Conductive compound PTP, preparation method and application thereof

Abstract

The invention discloses a conductive compound PTP and a preparation method and application thereof.The conductive compound PTP is a water-soluble compound which is formed by crosslinking three groups including positively charged PEDOT, negatively charged TFA and PSS and is stable in structure, and the conductive compound PTP is prepared from raw materials including EDOT, trifluoroacetic acid and PSS. The problems of low conductivity, low solution stability and poor film-forming property in the prior art are solved.

Description

Technical Field

[0001] The present invention relates to the fields of flexible electronics and advanced energy, and particularly relates to a conductive composite PTP, a preparation method thereof, and an application thereof. Background Art

[0002] In recent years, with the rapid development of flexible electronic devices and energy devices, flexible electrode materials with multifunctions of charge collection, transmission, and storage have received increasing attention. Among many materials, the conductive polymer PEDOT:PSS has attracted much attention due to its many advantages such as high conductivity, high light transmittance, high stability, and aqueous solution processability, and has become the focus of current research and industry. At present, PEDOT:PSS produced by Heraeus in Germany dominates the market. There is no mature formula in China that can replace it, and the applications in the frontier fields basically still purchase products from Heraeus. Therefore, developing a new formula for high-performance novel PEDOT-based composites is beneficial to solving the bottleneck problem in the field of conductive polymers in China. The conductivity of the poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) PEDOT:PSS stock solution PH1000 produced by Heraeus is poor, and its conductivity is only ~1 S / cm. It is necessary to improve the conductivity through secondary doping or post-treatment of film formation.

[0003] In the PEDOT:PSS composite system, the conductive component is PEDOT. Poly(styrenesulfonic acid) (PSS) is used as a dopant to improve the conductivity of PEDOT and endow PEDOT with excellent aqueous solution processability at the same time. However, the introduction of a large amount of insulating phase PSS cuts off the contact between some PEDOT molecules, resulting in a decrease in the conductivity of PEDOT. Specifically, in the preparation of PEDOT:PSS, PSS with Mw ~70000 is commonly used, and the molecular chain is relatively long, which is extremely easy to coat PEDOT, thus reducing the conductivity of the product. Summary of the Invention

[0004] The present invention provides a conductive composite PTP, a preparation method thereof, and an application thereof, which solve the problems of low conductivity and poor performance existing in the prior art.

[0005] To solve this technical problem, the present invention provides the following technical solutions:

[0006] A conductive composite PTP, wherein the conductive composite PTP is a water-soluble composite with a stable structure formed by cross-linking three groups: positively charged PEDOT, negatively charged organic small molecule acid radicals, and PSS. The conductive composite PTP is prepared using raw materials including EDOT, an organic small molecule acid with a PKa lower than PSS, and PSS.

[0007] Preferably, the organic small molecule acid is selected from trifluoroacetic acid, difluoroacetic acid, trichloroacetic acid, or trifluoromethanesulfonic acid.

[0008] Taking trifluoroacetic acid as an example, TFA — The introduction of the group, on the one hand, through its steric hindrance effect, reduces the coating degree of PSS on PEDOT, increases the contact between PEDOTs, and raises the conductivity of the PEDOT composite to 7.88 S / cm; on the other hand, due to the change in molecular structure and the increase in conductivity, without any post-treatment, compared with PH1000 produced by Heraeus in Germany, the capacitance performance of the film is increased from 100 F / cm 3 to 184 F / cm 3 ; In addition, due to the introduction of the TFA — group, the PEDOT-based composite exhibits excellent film-forming properties and solution stability. Its solution is placed for 3 months or more without obvious sedimentation.

[0009] The preparation method of the above conductive composite PTP includes the following steps:

[0010] S1. Place the organic small molecule acid, PSS, the catalyst iron(III) trifluoromethanesulfonate Fe(OTf)3 and sodium persulfate Na2S2O8 in a reactor, add water as a solvent, and finally add EDOT;

[0011] S2. Stir and react at room temperature to obtain the initial PTP solution;

[0012] S3. Transfer the above-prepared initial PTP solution to an ion exchange resin membrane, place it in deionized water for ion exchange, remove the excess ions in the PTP solution, and obtain the conductive composite PTP.

