CN114032688A - Intrinsic stretchable conductive polymer material and preparation method and application thereof - Google Patents

Intrinsic stretchable conductive polymer material and preparation method and application thereof Download PDF

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CN114032688A
CN114032688A CN202111177949.5A CN202111177949A CN114032688A CN 114032688 A CN114032688 A CN 114032688A CN 202111177949 A CN202111177949 A CN 202111177949A CN 114032688 A CN114032688 A CN 114032688A
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conductive polymer
polymer material
stretchable conductive
intrinsic
strain
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CN114032688B (en
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毛吉富
李沂蒙
王富军
王璐
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Donghua University
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Abstract

The invention relates to an intrinsic stretchable conductive polymer material and a preparation method and application thereof, wherein the preparation method comprises the following steps: the intrinsic stretchable conductive polymer material is prepared by depositing polypyrrole on the surface of an elastic material by an in-situ polymerization method by taking sodium sulfosalicylate as a doping agent and ferric chloride as an oxidizing agent; the prepared intrinsic stretchable conductive polymer material consists of an elastic material matrix and a polypyrrole coating doped with sodium sulfosalicylate; the intrinsic stretchable conductive polymer material is used as a stretchable electronic circuit of a flexible electronic device, or used as an electrode of a flexible supercapacitor, or used for manufacturing a corrugated conductive polymer material. The preparation method is simple, the sodium sulfosalicylate is used as a doping agent, and the ferric chloride is used as an oxidizing agent, so that the high conductivity of the polypyrrole coating is ensured, the molecular chain spacing of the polypyrrole is increased, the stretchability of the polypyrrole coating is improved, and the resistance variation of the product when the strain is 100% is far lower than that of the prior art.

Description

Intrinsic stretchable conductive polymer material and preparation method and application thereof
Technical Field
The invention belongs to the field of flexible electronics, and particularly relates to an intrinsic stretchable conductive polymer material, and a preparation method and application thereof.
Background
Due to the advantages of high flexibility, low-cost manufacturing, lightness, portability and the like, the flexible electronic device is widely researched in the fields of electronic skin, soft robots, wearable electronic devices, personal health monitoring and the like. However, flexible electronics are challenging in applications that undergo large tensile deformations or that are tightly bound to curved surfaces (e.g., human skin), which has prompted the emergence of flexible, stretchable electronics.
Intrinsically stretchable conductive materials are an effective way to realize stretchable electronic devices, which are inexpensive to manufacture and can be fabricated on a large scale. Blending conductive materials with stretchable materials is an effective means of imparting stretchability to rigid conductive materials, but non-conductive stretchable materials greatly reduce the conductive properties of the materials. Depositing a coating of conductive material on the surface of a material is an effective strategy to ensure high conductivity.
Among them, conductive polymers have been widely studied in the fields of wearable devices (strain > 100%) and biomedical devices due to their light weight, low cost, excellent conductivity, and good biocompatibility. Document 1 (a novel hydrogen bond crosslinking stretchable conductive polymer and a synthesis method: china, 201811466213.8P. 2019.04.19.) developed an intrinsically stretchable conductive polymer composed of a conductive high molecular group and a stretchable group, wherein the conductive high molecular group provides a conductive flexible group to impart stretchability, but the non-conductive flexible group tends to hinder electron transport, and more importantly, has an electrical conductivity of 0.9 times the initial electrical conductivity at a strain of 50% and an electrical conductivity of 0.4 times the initial electrical conductivity at a strain of 100%. Poly-2, 3-ethylenedioxythiophene (PEDOT: PSS) doped with flexible macromolecular polystyrene sulfonate is of interest because the flexible PSS chains provide some stretchability (much less than 50%) to it. Document 2(a high strain, transient, and conductive polymer [ J ] Science Advances, 2017; 3: e1602076.) prepares a conductive material capable of reaching 100% tensile strain after mixing PEDOT: PSS and a conductive ionic liquid, but the huge difference between the ionic liquid concentration (40 wt% to 70 wt%) and the PEDOT: PSS concentration (1.1 wt% to 1.3 wt%) makes the conductive Polymer (PEDOT) content in the conductive coating extremely small, and the toxic ionic liquid also makes the conductive composite lose the possibility of application in wearable and biomedical devices. In document 3(Biocompatible polymeric Materials with High Conductivity and High tensile properties [ J ]. Applied Materials & Interfaces, 2019; 11(29):26185-26193.), the addition of a plasticizer weakens the hydrogen bonding between the dopants PSS in the PEDOT: PSS, and further improves the tensile properties of the PEDOT: PSS, and the results show that the resistance change of the PEDOT: PSS using sorbitol as the plasticizer is more than 1 time of the initial resistance at 60% strain and more than 11 times of the initial resistance at 100% tensile strain.
So far, research on intrinsically stretchable conductive polymer materials has focused only on improving the flexibility of the dopant PSS in PEDOT: PSS, and does not really solve the problem of intrinsic rigidity of the conductive polymer. More importantly, the improved conductive polymer material coating is difficult to meet the requirements (strain 100%) of wearable devices or biomedical devices.
Disclosure of Invention
The invention aims to solve the problem that the resistance change of a conductive high polymer material coating of an intrinsic stretchable conductive material is too large when the strain is 100% in the prior art, and the requirement of a wearable device or a biomedical device is difficult to meet, and provides a polypyrrole coating with stretchability, and a preparation method and application thereof.
