Graded porous conductive polymer, preparation method and application thereof

Abstract

The invention discloses a graded porous conductive polymer and a preparation method and application thereof, pyrrole / aniline / thiophene is used as a raw material, a ferric trichloride aqueous solution is added, freeze drying is performed, washing and drying are performed after low-temperature treatment in an air atmosphere, and the graded porous conductive polymer is obtained and has dual functions. The composite material is used as an active material and is combined with a gel electrolyte to assemble a micro supercapacitor. The composite material is used as a sensing material to construct a pressure, gas or humidity sensor. A miniature supercapacitor and a sensor are subjected to coplanar integration, and self-powered and flexible wearable application is realized. The system is low in interface resistance, high in electron transmission efficiency, simplified in integration process, reduced in overall size, reduced in preparation cost and difficulty, capable of meeting the small-size and light-weight development requirements of electronic equipment and excellent in performance.

Description

Technical Field

[0001] This invention belongs to the field of energy storage-sensing system preparation technology, specifically relating to a conductive polymer, its preparation method, and its energy storage and sensing applications. Background Technology

[0002] With the rapid development of portable electronic products, smart wearable devices, implantable medical devices, and self-powered microsystems, there is an urgent need to develop matching micro energy storage devices and their integrated sensing systems. However, the currently reported micro energy storage device-sensor integrated systems use a wide variety of materials (including different electrode materials, sensing materials, current collectors, and conductive additives), leading to poor compatibility between energy storage and sensing elements and complex device connections, which seriously affects the overall performance of the integrated system.

[0003] Existing methods for preparing porous conductive polymer materials and energy storage devices include, for example, Chinese patent CN114497705 A, which reports an MXene / mesoporous polypyrrole composite material and its preparation method. This composite material uses MXene as a two-dimensional substrate and micelles of a nonionic surfactant, polyoxyethylene-polyoxypropylene ether block copolymer, as a mesoporous template to construct a mesoporous polypyrrole layer on the surface of the MXene sheets, forming a unique sandwich structure, which can be further applied in zinc-ion batteries or capacitors. Another Chinese patent, CN119419206 A, reports an energy storage device with a conductive polymer sponge and its intelligent monitoring system. The conductive polymer sponge is a porous network sponge prepared by in-situ chemical oxidative polymerization technology. Its three-dimensional structure increases the effective surface area of ​​the electrodes, improving electrochemical energy storage properties. The porous conductive polymer materials prepared in the above patents primarily function as energy storage devices but do not possess sensing capabilities.

[0004] Existing technologies for fabricating flexible sensors, such as those proposed in Chinese patent CN 117487298 B, employ supramolecular cyclodextrin, chain polymer polyvinyl alcohol, conductive polymer PEDOT, and MXene to create electrode materials through a cross-linking reaction. These are then combined with an electrolyte-containing dielectric layer to form a sandwich structure. The electrodes or dielectric layer are designed with raised microstructures to improve the pressure / stress detection accuracy, multi-directional force recognition capability, and capacitance change stability of the flexible sensor. Another example is Chinese patent CN118500586 A, which uses biomass and conductive nanomaterials as raw materials to prepare a biodegradable biomass-based pressure sensor. While the materials and devices in these patents possess sensing capabilities, they lack energy storage capacity. Furthermore, in constructing integrated energy storage-sensing microsystems, current strategies mostly combine energy storage batteries and sensors via external wires.

[0005] Most existing porous conductive polymer materials have only one pore size range (micropores, mesopores, or macropores), which can only achieve a single function, such as energy storage, and cannot meet the needs of electronic devices for multifunctional materials. Moreover, the fabrication of micro supercapacitor-sensor integrated microsystems often uses multiple active materials, which leads to process complexity and incompatibility, affects electron transmission efficiency, increases fabrication cost and difficulty, and is not conducive to the miniaturization and lightweight development of electronic devices. Summary of the Invention

[0006] To address the limitations of existing porous conductive polymer materials, such as their limited functionality and the complex fabrication processes required for integrating micro-supercapacitors and sensors into microsystems, this invention develops a class of multifunctional hierarchical porous conductive polymer materials. Through innovative structural and compositional design, these materials are endowed with dual energy storage and sensing properties, enabling synergistic energy storage and sensing functions within a single material system. Furthermore, high-performance integrated microsystems based on this material are constructed, achieving the integrated integration of micro-supercapacitors and sensors on a single flexible substrate. This meets the demands of modern electronic devices for multifunctional, miniaturized, and high-performance materials and multifunctional integrated microsystems.