[0013] Preferably, in the above step S1, 625 mg of PSS, 10 mg of Fe(OTf)3, and 98 mg of Na2S2O8 are successively weighed and placed in a reactor, 10 - 100 mg of the organic small molecule acid is added, 10 ml of water is added and stirred until completely dissolved, 50 mg of EDOT monomer is added under stirring, the solution gradually turns blue and finally dark blue, and react at room temperature for 24 hours to obtain the initial PTP solution.

[0014] Preferably, in the above step S2, the stirring reaction time is 24 hours.

[0015] Preferably, in the above step S3, transfer the prepared initial PTP solution to an ion exchange resin membrane, place it in 250 ml of deionized water for ion exchange, the ion exchange is carried out 3 times, 4 hours each time, remove the excess ions in the PTP solution, add a magnetic stirrer at the bottom of the beaker to improve the exchange speed; after the exchange is completed, the prepared water-soluble conductive composite PTP is obtained.

[0016] Preferably, the ion exchange resin membrane is first boiled in boiling water for 10 minutes.

[0017] The application of the above-mentioned conductive composite PTP in the fields of solar cells, light-emitting devices, photodetectors, electromagnetic shielding, etc.

[0018] The application of the above-mentioned conductive composite PTP in supercapacitors.

[0019] Preferably, the above application is to process the PTP composite onto glass by spin coating to obtain a uniform conductive film, and test its conductivity ≥ 2.68 S / cm.

[0020] Preferably, the above application is to process the PTP composite onto ITO glass by spin coating to prepare an ITO / PTP electrode. Under a three-electrode system with Ag / AgCl as the reference electrode, Pt as the counter electrode, and ITO / PTP electrode as the working electrode, using 1M H2SO4 as the electrolyte, a supercapacitor is prepared.

[0021] Compared with the prior art, the present invention has the following advantages:

[0022] By introducing TFA into the molecule — , a new PEDOT-based conductive composite that can be processed in aqueous solution was designed and synthesized. Compared with Clevios TM PH1000 (~1 S / cm) which dominates the current market, PTP has higher conductivity (7.88 S / cm), better capacitance performance, comparable film-forming property and comparable solution stability. Compared with the conductive composite PEDOT:PSS prepared without introducing the TFA — group, PTP has a qualitative improvement in film-forming property, solution stability and capacitance performance. This formulation provides a new solution to solve the bottleneck problem in the field of conductive polymers in our country. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The drawings described herein are used to provide a further understanding of the embodiments of the present invention, form a part of this application, and do not limit the embodiments of the present invention. In the drawings:

[0024] Figure 1 is a schematic diagram of the preparation process of the conductive composite PTP of the present invention;

[0025] Figure 2 is a comparison diagram of film-forming photos before and after introducing CF3COOH during the preparation process of the conductive composite PTP;

[0026] Figure 3 is a statistical chart of the conductivity of the PTP composite prepared under different CF3COOH ingredient ratios;

[0027] Figure 4(a) Cyclic voltammetry test curves of PTP composites prepared with different proportions of CF3COOH feedstock; Figure 4 (b) Charge-discharge curves of PTP composites prepared with different proportions of CF3COOH feedstock. Detailed implementation manners

[0028] To make the objectives, technical solutions and advantages of the present invention clearer and more understandable, the present invention will be further described in detail below in conjunction with embodiments. The illustrative embodiments and descriptions thereof of the present invention are only used to explain the present invention and are not intended to limit the present invention.

[0029] Embodiment 1

[0030] The synthesis process of the novel water-soluble conductive composite PTP1 is as Figure 1 shown. The raw materials used are EDOT, trifluoroacetic acid and PSS. The solvent used for preparation is water, and the catalysts used are iron(III) trifluoromethanesulfonate Fe(OTf)3 and sodium persulfate Na2S2O8;

[0031] Its preparation process flow is as follows:

[0032] Step 1: Weigh 625 mg of PSS, 10 mg of Fe(OTf)3, 98 mg of Na2S2O8, place them in a reactor, add 10 mg (0.1 wt%) of TFA, add 10 ml of water and stir until completely dissolved; dropwise add 50 mg of EDOT monomer under stirring conditions, the solution gradually turns blue and finally dark blue, and react at room temperature for 24 hours to obtain the initial PTP solution;

[0033] Step 2: Boil the ion exchange resin membrane in boiling water for 10 minutes and set aside for use;

[0034] Step 3: Transfer the above-synthesized initial PTP1 solution into the ion exchange resin membrane, place it in 250 ml of deionized water for ion exchange, and perform ion exchange 3 times, 4 hours each time, to remove the excess ions in the PTP1 solution; add a magnetic stirrer at the bottom of the beaker to improve the exchange speed. After the exchange is completed, obtain the PTP aqueous solution and set aside for use;