The stretchability of the polypyrrole coating is achieved by doping, and although the macromolecular dopants can increase the molecular chain gaps compared with the micromolecular dopants in the prior art, the stretchability of the polypyrrole coating is not applied. The document discloses that an ionic compound containing a sulfonic acid group or a plasticizer of an ionic liquid and sorbitol can enhance the tensile property of a conductive polymer (PEDOT: PSS), but the molecular structure of the PEDOT: PSS is that a flexible PSS long chain occupies the main body, a rigid conductive PEDOT chain occupies a small part, and the ionic compound containing the sulfonic acid group and the sorbitol are introduced to reduce the acting force (such as hydrogen bonds) between the PSS long chains so as to improve the flexibility. In general, materials that achieve intrinsic stretchability are largely divided into two categories: 1. the presence of flexible groups (dissipative strain energy), which is the method of document 1 inserting flexible molecular segments between rigid molecular chains; 2. there is movement of the molecular chains (bending of the molecular chains to straighten, or movement between molecular chains). The conductive coating is formed by blending a plasticizer (an ionic compound or an ionic liquid of a sulfonic group, sorbitol) and a molded (polymerized) conductive polymer material PEDOT: PSS. The plasticizer is used for weakening the interaction between PSS side chain groups and improving the mutual movement between polymer chains. The polypyrrole has only rigid polypyrrole chains, the polypyrrole molecular chains have no abundant side chain groups, and no action constraint such as hydrogen bonds or ionic bonds is generated among the molecular chains. This set of theoretical systems does not teach the design of stretchable polypyrrole coatings. The technical problem is solved through the combined action of doping of sodium sulfosalicylate and oxidation of ferric chloride, as shown in figure 1, the polypyrrole molecular chain is mostly of a linear structure due to the complexing action of the sodium sulfosalicylate and the ferric chloride, the introduction of the sodium sulfosalicylate increases the distance between the polypyrrole molecular chains, and the stretchability of the polypyrrole conductive coating is realized through the combined action of the two aspects.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of an intrinsic stretchable conductive polymer material comprises the steps of depositing polypyrrole on the surface of an elastic material by an in-situ polymerization method by taking sodium sulfosalicylate as a doping agent and ferric chloride as an oxidizing agent to prepare the intrinsic stretchable conductive polymer material, wherein the elongation at break of the elastic material is more than 100%;
the resistance change of the intrinsic stretchable conductive polymer material (i.e. the resistance value R and the initial resistance value R of the intrinsic stretchable conductive polymer material at the strain of 100%) is 100% (the strain represents the relative change of the length, which is the ratio of the deformation to the original length dimension)0A difference of (A), (B) R-R0) The intrinsic stretchable conductive polymer material is 1-2 times of the initial resistance (the resistance change amount of the intrinsic stretchable polymer conductive coating in the prior art is at least 10 times of the initial resistance when the strain is 100%, the resistance change amount of the intrinsic stretchable conductive polymer material in the invention is only 1-2 times of the initial resistance when the strain is 100%, which is far lower than that in the prior art), and the conductivity when the strain is 100% is 1-2.15 times of the initial conductivity (the conductivity of the stretchable intrinsic polymer conductive coating in the prior art is reduced when the strain is 100%, and the conductivity of the intrinsic stretchable conductive polymer material in the invention is not reduced but increased when the strain is 100%, which is caused by the rearrangement of the polypyrrole molecular chains.
Polypyrrole has received much attention because of its light weight, low cost, excellent electrical conductivity, and good biocompatibility. However, polypyrrole has very limited stretch properties due to its inherent rigidity, which greatly limits its use in stretchable electronics. Although blending of the conductive polymer with the flexible polymer or elastomer can improve the tensile properties of the composite, the conductivity of the soft polymer or elastomer is greatly reduced due to the insulating properties of the flexible polymer or elastomer. The deposition of an azole coating on the surface of a material is an effective strategy to ensure high conductivity. However, the mismatch of mechanical properties between the polypyrrole coating and the elastic material leads to cracking of the conductive coating during stretching of the polypyrrole coating material.
The invention prepares stretchable polypyrrole, and the principle of stretchability is as follows: the introduction of the doping agent sodium sulfosalicylate increases the molecular chain distance of the polypyrrole, and the increase of the molecular distance can weaken the interaction force between two molecular chains, so that the stretchability of the polypyrrole is improved. However, the increase in the intermolecular distance also leads to a decrease in the electrical conductivity, and the present invention is directed to the preparation of a polypyrrole coating having both stretchability and high electrical conductivity, therefore, the invention selects the sodium sulfosalicylate as the doping agent and selects the ferric chloride as the oxidant at the same time, the oxidant on one hand enables pyrrole monomers to be polymerized into polypyrrole, and complexation can be generated between ferric chloride and sodium sulfosalicylate (the complexation of the oxidant and the dopant is used for controlling the polymerization speed of the pyrrole monomers into the polypyrrole, so that the polypyrrole is mostly in a linear structure), the concentration of ferric ions in the solution is reduced, the polypyrrole peroxidation and crosslinking caused by too strong oxidizability are avoided, the reduction of the conductivity is avoided, in addition, the doping amount of the sodium sulfosalicylate is increased due to slow polymerization, the molecular distance is further increased, and the stretchability of the polypyrrole layer on the elastic material is further improved; at the same time, the increased doping level and the avoidance of peroxidation in the process will further increase the conductivity, and finally the result will not show a decrease or even an increase in conductivity.