[0007] To solve the above-mentioned technical problems, the present invention adopts the following technical solution: The multifunctional hierarchical porous conductive polymer described in this invention is used as a bifunctional active material for both micro supercapacitors and sensors to construct a coplanar integrated micro supercapacitor-pressure, gas, or humidity sensor microsystem, which is achieved through the following steps: Using pyrrole / aniline / thiophene as raw materials, an aqueous solution of ferric chloride is added, followed by freeze-drying, low-temperature treatment in air atmosphere, washing, and drying to obtain a hierarchical porous conductive polymer with bifunctional properties. This polymer is used as an active material, combined with a gel electrolyte, to assemble micro-supercapacitors. It is also used as a sensing material to construct pressure, gas, or humidity sensors. By coplanarly integrating the micro-supercapacitors and sensors, self-powered, flexible wearable applications can be realized.

[0008] The specific plan is as follows: A method for preparing a hierarchical porous conductive polymer, using polymer monomers as raw materials and ferric chloride (FeCl3) as a pore template and initiator, includes the following steps: adding polymer monomers to a reaction flask, then adding FeCl3 aqueous solution and stirring for 1-2 minutes, followed by freeze drying, then heat treatment in air, and finally washing and drying with acid solution to obtain a hierarchical porous conductive polymer.

[0009] As a preferred embodiment of the present invention, the polymer monomer is pyrrole, aniline or thiophene, the concentration of FeCl3 aqueous solution is 20-40 mg / mL, and the ratio of polymer monomer to ferric chloride is (30-70 μL): (0.1-0.2 g).

[0010] As a preferred embodiment of the present invention, the freeze-drying temperature is -30~-10℃ and the time is 6-12 h; the heat treatment temperature is 100-300℃ and the heat treatment time is 0.5-3 h.

[0011] As a preferred embodiment of the present invention, the acid solution is a hydrochloric acid solution or an acetic acid solution with a concentration of 0.2-2 mol / L, a drying temperature of 60-100℃, and a drying time of 2-10 h.

[0012] The present invention also provides a hierarchical porous conductive polymer prepared by the above preparation method. The hierarchical porous conductive polymer is composed of interconnected nanosheets and has a large number of macropores and mesopores, with a specific capacity >180 F / g and a cycle life >80% after 5000 cycles.

[0013] This invention also provides the application of the hierarchical porous conductive polymer in constructing a micro supercapacitor-pressure / gas / humidity sensor integrated microsystem, comprising the following steps: on a flexible substrate, using the hierarchical porous conductive polymer as the electrode active material, two planar interdigitated microelectrodes are constructed using mask-assisted filtration technology; one planar interdigitated microelectrode is coated with an ion gel electrolyte to construct a micro supercapacitor; the other planar interdigitated microelectrode is drop-coated with a sensing unit to construct a pressure / gas / humidity sensor; the micro supercapacitor and the pressure / gas / humidity sensor are assembled on the same flexible substrate to form a coplanar, flexible micro supercapacitor-pressure / gas / humidity sensor integrated microsystem, wherein the sensing unit of the pressure / gas / humidity sensor is made of the hierarchical porous conductive polymer.

[0014] The ion gel electrolyte is made of polyvinyl alcohol / sulfuric acid (PVA-H2SO4) or silicon dioxide / lithium chloride (SiO2-LiCl), with a coating thickness of 50 μm-1 mm; the flexible substrate is made of polytetrafluoroethylene, polyvinylidene fluoride or nylon filter membrane.

[0015] The specific construction method of the pressure / gas / humidity sensor is as follows: A conductive hydrogel is prepared by mixing hierarchical porous conductive polymer, PVA and borax in a mass ratio of 1:(50~100):5. This hydrogel is then coated onto a planar interdigitated microelectrode as the sensing unit of the pressure sensor, with a coating thickness of 50 μm-1 mm, to prepare the pressure sensor. 10~50 μL of an ethanol dispersion of hierarchical porous conductive polymer with a concentration of 0.5-2.0 mg / mL is drop-coated onto the planar interdigitated microelectrode, and after drying, an ammonia sensor is obtained. 0.1~1.0 mL of an aqueous dispersion of hierarchical porous conductive polymer with a concentration of 0.5-2.0 mg / mL is drop-coated onto the planar interdigitated microelectrode, and after drying, a humidity sensor is obtained.

