretched line after stretching 500 times, and record it in the following table 1. At the same time, calculate the change rate of the resistance value after stretching and record it in the following table 1 .

In addition, the 4 kinds of conductive films prepared in Examples 1-4 and the 3 kinds of conductive films prepared in Comparative Examples 1-3 were tested for their self-healing ability, and the test results are recorded in Table 1 below. The specific test method is as follows: fix both ends of each conductive film, stretch the conductive film by 100%, stretch it again by 100% after recovery, and loop it 500 times. If it cannot be recovered after 500 cycles or during the process, the conductive film cannot be self-repaired. If it can recover again after 500 cycles or during the process, the conductive film can be self-healed.

It can be seen from the above Table 1 that the conductive film prepared in the present application has good electrical conductivity and good stretching effect, and also has self-healing ability. On the other hand, if the content of the repairing linking agent is too low, the ability of the conductive film to form hydrogen bonds will decrease, which will lead to a decrease in the self-repairing ability of the conductive film, making it impossible to self-repair.

Claims (10)

A method for preparing a stretchable conductive material, comprising the following steps: dissolving 100 parts by weight of poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid in water, and then sequentially adding 200 to 1000 parts by weight of repairing Connecting agent and ionic liquid plasticizer of 15～300 parts by weight are mixed to obtain a mixed solution, wherein the repairing connecting agent is selected from at least one of polyethylene glycol and polyethylene oxide; the carbon material particles are dispersed In isopropanol, a dispersion liquid is prepared; the mixed solution is mixed with the dispersion liquid to form a conductive paste, and in the conductive paste, the carbon material particles and the poly(3,4-ethylene The weight ratio of dioxythiophene)-polystyrene sulfonic acid is 3:20~2:1; and the conductive paste is coated and dried to form a stretchable conductive material. The preparation method of the stretchable conductive material according to claim 1, wherein the polyethylene glycol has a molecular weight of 100-500, and the polyethylene oxide has a molecular weight of 50,000-150,000. The preparation method of the stretchable conductive material as claimed in item 1, wherein, the ionic liquid plasticizer comprises 1-ethyl-3-methylimidazolium tetracyanoborate, bistrifluoromethanesulfonimide lithium , at least one of 1-butyl-3-methylimidazolium octyl sulfate, dioctyl lipoic acid sodium salt and sodium dodecylbenzenesulfonate. The preparation method of the stretchable conductive material according to claim 1, wherein the carbon material particles are selected from at least one of carbon nanotubes and graphene, and the aspect ratio of the carbon nanotubes is 100:1~1000 : 1, the diameter of the carbon nanotube is 45nm~55nm. The method for preparing a stretchable conductive material according to claim 1, wherein the mass percentage of the carbon material particles in the dispersion is 0.5%-5%. A stretchable conductive material, the improvement of which includes: 100 parts by weight of poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid; 200-1000 parts by weight of repairing linking agent; An ionic liquid plasticizer; and 15 to 200 parts by weight of carbon material particles; Wherein, the repairing linking agent is selected from at least one of polyethylene glycol and polyethylene oxide, and the repairing linking agent, the ionic liquid plasticizer and the carbon material particles are doped in the poly( 3,4-ethylenedioxythiophene)-polystyrenesulfonic acid. The stretchable conductive material according to claim 6, wherein the polyethylene glycol has a molecular weight of 100-500, and the polyethylene oxide has a molecular weight of 50,000-150,000. The stretchable conductive material as claimed in item 6, wherein the ionic liquid plasticizer comprises 1-ethyl-3-methylimidazolium tetracyanoborate, lithium bistrifluoromethanesulfonyl imide, 1- At least one of butyl-3-methylimidazolium octyl sulfate, dioctyl lipoate sodium salt and sodium dodecylbenzenesulfonate. The stretchable conductive material according to claim 6, wherein the carbon material particles are selected from at least one of carbon nanotubes and graphene, and the aspect ratio of the carbon nanotubes is 100:1 to 1000:1, The diameter of the carbon nanotube is 45nm-55nm. A stretchable device, the improvement of which includes the stretchable conductive material as described in any one of claims 6-9.