As a preferred technical scheme:
the preparation method of the intrinsic stretchable conductive polymer material is characterized in that the in-situ polymerization method is a liquid phase polymerization method, and the preparation method comprises the following specific steps:
(1) immersing the elastic material into an aqueous solution of pyrrole monomer with the concentration of 4-20 wt% (preferably 12 wt%) for 0.5-6 h (preferably 1h), wherein the immersion bath ratio is not limited, and the immersion is ensured;
(2) transferring the product obtained in the step (1) into a solution containing ferric chloride and sodium sulfosalicylate to react for 1-12 h (preferably 8h) at room temperature, wherein the soaking bath ratio is not limited, and the product is immersed; too long reaction time can cause side reactions to increase (namely polypyrrole is over-oxidized, the crosslinking state of the polypyrrole is increased), the stretchability and the conductivity of the product are influenced, and too short reaction time can cause the polymerization degree and the coating thickness of the polypyrrole to be too small and the conductivity to be poor;
(3) and (3) washing the product obtained in the step (2) with deionized water for 1-5 times, and drying to obtain the intrinsic stretchable conductive polymer material.
The preparation method of the intrinsic stretchable conductive polymer material comprises the following steps that:
(1) immersing the elastic material into a solution containing ferric chloride and sodium sulfosalicylate for 0.5-6 h (preferably 1h), wherein the immersion bath ratio is not limited, and the immersion is ensured;
(2) fumigating the product in the step (1) for 1-24 h (preferably 12h) by using a pyrrole monomer, namely suspending the product in the step (1) above a pyrrole solution, and allowing the evaporated gaseous pyrrole monomer to rise to meet the in-situ polymerization of an oxidant and a dopant on the surface of the material; too long reaction time can cause side reactions to increase (namely polypyrrole is over-oxidized, the crosslinking state of the polypyrrole is increased), the stretchability and the conductivity of the product are influenced, and too short reaction time can cause the polymerization degree and the coating thickness of the polypyrrole to be too small and the conductivity to be poor;
(3) and (3) washing the product obtained in the step (2) with deionized water for 1-5 times, and drying to obtain the intrinsic stretchable conductive polymer material.
The method for preparing the intrinsic stretchable conductive polymer material comprises the steps of enabling the concentration of ferric chloride in a solution containing ferric chloride and sodium sulfosalicylate to be 4-12 wt% (preferably 10 wt%), and enabling the molar ratio of the ferric chloride to the sodium sulfosalicylate to be 0.5-4: 1 (preferably 1: 1).
In the preparation method of the intrinsic stretchable conductive polymer material, the elastic material is a one-dimensional fiber material, a two-dimensional film material or a three-dimensional material.
In the preparation method of the intrinsic stretchable conductive polymer material, the elastic material is made of polyurethane, polycaprolactone, polydimethylsiloxane or rubber.
The invention also provides an intrinsic stretchable conductive high polymer material prepared by the preparation method, which consists of an elastic material matrix and a polypyrrole coating doped with sodium sulfosalicylate, wherein an alpha carbon peak in a C1s peak in an XPS spectrogram of the polypyrrole coating doped with sodium sulfosalicylate accounts for less than 45% of the total carbon peak area, so that a polypyrrole chain is mostly in a linear form.
As a preferred technical scheme:
the intrinsic stretchable conductive polymer material has an initial resistance (i.e., resistance of the intrinsic stretchable conductive polymer material in an initial state when it is not stretched) of 1 to 100k Ω/cm, and an initial conductivity (i.e., conductivity of the intrinsic stretchable conductive polymer material in an initial state when it is not stretched) of 1 to 1000S/m.
According to the intrinsic stretchable conductive polymer material, when the strain of the intrinsic stretchable conductive polymer material is 70-100%, the polypyrrole coating starts to crack.
The present invention also provides the use of an intrinsically stretchable conductive polymer material as described above as a stretchable electronic circuit for flexible electronic devices (including many parts of power supplies, sensors, stretchable electronic circuits, displays, etc.) or as an electrode for flexible supercapacitors;
the invention also provides the application of the intrinsic stretchable conductive polymer material, the intrinsic stretchable conductive polymer material is stretched and then the stretching force is removed to prepare the wrinkled conductive polymer material, wherein the stretching multiple is 1.2 to (1+ x), and x is the elongation at break of the polypyrrole coating in the intrinsic stretchable conductive polymer material (namely the strain when the polypyrrole coating in the intrinsic stretchable conductive polymer material begins to crack).
In the prior art, the conductive stability of the material under large deformation is usually realized by constructing a fold structure, the fold structure is mainly characterized in that a fold-shaped conductive coating is gradually flattened in the stretching process, the resistance is almost unchanged in the process, and the intrinsic stretching behavior can be avoided. At present, in the prior art, a conductive material is coated on a substrate in a stretching state, and then stretching strain is released to obtain a corrugated conductive coating, and the finishing process of pre-stretching is limited by the size of pre-stretching equipment and is difficult to continuously produce, so that the wide application of the corrugated conductive material is greatly limited. The invention prepares the wrinkled conductive polymer material on the basis of preparing the intrinsic stretchable conductive polymer material, solves the problem of difficult continuous production in the prior art, and has the wrinkle forming principle as follows: the elastic material matrix and the polypyrrole coating doped with the sodium sulfosalicylate are synchronously drawn, the elastic material matrix shows recoverable plastic deformation, the polypyrrole coating doped with the sodium sulfosalicylate shows unrecoverable plastic deformation, and after the drawing force is removed, the polypyrrole coating doped with the sodium sulfosalicylate, which can not be restored, is compressed into folds under the action of the resilience force of the elastic material matrix.