[0016] The specific construction method of the coplanar, flexible micro supercapacitor-pressure / gas / humidity sensor integrated microsystem is as follows: On the same flexible substrate, with the assistance of an interdigitated mask, a dispersion of hierarchical porous conductive polymer with a concentration of 0.1-0.5 mg / mL is injected into each electrode. After filtration and drying, the mask is removed to obtain two microelectrodes. The corresponding ion gel electrolyte and the sensing unit of the pressure / gas / humidity sensor are then coated to obtain the micro supercapacitor and the corresponding sensor, forming a coplanar, flexible micro supercapacitor-pressure / gas / humidity sensor integrated microsystem.

[0017] Reaction mechanism: After mixing pyrrole / aniline / thiophene monomers with ferric chloride, the two are co-cured by freeze drying. Ferric chloride acts as both a polymerization initiator and a pore template, allowing the pyrrole / aniline / thiophene monomers to polymerize on the surface of ferric chloride crystals. The polymerization is further completed under an air atmosphere. The iron ions and iron oxide are removed by washing with an acid solution, resulting in a hierarchical porous conductive polymer.

[0018] The beneficial effects of this invention are as follows: This invention innovatively designs and prepares a class of multifunctional hierarchical porous conductive polymers and successfully constructs a micro-supercapacitor-pressure, gas, or humidity sensor integrated microsystem. The material's unique hierarchical porous structure can increase reactive sites, thereby achieving more efficient ion, molecular, and electron transport; furthermore, the coexistence of macropores and mesopores, due to its low elastic modulus, high porosity, large specific surface area, and fast mass transfer rate, can effectively improve the sensor's sensitivity.

[0019] This invention utilizes a porous conductive polymer material possessing both high electrochemical activity and excellent sensing performance to construct a micro-energy storage device-sensor integrated system on a single substrate. This material preparation method overcomes the shortcomings of existing porous material preparation methods, which are complex and have limited functionality. The prepared material exhibits a unique hierarchical porous structure and possesses both energy storage and sensing functions. It is used as the active material for a micro-supercapacitor-sensor integrated microsystem. This system exhibits low interfacial resistance, high electron transport efficiency, simplified integration process, reduced overall size, and lower manufacturing costs and difficulty, meeting the demands for miniaturization and lightweight electronic devices, and demonstrating superior performance. Applying the integrated pressure sensing microsystem patch to the throat allows for reliable recording and identification of various acoustic signals. The gas sensing microsystem and humidity sensing microsystem exhibit sensitive ammonia and humidity responses, respectively, under bending conditions, demonstrating the excellent flexibility and wireless monitoring capabilities of this integrated microsystem, showing promising application prospects. Attached Figure Description

[0020] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0021] Figure 1 This is a transmission electron microscope image of Example 1.

[0022] Figure 2 This is a transmission electron microscope image of Example 2.

[0023] Figure 3 The graph shows the electrochemical performance of Example 3.

[0024] Figure 4 This is a schematic diagram of the microelectrode in Application Example 1.

[0025] Figure 5 This is a physical diagram of the integrated microsystem used in Application Example 1.

[0026] Figure 6 The pressure sensing performance diagram is for the pressure sensing microsystem in Application Example 1.

[0027] Figure 7 The graph shows the ammonia sensing performance of the gas sensing microsystem in Application Example 2.

[0028] Figure 8 The diagram shows the humidity sensing performance of the humidity sensing microsystem in Application Example 3. Detailed Implementation

[0029] The present invention will be further described below with reference to specific embodiments. It should be understood that the following embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Those skilled in the art can make some non-essential improvements and adjustments based on the above-described invention.

[0030] Example 1 The preparation method of the hierarchical porous conductive polymer in this embodiment is as follows: 30 μL of aniline was added to the reaction flask, followed by 5 mL of FeCl3 aqueous solution (20 mg / mL) and stirred for 2 minutes; freeze-dried at -30℃ for 6 h, then treated in air at 100℃ for 3 h; finally washed with hydrochloric acid (0.5 mol / L) solution and dried at 60℃ for 10 h to obtain hierarchical porous polyaniline.