[0035] Step 4: Ultrasonically clean the glass and ITO conductive glass with dishwashing liquid, deionized water, acetone and isopropanol for 25 - 35 minutes each; dry with nitrogen and set aside for use;

[0036] Step 5: Perform surface plasma treatment on the glass surface with a Plasma cleaner for 1 - 2 minutes, then drop the prepared PTP1 solution on the glass substrate, spin-coat at 900 revolutions per minute for 1 minute, and then place it on a hot stage and heat at 120 °C for 10 minutes. Test the sheet resistance (R □) is 35.7 kΩ / sq and the thickness is 105 nm. Then, according to the conductivity calculation formula, the conductivity of the thin film is calculated to be 2.68 S / cm( Figure 3 ).

[0037] Step 6: Perform Plasma treatment on the cleaned ITO glass for 1 - 2 min, then drop the PTP1 solution onto the ITO glass. First, spin at 900 revolutions per minute for 30 s, and then spin at 1200 revolutions per minute for 30 s to obtain the PTP1 thin film. Heat the thin film at 150 °C for 10 min. After testing with a profilometer, the thickness of the thin film is 125 nm. Using a three - electrode system, with Ag / AgCl as the reference electrode, Pt as the counter electrode, and ITO / PTP1 electrode as the working electrode, and 1 M H2SO4 as the electrolyte, test the cyclic voltammetry characteristics and charge - discharge characteristics of the PTP1 thin film( Figure 4 ), and calculate that the volume capacitance of PTP1 is 122 F / cm 3 .

[0038] Example 2

[0039] The raw materials used for preparing the novel water - soluble conductive composite PTP5 are EDOT, trifluoroacetic acid, and PSS. The preparation process is as Figure 1 shown. The solvent used for preparation is water, and the catalysts used are iron(III) trifluoromethanesulfonate Fe(OTf)3 and sodium persulfate Na2S2O8;

[0040] Its preparation process flow is as follows:

[0041] Step 1: Weigh 625 mg of PSS, 10 mg of Fe(OTf)3, and 98 mg of Na2S2O8, place them in a reactor, add 50 mg (0.5 wt%) of TFA, and add 10 ml of water and stir until completely dissolved; under stirring conditions, gradually dropwise add 50 mg of EDOT monomer. The solution gradually turns blue and finally turns dark blue. React at room temperature for 24 hours to obtain the PTP initial solution;

[0042] Step 2: Boil the ion - exchange resin membrane in boiling water for 10 minutes and set it aside for later use;

[0043] Step 3: Transfer the above - synthesized PTP5 initial solution into the ion - exchange resin membrane, place it in 250 ml of deionized water for ion exchange. The number of ion - exchange times is 3 times, 4 hours each time, to remove the excess ions in the PTP solution; add a magnetic stirrer at the bottom of the beaker to enhance the exchange speed. After the exchange is completed, obtain the PTP5 aqueous solution and set it aside for later use;

[0044] Step 4: Ultrasonically clean the glass and ITO conductive glass with dishwashing liquid, deionized water, acetone, and isopropanol for 25 - 35 minutes each in turn; dry with nitrogen and set aside for later use;

[0045] Step Five: Perform surface plasma treatment on the glass surface with a Plasma cleaner for 1 - 2 minutes, then drop the prepared PTP5 solution onto the glass substrate, spin - coat it at 900 revolutions per minute for 1 minute, and then place it on a hot stage and heat it at 120 °C for 10 minutes. Test the sheet resistance (R □ ) of the thin film, which is 10.2 kΩ / sq, and the thickness is 125 nm. Then calculate the conductivity of the thin film according to the conductivity calculation formula, and the conductivity is 7.88 S / cm( Figure 3 ).

[0046] Step Six: Perform 1 - 2 min Plasma treatment on the cleaned ITO glass, then drop the PTP5 solution onto the ITO glass, first spin - coat it at 900 revolutions per minute for 30 s, and then spin - coat it at 1200 revolutions per minute for 30 s to obtain the PTP thin film. Heat the thin film at 150 °C for 10 minutes. Test the thickness of the thin film with a profilometer, and the thickness is 90 nm. Adopt a three - electrode system, use Ag / AgCl as the reference electrode, Pt as the counter electrode, and ITO / PTP5 electrode as the working electrode, and use 1 M H2SO4 as the electrolyte to test the cyclic voltammetry characteristics and charge - discharge characteristics of the PTP5 thin film( Figure 4 ), and calculate that the volume capacitance of PTP5 is 184 F / cm 3 .