As a preferred technical scheme:
according to the application, the drafting mechanism is adopted for drafting, the drafting mechanism comprises a front roller and a rear roller, the drafting multiple is the ratio of the rotating speed of the front roller to the rotating speed of the rear roller, and the rotating speed of the front roller is 50-400 rpm.
In the above-mentioned application, the initial resistance of the corrugated conductive polymer material (i.e. the resistance of the corrugated conductive polymer material in the initial state when the corrugated conductive polymer material is not stretched) is 1.1 to 140k Ω/cm, the initial conductivity (i.e. the conductivity of the corrugated conductive polymer material in the initial state when the corrugated conductive polymer material is not stretched) is 0.7 to 900S/m, the resistance change amount when the strain is 50% (i.e. the difference between the resistance value of the corrugated conductive polymer material when the strain is 50% and the initial resistance value) is less than 0.2 times of the initial resistance, and the conductivity when the strain is 50% is 1 to 2.17 times of the initial conductivity.
Has the advantages that:
(1) the polypyrrole-based conductive coating of the intrinsic stretchable conductive polymer material has high conductivity and good stretchability;
(2) according to the preparation method of the intrinsic stretchable conductive polymer material, sodium sulfosalicylate is used as a doping agent, and ferric chloride is used as an oxidizing agent, so that the high conductivity of the polypyrrole coating is ensured, and the molecular chain spacing of polypyrrole is increased, so that the stretchability of the polypyrrole coating is improved;
(3) the corrugated conductive polymer material obtained by the application of the invention can be continuously produced, thereby avoiding the limitation that the pre-drafting process cannot be continuously prepared;
(4) the corrugated conductive polymer material obtained by the application of the invention can keep good conductive performance under 50% of tensile strain.
Drawings
FIG. 1 is a schematic diagram of the stretching property mechanism of the intrinsically stretchable conductive polymer material of the present invention;
FIG. 2 is an electron micrograph of an intrinsically stretchable conductive polymer material of example 4;
FIG. 3 is a graph showing the relative resistance change of the intrinsically stretchable conductive polymer material of example 1 and the conductive polymer material of comparative example 1 under stretching motion;
FIG. 4 is a graph showing the change in conductivity of the intrinsically stretchable conductive polymer material of example 1 and the conductive polymer material of comparative example 1 under stretching motion;
FIG. 5 is XPS charts of an intrinsically stretchable conductive polymer material of example 1 and a conductive polymer material of comparative example 1;
FIG. 6 is a graph showing the relative resistance change of the intrinsically stretchable conductive polymer material of example 1 and the conductive polymer material of comparative example 2 under stretching motion;
FIG. 7 is a graph showing the change in conductivity of the intrinsically stretchable conductive polymer material of example 1 and the conductive polymer material of comparative example 2 under stretching motion;
FIG. 8 is a flowchart of a process of making the intrinsically stretchable conductive polymer material into the corrugated conductive polymer material according to example 1;
FIG. 9 is an electron microscope image of the corrugated conductive polymer material prepared from the intrinsically stretchable conductive polymer material of example 1;
FIG. 10 is an electron microscope image of the intrinsically stretchable conductive polymer material of example 1;
FIG. 11 is a graph showing the relative resistance changes of the intrinsically stretchable conductive polymer material and the prepared corrugated conductive polymer material under stretching motion in example 1;
wherein, 1-basal body, 2-coating, 3-front roller and 4-back roller.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of an intrinsic stretchable conductive polymer material comprises the following specific steps:
(1) immersing the elastic material in an aqueous solution of pyrrole monomer with the concentration of 6 wt% for 2 h; the elastic material is a one-dimensional fiber material, the material is rubber, and the elongation at break is 1000%;
(2) transferring the product obtained in the step (1) into a mixed aqueous solution of ferric chloride and sodium sulfosalicylate to react for 8 hours at room temperature; the concentration of ferric chloride in the mixed aqueous solution of ferric chloride and sodium sulfosalicylate is 8 wt%, and the molar ratio of ferric chloride to sodium sulfosalicylate is 0.5: 1;
(3) and (3) washing the product obtained in the step (2) with deionized water for 3 times, and drying to obtain the intrinsic stretchable conductive polymer material.
The prepared intrinsic stretchable conductive high polymer material consists of a rubber substrate and a polypyrrole coating doped with sodium sulfosalicylate, wherein an alpha carbon peak in a C1s peak in an XPS spectrum of the polypyrrole coating doped with sodium sulfosalicylate accounts for 38.31% of the total carbon peak area; the intrinsically stretchable conductive polymer material is shown in fig. 10; the intrinsic stretchable conductive polymer material has an initial resistance of 1k omega/cm and an initial conductivity of 900S/m; the polypyrrole coating starts to crack when the strain of the intrinsic stretchable conductive polymer material is 100%, the resistance change amount at the strain of 100% is 1 time of the initial resistance, and the conductivity at the strain of 100% is 2 times of the initial conductivity.