[0031] Depend on Figure 1 Transmission electron microscopy (TEM) images show that the hierarchical porous polyaniline is composed of interconnected nanosheets and possesses a large number of macropores and mesopores; three-electrode measurements show that at 1 A g... -1 At that time, the specific capacity was 425 F g. -1 After 5000 cycles, the capacity retention rate is ~86%, indicating excellent electrochemical performance.

[0032] Example 2 The preparation method of the hierarchical porous conductive polymer in this embodiment is as follows: 50 μL of pyrrole was added to the reaction flask, followed by 5 mL of FeCl3 aqueous solution (30 mg / mL) and stirred for 2 minutes; freeze-dried at -20℃ for 9 h, then treated in air at 200℃ for 1 h; finally washed with acetic acid (1.0 mol / L) solution and dried at 70℃ for 8 h to obtain hierarchical porous polypyrrole.

[0033] Depend on Figure 2 Transmission electron microscopy (TEM) images show that the hierarchical porous polypyrrole possesses an interconnected nanosheet structure of macropores and mesopores; three-electrode measurements at 0.5 A g... -1 At that time, the specific capacity was 368 F g. -1 After 5000 cycles, the capacity retention rate is ~92%.

[0034] Example 3 The preparation method of the hierarchical porous conductive polymer in this embodiment is as follows: 70 μL of thiophene was added to the reaction flask, followed by 5 mL of FeCl3 aqueous solution (40 mg / mL) and stirred for 2 minutes; freeze-dried at -10℃ for 12 h, then treated in air at 300℃ for 0.5 h; finally washed with hydrochloric acid (1.5 mol / L) solution and dried at 80℃ for 5 h to obtain hierarchical porous polythiophene.

[0035] Hierarchical porous polythiophene exhibits a structural feature of coexisting macropores and mesopores, and interconnected nanosheets; composed of Figure 3 The three-electrode performance test graph of the graded porous polythiophene shows that 0.2 A g -1 The specific capacity of GCD at that time was 188 F g. -1 After 5000 cycles, the capacity retention rate is ~95%.

[0036] Example 4 The preparation method of the hierarchical porous conductive polymer in this embodiment is as follows: 50 μL of aniline was added to the reaction flask, followed by 5 mL of FeCl3 aqueous solution (30 mg / mL) and stirred for 2 minutes; freeze-dried at -20℃ for 9 h, then treated in air at 200℃ for 1 h; finally washed with acetic acid (2.0 mol / L) solution and dried at 90℃ for 3 h to obtain hierarchical porous polyaniline.

[0037] Example 5 The preparation method of the hierarchical porous conductive polymer in this embodiment is as follows: 70 μL of aniline was added to the reaction flask, followed by 5 mL of FeCl3 aqueous solution (40 mg / mL) and stirred for 2 minutes; freeze-dried at -10℃ for 12 h, then treated in air at 300℃ for 0.5 h; finally washed with hydrochloric acid (0.3 mol / L) solution and dried at 100℃ for 2 h to obtain hierarchical porous polyaniline.

[0038] Example 6 The preparation method of the hierarchical porous conductive polymer in this embodiment is as follows: 30 μL of pyrrole was added to the reaction flask, followed by 5 mL of FeCl3 aqueous solution (20 mg / mL) and stirred for 2 minutes; freeze-dried at -30℃ for 6 h, then treated in air at 100℃ for 3 h; finally washed with hydrochloric acid (0.8 mol / L) solution and dried at 85℃ for 4 h to obtain hierarchical porous polypyrrole.

[0039] Example 7 The preparation method of the hierarchical porous conductive polymer in this embodiment is as follows: 70 μL of pyrrole was added to the reaction flask, followed by 5 mL of FeCl3 aqueous solution (40 mg / mL) and stirred for 2 minutes; freeze-dried at -10℃ for 12 h, then treated in air at 300℃ for 0.5 h; finally washed with hydrochloric acid (1.2 mol / L) solution and dried at 75℃ for 6 h to obtain hierarchical porous polypyrrole.

[0040] Example 8 The preparation method of the hierarchical porous conductive polymer in this embodiment is as follows: 30 μL of thiophene was added to the reaction flask, followed by 5 mL of FeCl3 aqueous solution (20 mg / mL) and stirring for 2 minutes; the mixture was freeze-dried at -30℃ for 6 h, then treated in air at 100℃ for 3 h; finally, it was washed with hydrochloric acid (1.6 mol / L) solution and dried at 65℃ for 9 h to obtain hierarchical porous polythiophene.