[0047] Example 3

[0048] The raw materials used for preparing the novel water - soluble conductive composite PTP10 are EDOT, trifluoroacetic acid, and PSS. The solvent used for preparation is water, and the catalysts used are iron(III) trifluoromethanesulfonate Fe(OTf)3 and sodium persulfate Na2S2O8;

[0049] The preparation process flow is as follows:

[0050] Step One: Weigh 625 mg of PSS, 10 mg of Fe(OTf)3, 98 mg of Na2S2O8, place them in a reactor, add 100 mg (0.1 wt%) of TFA, add 10 ml of water and stir until completely dissolved; dropwise add 50 mg of EDOT monomer under stirring conditions. The solution gradually turns blue and finally turns dark blue. React at room temperature for 24 hours to obtain the PTP initial solution;

[0051] Step Two: Boil the ion - exchange resin membrane in boiling water for 10 minutes and set it aside for later use;

[0052] Step 3: Transfer the synthesized initial PTP10 solution into an ion-exchange resin membrane and place it in 250 ml of deionized water for ion exchange. Conduct the ion exchange 3 times, 4 hours each time, to remove the excess ions in the PTP10 solution. Add a magnetic stirrer at the bottom of the beaker to enhance the exchange rate. After the exchange is completed, obtain the PTP10 aqueous solution and set it aside for later use;

[0053] Step 4: Ultrasonically clean the glass and ITO conductive glass with dishwashing liquid, deionized water, acetone, and isopropanol for 25 - 35 minutes each; dry them with nitrogen and set aside for later use;

[0054] Step 5: Perform surface plasma treatment on the glass surface with a Plasma cleaner for 1 - 2 minutes. Then, drop the prepared PTP10 solution onto the glass substrate, spin-coat it at 1000 revolutions per minute for 1 minute, and then place it on a hot plate and heat it at 120 °C for 10 minutes. Test the sheet resistance (R □ ) of the thin film, which is 23.3 kΩ / sq, and the thickness is 112 nm. Then, calculate the conductivity of the thin film according to the conductivity calculation formula, which is 3.83 S / cm( Figure 3 ).

[0055] Step 6: Perform 1 - 2 min Plasma treatment on the cleaned ITO glass. Then, drop the PTP10 solution onto the ITO glass, first spin it at 900 revolutions per minute for 30 s, and then spin it at 1200 revolutions per minute for 30 s to obtain the PTP10 thin film. Heat the thin film at 150 °C for 10 minutes. Test the thickness of the thin film with a profilometer, which is 90 nm. Adopt a three-electrode system, use Ag / AgCl as the reference electrode, Pt as the counter electrode, and ITO / PTP10 electrode as the working electrode, and use 1M H2SO4 as the electrolyte to test the cyclic voltammetry characteristics and charge-discharge characteristics of the PTP10 thin film( Figure 4 ), and calculate the volume capacitance of PTP10 to be 126 F / cm 3 .

[0056] Comparative Example 1

[0057] Use the highly conductive PEDOT:PSS (PH1000) produced by Heraeus of Germany as Comparative Example 1 for performance characterization and comparison. Currently, PH1000 produced by Heraeus of Germany occupies a dominant position in the highly conductive PEDOT:PSS market and is representative as a comparative example with the PTP series.

[0058] Step 1: Ultrasonically clean the glass and ITO conductive glass with dishwashing liquid, deionized water, acetone, and isopropanol for 25 - 35 minutes each; dry them with nitrogen and set aside for later use;

[0059] Step 2: Perform surface plasma treatment on the glass surface with a Plasma cleaner for 1 - 2 minutes. Then, drop the purchased PH1000 solution onto the glass substrate, spin - coat it at 900 revolutions per minute for 1 minute, and then place it on a hot stage and heat it at 120 °C for 10 minutes. The measured sheet resistance (R□) of the film is 101 kΩ / sq, and the thickness is 104 nm. Then, calculate the conductivity of the film according to the conductivity calculation formula, and the conductivity of the film is 0.96 S / cm.