Application 1: the intrinsically stretchable conductive polymer material is used as a stretchable electronic circuit of a flexible electronic device.
Application 2: as shown in fig. 8, a drafting mechanism comprising a front roller 3 and a back roller 4 is used to draft the intrinsic stretchable conductive polymer material (composed of the substrate 1 and the coating 2), and then the drafting force is removed, so as to obtain the corrugated conductive polymer material, wherein an electron microscope image of the corrugated conductive polymer material is shown in fig. 9; wherein the drafting multiple is the ratio of the rotating speed of the front roller to the rotating speed of the rear roller, and is 1.7, and the rotating speed of the front roller is 50 rpm.
The initial resistance of the prepared wrinkled conductive polymer material is 1.1k omega/cm, the initial conductivity is 820S/m, the resistance variation amount is 0.035 times of the initial resistance when the strain is 50%, and the conductivity is 2.17 times of the initial conductivity when the strain is 50%.
As shown in fig. 11, compared with the intrinsic stretchable conductive polymer material, under 50% stretching strain, the relative resistance change of the conductive polymer material is only 3.5%, while under 50% stretching strain, the relative resistance change of the intrinsic stretchable conductive polymer material exceeds 25%, because the conductive polymer material is mainly flattened by the conductive coating in the initial stretching stage, which avoids the larger resistance change caused by the intrinsic stretching behavior.
Comparative example 1
A method for preparing a conductive polymer material, which is substantially the same as example 1, except that the aqueous solution in step (2) does not contain sodium sulfosalicylate.
The prepared conductive polymer material consists of a rubber substrate and a polypyrrole coating, and an alpha carbon peak in a C1s peak in an XPS spectrogram of the polypyrrole coating accounts for 46.26% of the total carbon peak area; the initial resistance is 10k omega/cm, and the initial conductivity is 110S/m; the polypyrrole coating starts to crack when the strain of the conductive polymer material is 5%, the resistance change amount is 10 times of the initial resistance when the strain is 20%, and the conductivity is 0.51 times of the initial conductivity when the strain is 10%.
As shown in fig. 3, the amount of resistance change of comparative example 1 at 100% strain was much more than example 1 by a factor of the initial resistance; as shown in fig. 4, the electrical conductivity of comparative example 1 began to decrease significantly after exceeding 7% strain, while the electrical conductivity of example 1 did not have a tendency to decrease within 100% strain because the addition of sodium sulfosalicylate in example 1 imparted the polypyrrole coating with high tensile properties, resulting in no drastic increase in the electrical conductivity during the tensile process due to cracking of the conductive coating; as shown in fig. 5, the XPS spectrum of comparative example 1 showed that the area of the total carbon peak occupied by the α carbon peak in the C1s peak was much higher than that of example 1, indicating that the addition of sodium sulfosalicylate in example 1 promoted the polypyrrole molecular chains to have a more linear structure.
Comparative example 2
A method for preparing a conductive polymer material, which is substantially the same as that in example 1, except that the oxidant in the aqueous solution in the step (2) is ammonium persulfate instead of ferric chloride.
The prepared conductive polymer material consists of a rubber substrate and a polypyrrole coating doped with sodium sulfosalicylate, wherein an alpha carbon peak in a C1s peak in an XPS spectrogram of the polypyrrole coating doped with sodium sulfosalicylate accounts for 45.94% of the total carbon peak area; the intrinsic stretchable conductive polymer material has an initial resistance of 6k omega/cm and an initial conductivity of 300S/m; the polypyrrole coating starts to crack at a strain of 7%, the amount of change in resistance at 20% strain is 40 times the initial resistance, and the electrical conductivity at 10% strain is 0.89 times the initial electrical conductivity.
As shown in fig. 6, the amount of resistance change of comparative example 2 at 100% strain was much more than example 1 by a factor of the initial resistance; as shown in fig. 7, the conductivity of comparative example 2 began to decrease significantly after exceeding 10% strain, while the conductivity of example 1 did not tend to decrease within 100% strain because there was no complexation between ammonium persulfate and sodium sulfosalicylate, and thus polypyrrole peroxidation and crosslinking due to strong oxidizing property could not be avoided.
Example 2
A preparation method of an intrinsic stretchable conductive polymer material comprises the following specific steps:
(1) immersing the elastic material in an aqueous solution of pyrrole monomer with the concentration of 12 wt% for 1 h; the elastic material is a three-dimensional material, the material is polyurethane, and the elongation at break is 800%;
(2) transferring the product obtained in the step (1) into a mixed aqueous solution of ferric chloride and sodium sulfosalicylate to react for 16h at room temperature; the concentration of ferric chloride in the mixed aqueous solution of ferric chloride and sodium sulfosalicylate is 12 wt%, and the molar ratio of ferric chloride to sodium sulfosalicylate is 4: 1;
(3) and (3) washing the product obtained in the step (2) with deionized water for 5 times, and drying to obtain the intrinsic stretchable conductive polymer material.