[0041] Example 9 The preparation method of the hierarchical porous conductive polymer in this embodiment is as follows: 50 μL of thiophene was added to the reaction flask, followed by 5 mL of FeCl3 aqueous solution (30 mg / mL) and stirred for 2 minutes; freeze-dried at -20℃ for 9 h, then treated in air at 200℃ for 1 h; finally washed with acetic acid (1.8 mol / L) solution and dried at 95℃ for 3 h to obtain hierarchical porous polythiophene.

[0042] Application Example 1 Construction of a micro-supercapacitor-pressure sensor integrated microsystem: Using hierarchical porous polyaniline prepared in Example 1 as the active material, an aqueous dispersion of hierarchical porous polyaniline at a concentration of 0.1 mg / mL was injected into each electrode on a polytetrafluoroethylene (PTFE) filter membrane with the aid of an interdigitated mask. After filtration and drying, the mask was removed, yielding two microelectrodes. One microelectrode was coated with an ionomer gel electrolyte PVA-H₂SO₄ (~100 μm) to prepare a micro-supercapacitor. A conductive hydrogel was prepared by mixing hierarchical porous polyaniline, PVA, and borax in a mass ratio of 1:70:5, serving as the sensing unit for the pressure sensor. This hydrogel was coated 100 μm thickly onto another hierarchical porous polyaniline microelectrode to prepare the pressure sensor. The micro-supercapacitor and pressure sensor were assembled on a PTFE filter membrane to form a coplanar, flexible micro-supercapacitor-pressure sensor integrated microsystem.

[0043] like Figure 4-6 As shown, a micro supercapacitor-pressure sensor integrated microsystem patch, when applied to the throat, can reliably record and identify various acoustic signals. It exhibits a fast and repeatable response at bending angles of 0-180°, demonstrating the excellent flexibility and wireless monitoring capabilities of the integrated microsystem.

[0044] Application Example 2 Construction of a micro-supercapacitor-gas sensor integrated microsystem: Using hierarchical porous polypyrrole prepared in Example 2 as the active material, an aqueous dispersion of hierarchical porous polypyrrole at a concentration of 0.2 mg / mL was injected into each electrode on a polyvinylidene fluoride (PVDF) filter membrane with the aid of an interdigitated mask. After filtration and drying, the mask was removed, yielding two microelectrodes. One microelectrode was coated with the ionogel electrolyte SiO2-LiCl (~500 μm) to prepare a micro-supercapacitor. 20 μL of an ethanol solution (1.0 mg / mL) of hierarchical porous polypyrrole was drop-coated onto the other hierarchical porous polypyrrole microelectrode, and after drying, an ammonia sensor was obtained. The micro-supercapacitor and ammonia sensor were assembled on a PVDF filter membrane to form a coplanar, flexible micro-supercapacitor-gas sensor integrated microsystem. Figure 7 As shown, the integrated microsystem, using a miniature supercapacitor as the power supply element, exhibited a response of 50% and 40% to 40 ppm and 30 ppm ammonia gas, respectively, at a 90° bending angle.

[0045] Application Example 3 Construction of a micro-supercapacitor-humidity sensor integrated microsystem: Using hierarchical porous polythiophene prepared in Example 3 as the active material, an aqueous dispersion of hierarchical porous polythiophene with a concentration of 0.3 mg / mL was injected into each electrode on a nylon filter membrane using an interdigitated mask. After filtration and drying, the mask was removed, resulting in two microelectrodes. Two planar interdigitated microelectrodes were constructed using mask-assisted filtration technology. One microelectrode was coated with the ionogel electrolyte SiO2-LiCl (~800 μm) to prepare a micro-supercapacitor. 0.5 mL of an aqueous solution of hierarchical porous polythiophene (1.0 mg / mL) was drop-coated onto the other microelectrode, and after drying, a humidity sensor was obtained. The micro-supercapacitor and humidity sensor were assembled on a nylon filter membrane to form a coplanar, flexible micro-supercapacitor-humidity sensor integrated microsystem. Figure 8 As shown, the integrated microsystem uses a miniature supercapacitor as a power supply element and exhibits a sensitive and stable response under humidity conditions of 40%-80%.