[0060] Step 3: Perform 1 - 2 min Plasma treatment on the cleaned ITO glass. Then, drop the PH1000 solution onto the ITO glass, first spin at 900 revolutions per minute for 30 s, and then spin at 1200 revolutions per minute for 30 s to prepare the PST film. Heat the film at 150 °C for 10 minutes. The thickness of the film is measured to be 104 nm by a step profiler. Using a three - electrode system, with Ag / AgCl as the reference electrode, Pt as the counter electrode, and ITO / PH1000 as the working electrode, and 1M H2SO4 as the electrolyte, test the cyclic voltammetry characteristics and charge - discharge characteristics ( Figure 4 ) of the PTP film. Calculate the volume capacitance of PH1000 to be 100 F / cm 3 .

[0061] Comparative Example 2

[0062] The raw materials used for the preparation of the water - soluble conductive composite PST are EDOT and PSS, the solvent used for the preparation is water, and the catalysts used are iron(III) trifluoromethanesulfonate Fe(OTf)3 and sodium persulfate Na2S2O8; compared with Examples 1 - 3, we did not introduce trifluoroacetic acid in the preparation of PST.

[0063] The preparation process flow is as follows:

[0064] Step 1: Weigh 625 mg of PSS, 10 mg of Fe(OTf)3, and 98 mg of Na2S2O8, place them in a reactor, add 10 ml of water, and stir until completely dissolved; drop 50 mg of EDOT monomer drop - by - drop under stirring conditions. The solution gradually turns blue and finally turns dark blue. React at room temperature for 24 hours to obtain the initial PEDOT:PSS solution;

[0065] Step 2: Boil the ion - exchange resin membrane in boiling water for 10 minutes and set it aside for use;

[0066] Step 3: Transfer the above - synthesized initial PEDOT:PSS solution to the ion - exchange resin membrane, place it in 250 ml of deionized water for ion exchange. The number of ion - exchange times is 3 times, 4 hours each time, to remove the excess ions in the PST solution; add a magnetic stirrer at the bottom of the beaker to enhance the exchange speed. After the exchange is completed, obtain the PST aqueous solution and set it aside for use;

[0067] Step 4: Ultrasonically clean the glass and ITO conductive glass with dishwashing liquid, deionized water, acetone, and isopropanol for 25 - 35 minutes each; dry with nitrogen and set aside for later use.

[0068] Step 5: Perform surface plasma treatment on the glass surface with a Plasma cleaner for 1 - 2 minutes. Then, drop the prepared PST solution onto the glass substrate, spin - coat it at 900 revolutions per minute for 1 minute, and then place it on a hot stage and heat it at 120 °C for 10 minutes. Since the film - forming property of the thin film is poor ( Figure 2 a), the sheet resistance (R □ ) of the thin film was not measured.

[0069] Step 6: Perform 1 - 2 min Plasma treatment on the cleaned ITO glass. Then, drop the PST solution onto the ITO glass, first spin - coat it at 900 revolutions per minute for 30 s, and then spin - coat it at 1200 revolutions per minute for 30 s to obtain a PST thin film. Heat the thin film at 150 °C for 10 minutes. The thickness of the thin film was measured to be 131 nm by a step profiler. Using a three - electrode system, with Ag / AgCl as the reference electrode, Pt as the counter electrode, and ITO / PST electrode as the working electrode, and 1M H2SO4 as the electrolyte, test the cyclic voltammetry characteristics and charge - discharge characteristics of the PST thin film ( Figure 4 ), and calculate that the volume capacitance of PST is 110 F / cm 3 .

[0070] The thin film prepared from the PTP5 sample obtained in Example 2 is as Figure 2 shown. Figure 2 As shown in a, the thin film prepared from the PEDOT:PSS (PST) synthesized in Comparative Example 2. By comparison, it is found that after introducing CF3COOH during the synthesis process of the PTP series products, the conductive composite PTP exhibits excellent film - forming property and light transmittance. After being placed in air for 3 months, no sedimentation of micelles was observed, indicating its good stability; a uniform and transparent conductive thin film can be prepared by simple processes such as spin - coating and blade - coating ( Figure 2 b). By introducing trifluoroacetic acid (TFA) with strong ionization characteristics into the reaction raw materials, and relying on the Coulomb force between cations and anions, TFA — , PEDOT + , and PSS — are cross - linked to prepare a new conductive composite PEDOT:TFA:PSS (PTP).

[0071] The film properties of Examples 1 - 3 and Comparative Examples 1 - 2 are shown in Table 1.