The prepared intrinsic stretchable conductive high polymer material consists of a polyurethane matrix and a polypyrrole coating doped with sodium sulfosalicylate, wherein an alpha carbon peak in a C1s peak in an XPS spectrum of the polypyrrole coating doped with sodium sulfosalicylate accounts for 44.5% of the total carbon peak area; the intrinsic stretchable conductive polymer material has an initial resistance of 10k omega/cm and an initial conductivity of 100S/m; the polypyrrole coating starts to crack when the strain of the intrinsic stretchable conductive polymer material is 70%, the resistance change amount is 2 times of the initial resistance when the strain is 100%, and the conductivity is 1 time of the initial conductivity when the strain is 100%.
Application 1: the intrinsically stretchable conductive polymer material is used as an electrode of a flexible supercapacitor.
Application 2: drafting the intrinsic stretchable conductive polymer material by adopting a drafting mechanism comprising a front roller and a rear roller, and then removing the drafting force to prepare a corrugated conductive polymer material; wherein the drafting multiple is the ratio of the rotating speed of the front roller to the rotating speed of the rear roller, and is 1.3, and the rotating speed of the front roller is 70 rpm.
The prepared wrinkled conductive polymer material has the initial resistance of 16k omega/cm, the initial conductivity of 63S/m, the resistance change amount of 50% of strain is 0.15 times of the initial resistance, and the conductivity of 50% of strain is 1.5 times of the initial conductivity.
Example 3
A preparation method of an intrinsic stretchable conductive polymer material comprises the following specific steps:
(1) immersing the elastic material in an aqueous solution of pyrrole monomer with the concentration of 18 wt% for 6 h; the elastic material is a three-dimensional material, the material is polydimethylsiloxane, and the elongation at break is 500%;
(2) transferring the product obtained in the step (1) into a mixed aqueous solution of ferric chloride and sodium sulfosalicylate to react for 12 hours at room temperature; the concentration of ferric chloride in the mixed aqueous solution of ferric chloride and sodium sulfosalicylate is 10 wt%, and the molar ratio of the ferric chloride to the sodium sulfosalicylate is 2: 1;
(3) and (3) washing the product obtained in the step (2) with deionized water for 4 times, and drying to obtain the intrinsic stretchable conductive polymer material.
The prepared intrinsic stretchable conductive high polymer material consists of a polydimethylsiloxane substrate and a polypyrrole coating doped with sodium sulfosalicylate, wherein an alpha carbon peak in a C1s peak in an XPS spectrum of the polypyrrole coating doped with sodium sulfosalicylate accounts for 42% of the total carbon peak area; the intrinsic stretchable conductive polymer material has an initial resistance of 1k omega/cm and an initial conductivity of 10S/m; the polypyrrole coating starts to crack when the strain of the intrinsic stretchable conductive polymer material is 80%, the resistance change amount at the strain of 100% is 1.2 times of the initial resistance, and the conductivity at the strain of 100% is 1.5 times of the initial conductivity.
Application 1: the intrinsically stretchable conductive polymer material is used as a stretchable electronic circuit of a flexible electronic device.
Application 2: drafting the intrinsic stretchable conductive polymer material by adopting a drafting mechanism comprising a front roller and a rear roller, and then removing the drafting force to prepare a corrugated conductive polymer material; wherein the drafting multiple is the ratio of the rotating speed of the front roller to the rotating speed of the rear roller, and is 1.5, and the rotating speed of the front roller is 80 rpm.
The initial resistance of the prepared wrinkled conductive polymer material is 1.6k omega/cm, the initial conductivity is 6.25S/m, the resistance change amount is 0.14 times of the initial resistance when the strain is 50%, and the conductivity is 1.9 times of the initial conductivity when the strain is 50%.
Example 4
A preparation method of an intrinsic stretchable conductive polymer material comprises the following specific steps:
(1) immersing the elastic material in a mixed aqueous solution of ferric chloride and sodium sulfosalicylate for 4 hours; the elastic material is a one-dimensional fiber material, the material is polycaprolactone, and the elongation at break is 300%; the concentration of ferric chloride in the mixed aqueous solution of ferric chloride and sodium sulfosalicylate is 10 wt%, and the molar ratio of the ferric chloride to the sodium sulfosalicylate is 1: 1;
(2) fumigating the product of step (1) with pyrrole monomer for 2 h;
(3) and (3) washing the product obtained in the step (2) with deionized water for 1 time, and drying to obtain the intrinsic stretchable conductive polymer material.
The prepared intrinsic stretchable conductive polymer material consists of a polycaprolactone matrix and a polypyrrole coating doped with sodium sulfosalicylate, as shown in figure 2, the polypyrrole coating forms a rough coating on the surface of a fiber, and an alpha carbon peak in a C1s peak in an XPS spectrogram of the polypyrrole coating doped with sodium sulfosalicylate accounts for 43.1% of the total carbon peak area; the intrinsic stretchable conductive polymer material has an initial resistance of 40k omega/cm and an initial conductivity of 200S/m; the polypyrrole coating began to crack when the strain of the intrinsic stretchable conductive polymer material was 76%, the amount of change in resistance at 100% strain was 1.8 times the initial resistance, and the electrical conductivity at 100% strain was 1.3 times the initial electrical conductivity.
Application 1: the intrinsically stretchable conductive polymer material is used as a stretchable electronic circuit of a flexible electronic device.
Application 2: drafting the intrinsic stretchable conductive polymer material by adopting a drafting mechanism comprising a front roller and a rear roller, and then removing the drafting force to prepare a corrugated conductive polymer material; wherein the drafting multiple is the ratio of the rotating speed of the front roller to the rotating speed of the rear roller, and is 1.6, and the rotating speed of the front roller is 100 rpm.