[0046] The foregoing has shown and described the basic principles and main features of the present invention, as well as its advantages. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of this invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a hierarchical porous conductive polymer, characterized in that, Using polymer monomers as raw materials and ferric chloride (FeCl3) as a pore template and initiator, the process includes the following steps: adding polymer monomers to a reaction flask, then adding FeCl3 aqueous solution, stirring, freeze-drying, then heat-treating in air, and finally washing and drying with acid solution to obtain a hierarchical porous conductive polymer.

2. The method for preparing the hierarchical porous conductive polymer according to claim 1, characterized in that: The polymer monomers are pyrrole, aniline or thiophene, and the concentration of FeCl3 aqueous solution is 20-40 mg / mL.

3. The method for preparing the hierarchical porous conductive polymer according to claim 1, characterized in that: The ratio of polymer monomer to ferric chloride is (30-70 μL): (0.1-0.2 g).

4. The method for preparing the hierarchical porous conductive polymer according to claim 1, characterized in that: The stirring time is 1-2 min, the freeze-drying temperature is -30~-10℃, and the time is 6-12 h; the heat treatment temperature is 100-300℃, and the heat treatment time is 0.5-3 h.

5. The method for preparing the hierarchical porous conductive polymer according to claim 1, characterized in that: The acid solution is a hydrochloric acid solution or an acetic acid solution with a concentration of 0.2-2 mol / L, a drying temperature of 60-100℃, and a drying time of 2-10 h.

6. The hierarchical porous conductive polymer prepared by any one of claims 1-5, characterized in that: The hierarchical porous conductive polymer is composed of interconnected nanosheets and has a large number of macropores and mesopores, with a specific capacity >180 F / g and a cycle life >80% after 5000 cycles.

7. The application of the hierarchical porous conductive polymer as described in claim 6 in constructing a micro supercapacitor-pressure / gas / humidity sensor integrated microsystem, characterized in that... Includes the following steps: On a flexible substrate, a hierarchical porous conductive polymer is used as the electrode active material. Two planar interdigitated microelectrodes are constructed using mask-assisted filtration technology. One planar interdigitated microelectrode is coated with an ion gel electrolyte to construct a micro supercapacitor; the other planar interdigitated microelectrode is drop-coated with a sensing unit to construct a pressure / gas / humidity sensor. A coplanar, flexible micro supercapacitor-pressure / gas / humidity sensor integrated microsystem is formed by assembling a micro supercapacitor and a pressure / gas / humidity sensor on the same flexible substrate. The sensing unit of the pressure / gas / humidity sensor is made of a hierarchical porous conductive polymer.

8. The application according to claim 7, characterized in that, The ion gel electrolyte uses polyvinyl alcohol / sulfuric acid (PVA-H2SO4) or silicon dioxide / lithium chloride (SiO2-LiCl) with a coating thickness of 50 μm-1 mm; the flexible substrate uses polytetrafluoroethylene, polyvinylidene fluoride or nylon filter membrane.

9. The application according to claim 7, characterized in that, A conductive hydrogel was prepared by mixing hierarchical porous conductive polymer, PVA, and borax in a mass ratio of 1:(50~100):

5. This hydrogel was then coated onto a planar interdigitated microelectrode as the sensing unit of a pressure sensor, with a coating thickness of 50 μm-1 mm. 10~50 μL of an ethanol dispersion of the hierarchical porous conductive polymer (0.5-2.0 mg / mL) was drop-coated onto the planar interdigitated microelectrode and dried to obtain an ammonia sensor. 0.1~1.0 mL of an aqueous dispersion of the hierarchical porous conductive polymer (0.5-2.0 mg / mL) was drop-coated onto the planar interdigitated microelectrode and dried to obtain a humidity sensor.

10. The application according to claim 7, characterized in that: On the same flexible substrate, with the aid of an interdigitated mask, a dispersion of hierarchical porous conductive polymer with a concentration of 0.1-0.5 mg / mL is injected into each electrode. After filtration and drying, the mask is removed to obtain two microelectrodes. By coating the corresponding ion gel electrolyte and the sensing unit of the pressure / gas / humidity sensor, a micro supercapacitor and a corresponding sensor can be obtained, forming a coplanar, flexible micro supercapacitor-pressure / gas / humidity sensor integrated microsystem.

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