[0072] Table 1

[0073]

[0074] Compared with Clevios currently on the market TM PH1000 (~1 S / cm), PTP exhibits higher conductivity (7.88 S / cm). In addition, due to the optimization of the molecular structure and the improvement of conductivity, PTP demonstrates better electrochemical storage capacity. Under the three-electrode test system, the capacitance of PTP is as high as 184 F / cm 3 , in contrast, under the same conditions, Clevios prepared by Heraeus TM PH1000 has a capacitance of only 100 F / cm 3 .

[0075] Introducing TFA into the reaction raw materials, first of all, TFA has a lower pKa value than PSS, and its ionization ability is stronger, ensuring the presence of a large amount of TFA in the solution under the same conditions — , providing guarantee for the synthesis of PTP; secondly, giving full play to the group occupation effect and steric hindrance effect of TFA — during the formation process of PTP, reducing the coating degree of PSS on PEDOT and increasing the contact between PEDOT; thirdly, the presence of the -CF3 chain in TFA — can improve the hydrophobicity of PTP and the air stability of the film; finally, introducing TFA — during the reaction process is beneficial to constructing a structurally stable PTP complex, because post-doping TFA will lead to an increase in the particle size of PEDOT:PSS and precipitation from the aqueous solution, making film processing impossible.

[0076] The specific embodiments described above further elaborate on the purpose, technical solutions, and beneficial effects of the present invention. It should be understood that the above are only specific embodiments of the present invention and are not used to limit the protection scope of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A conductive composite PTP, characterized in that, The conductive complex PTP is a water-soluble complex with a stable structure formed by cross-linking three groups: positively charged PEDOT, negatively charged organic small molecule acid radicals, and PSS. The conductive complex PTP is prepared using raw materials including EDOT, an organic small molecule acid with a pKa lower than that of PSS, and PSS.

2. The conductive composite PTP according to claim 1, characterized in that, The organic small molecule acid is selected from trifluoroacetic acid, difluoroacetic acid, trichloroacetic acid, or trifluoromethanesulfonic acid.

3. The preparation method of the conductive composite PTP according to claim 1, characterized in that, It includes the following steps: S1. Place the organic small molecule acid, PSS, the catalyst iron(III) trifluoromethanesulfonate Fe(OTf)3, and sodium persulfate Na2S2O8 in a reactor, add water as a solvent, and finally add EDOT. S2. Stir and react at room temperature to obtain an initial PTP solution. S3. Transfer the initially prepared PTP solution into an ion exchange resin membrane, place it in deionized water for ion exchange to remove excess ions in the PTP solution, and obtain the conductive complex PTP.

4. The preparation method of the conductive composite PTP according to claim 3, characterized in that, In the above step S1, first weigh 625 mg of PSS, 10 mg of Fe(OTf)3, and 98 mg of Na2S2O8, place them in a reactor, add 10 - 100 mg of the organic small molecule acid, add 10 ml of water and stir until completely dissolved, add 50 mg of EDOT monomer under stirring conditions, the solution gradually turns blue and finally dark blue, and react at room temperature for 24 hours to obtain the initial PTP solution.

5. The preparation method of the conductive composite PTP according to claim 3, characterized in that, In the above step S2, the stirring reaction time is 24 hours.

6. The preparation method of the conductive composite PTP according to claim 3, characterized in that, In the above step S3, transfer the initially prepared PTP solution into an ion exchange resin membrane, place it in 250 ml of deionized water for ion exchange, with the ion exchange carried out 3 times, 4 hours each time, to remove excess ions in the PTP solution, and add a magnetic stirrer at the bottom of the beaker to enhance the exchange rate; after the exchange is completed, the prepared water-soluble conductive complex PTP is obtained.

7. Application of the conductive complex PTP described in claim 1 in the fields of solar cells, light-emitting devices, photodetectors, electromagnetic shielding, etc.

8. Application of the conductive complex PTP described in claim 1 in supercapacitors.

9. The application according to claim 7, wherein The PTP complex is processed onto glass by spin coating to obtain a uniform conductive thin film with a conductivity ≥ 2.68 S / cm.

10. The application according to claim 8, characterized in that, The PTP complex is processed onto ITO glass by spin coating to prepare an ITO / PTP electrode. Under a three-electrode system with Ag / AgCl as the reference electrode, Pt as the counter electrode, and the ITO / PTP electrode as the working electrode, using 1 M H2SO4 as the electrolyte, a supercapacitor is prepared.

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