The prepared wrinkled conductive polymer material has initial resistance of 70 kOmega/cm, initial conductivity of 114S/m, resistance variation of 0.1 times of the initial resistance when the strain is 50%, and conductivity of 2 times of the initial conductivity when the strain is 50%.
Example 5
A preparation method of an intrinsic stretchable conductive polymer material comprises the following specific steps:
(1) immersing the elastic material in a mixed aqueous solution of ferric chloride and sodium sulfosalicylate for 0.5 h; the elastic material is a two-dimensional film material, the material is polydimethylsiloxane, and the elongation at break is 1000%; the concentration of ferric chloride in the mixed aqueous solution of ferric chloride and sodium sulfosalicylate is 4 wt%, and the molar ratio of ferric chloride to sodium sulfosalicylate is 2: 1;
(2) fumigating the product of step (1) with pyrrole monomer for 1 h;
(3) and (3) washing the product obtained in the step (2) with deionized water for 3 times, and drying to obtain the intrinsic stretchable conductive polymer material.
The prepared intrinsic stretchable conductive high polymer material consists of a polydimethylsiloxane substrate and a polypyrrole coating doped with sodium sulfosalicylate, wherein an alpha carbon peak in a C1s peak in an XPS spectrum of the polypyrrole coating doped with sodium sulfosalicylate accounts for 39% of the total carbon peak area; the intrinsic stretchable conductive polymer material has an initial resistance of 100k omega/cm and an initial conductivity of 3S/m; the polypyrrole coating starts to crack when the strain of the intrinsic stretchable conductive polymer material is 100%, the resistance change amount at the strain of 100% is 1.1 times of the initial resistance, and the conductivity at the strain of 100% is 1.9 times of the initial conductivity.
Application 1: the intrinsically stretchable conductive polymer material is used as an electrode of a flexible supercapacitor.
Application 2: drafting the intrinsic stretchable conductive polymer material by adopting a drafting mechanism comprising a front roller and a rear roller, and then removing the drafting force to prepare a corrugated conductive polymer material; wherein, the drafting multiple is the ratio of the rotating speed of the front roller to the rotating speed of the back roller, is 2, and the rotating speed of the front roller is 400 rpm.
The prepared wrinkled conductive polymer material has the initial resistance of 140k omega/cm, the initial conductivity of 2.1S/m, the resistance variation amount of 50% of strain is 0.06 times of the initial resistance, and the conductivity of 50% of strain is 2.1 times of the initial conductivity.
Example 6
A preparation method of an intrinsic stretchable conductive polymer material comprises the following specific steps:
(1) immersing the elastic material in a mixed aqueous solution of ferric chloride and sodium sulfosalicylate for 6 hours; the elastic material is a three-dimensional material, the material is rubber, and the elongation at break is 1600%; the concentration of ferric chloride in the mixed aqueous solution of ferric chloride and sodium sulfosalicylate is 12 wt%, and the molar ratio of ferric chloride to sodium sulfosalicylate is 3: 1;
(2) fumigating the product of step (1) with pyrrole monomer for 24 h;
(3) and (3) washing the product obtained in the step (2) with deionized water for 5 times, and drying to obtain the intrinsic stretchable conductive polymer material.
The prepared intrinsic stretchable conductive high polymer material consists of a rubber substrate and a polypyrrole coating doped with sodium sulfosalicylate, wherein an alpha carbon peak in a C1s peak in an XPS spectrum of the polypyrrole coating doped with sodium sulfosalicylate accounts for 44.7% of the total carbon peak area; the intrinsic stretchable conductive polymer material has an initial resistance of 5k omega/cm and an initial conductivity of 15S/m; the polypyrrole coating starts to crack when the strain of the intrinsic stretchable conductive polymer material is 70%, the resistance change amount is 1.9 times of the initial resistance when the strain is 100%, and the conductivity is 1.1 times of the initial conductivity when the strain is 100%.
Application 1: the intrinsically stretchable conductive polymer material is used as a stretchable electronic circuit of a flexible electronic device.
Application 2: drafting the intrinsic stretchable conductive polymer material by adopting a drafting mechanism comprising a front roller and a rear roller, and then removing the drafting force to prepare a corrugated conductive polymer material; wherein the drafting multiple is the ratio of the rotating speed of the front roller to the rotating speed of the back roller, and is 1.6, and the rotating speed of the front roller is 250 rpm.
The prepared wrinkled conductive polymer material has initial resistance of 7k omega/cm and initial conductivity of 10S/m, the resistance change amount is 0.08 times of the initial resistance when the strain is 50%, and the conductivity is 2 times of the initial conductivity when the strain is 50%.
Example 7
A preparation method of an intrinsic stretchable conductive polymer material comprises the following specific steps:
(1) immersing the elastic material in a mixed aqueous solution of ferric chloride and sodium sulfosalicylate for 6.5 h; the elastic material is a three-dimensional material, the material is rubber, and the elongation at break is 1600%; the concentration of ferric chloride in the mixed aqueous solution of ferric chloride and sodium sulfosalicylate is 13 wt%, and the molar ratio of ferric chloride to sodium sulfosalicylate is 3.5: 1;
(2) fumigating the product of step (1) with pyrrole monomer for 25 h;
(3) and (3) washing the product obtained in the step (2) with deionized water for 6 times, and drying to obtain the intrinsic stretchable conductive polymer material.
The prepared intrinsic stretchable conductive high polymer material consists of a rubber substrate and a polypyrrole coating doped with sodium sulfosalicylate, wherein an alpha carbon peak in a C1s peak in an XPS spectrum of the polypyrrole coating doped with sodium sulfosalicylate accounts for 45.0% of the total carbon peak area; the intrinsic stretchable conductive polymer material has an initial resistance of 6k omega/cm and an initial conductivity of 10S/m; the polypyrrole coating began to crack when the strain of the intrinsic stretchable conductive polymer material was 68%, the amount of change in resistance at 100% strain was 2.0 times the initial resistance, and the conductivity at 100% strain was 0.9 times the initial conductivity.
Application 1: the intrinsically stretchable conductive polymer material is used as a stretchable electronic circuit of a flexible electronic device.
Application 2: drafting the intrinsic stretchable conductive polymer material by adopting a drafting mechanism comprising a front roller and a rear roller, and then removing the drafting force to prepare a corrugated conductive polymer material; wherein the drafting multiple is the ratio of the rotating speed of the front roller to the rotating speed of the back roller, and is 1.68, and the rotating speed of the front roller is 410 rpm.
The initial resistance of the prepared wrinkled conductive polymer material is 11k omega/cm, the initial conductivity is 5S/m, the resistance variation amount is 0.14 times of the initial resistance when the strain is 50%, and the conductivity is 1.9 times of the initial conductivity when the strain is 50%.

Claims (10)

1. A preparation method of an intrinsic stretchable conductive polymer material is characterized in that polypyrrole is deposited on the surface of an elastic material by an in-situ polymerization method by taking sodium sulfosalicylate as a doping agent and ferric chloride as an oxidizing agent to prepare the intrinsic stretchable conductive polymer material, wherein the elongation at break of the elastic material is more than 100%;
the intrinsic stretchable conductive polymer material has a resistance variation amount of 1 to 2 times of an initial resistance when the strain is 100%, and an electrical conductivity of 1 to 2.15 times of the initial electrical conductivity when the strain is 100%.
2. The method for preparing an intrinsically stretchable conductive polymer material as claimed in claim 1, wherein the in-situ polymerization method is a liquid phase polymerization method, and comprises the following steps:
(1) immersing the elastic material into an aqueous solution of pyrrole monomer with the concentration of 4-20 wt% for 0.5-6 h;
(2) transferring the product obtained in the step (1) into a solution containing ferric chloride and sodium sulfosalicylate to react for 1-12 h;
(3) and (3) washing the product obtained in the step (2) with deionized water, and drying to obtain the intrinsic stretchable conductive polymer material.
3. The method for preparing an intrinsically stretchable conductive polymer material as claimed in claim 1, wherein the in-situ polymerization method is a gas phase polymerization method, and comprises the following steps:
(1) immersing the elastic material into a solution containing ferric chloride and sodium sulfosalicylate for 0.5-6 h;
(2) fumigating the product in the step (1) for 1-24 h by using a pyrrole monomer;
(3) and (3) washing the product obtained in the step (2) with deionized water, and drying to obtain the intrinsic stretchable conductive polymer material.
4. The method as claimed in claim 2 or 3, wherein the concentration of ferric chloride in the solution containing ferric chloride and sodium sulfosalicylate is 4-12 wt%, and the molar ratio of ferric chloride to sodium sulfosalicylate is 0.5-4: 1.
5. The intrinsically stretchable conductive polymer material prepared by the preparation method of any one of claims 1 to 4, which consists of an elastic material matrix and a polypyrrole coating doped with sodium sulfosalicylate, wherein an alpha carbon peak in a C1s peak in an XPS spectrum of the polypyrrole coating doped with sodium sulfosalicylate accounts for less than 45% of the total carbon peak area.
6. The intrinsically stretchable conductive polymer material as claimed in claim 5, wherein the polypyrrole coating starts to crack when the strain of the intrinsically stretchable conductive polymer material is 70 to 100%.
7. Use of an intrinsically stretchable conductive polymer material as claimed in claim 5 or 6, wherein the intrinsically stretchable conductive polymer material is used as a stretchable electronic circuit of a flexible electronic device or as an electrode of a flexible supercapacitor.
8. The use of the intrinsically stretchable conductive polymer material according to claim 5 or 6, wherein the intrinsic stretchable conductive polymer material is stretched to remove the stretching force to obtain the wrinkled conductive polymer material, wherein the stretching ratio is 1.2 to (1+ x), and x is the elongation at break of the polypyrrole coating in the intrinsically stretchable conductive polymer material.
9. The application of claim 8, wherein the drafting is performed by a drafting mechanism, the drafting mechanism comprises a front roller and a rear roller, the drafting multiple is the ratio of the rotating speed of the front roller to the rotating speed of the rear roller, and the rotating speed of the front roller is 50-400 rpm.
10. The use according to claim 9, wherein the corrugated conductive polymer material has an initial resistance of 1.1 to 140k Ω/cm, an initial conductivity of 0.7 to 900S/m, a resistance change amount of 50% strain of 0.2 times or less of the initial resistance, and a conductivity of 50% strain of 1 to 2.17 times of the initial conductivity.
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