Organic semiconductor material based on one-dimensional organic conjugated coordination polymer, preparation method thereof and supercapacitor application

Abstract

This invention discloses an organic semiconductor material based on a one-dimensional organic conjugated coordination polymer, its preparation method, and its application in supercapacitors. The material has the structure shown in Formula I. This invention achieves a one-pot synthesis of the material by reacting 2,3,5,6-tetrathiol-1,4-hydroquinone with a nickel source in an acetic acid-alkali aqueous solution. By controlling the reaction conditions, powders or flexible self-supporting films capable of self-assembly at the gas-liquid interface can be obtained. The material of this invention exhibits excellent mixed conductivity, with an electronic conductivity of 1 S·cm at 300 K. ‑1 The ionic conductivity reaches 10. ‑5 S·cm ‑1 The Ni-TTBQ-Na thin film exhibits an electronic conductivity as high as 219 S·cm. ‑1 The thin film of this invention can be used as an independent electrode in a symmetrical supercapacitor, at 0.3 A·g ‑1 The capacitance per unit current density reaches 249 F·g ‑1 3 A·g ‑1 After 5000 cycles, the capacity retention rate reaches 88%. The material provided by this invention has both high conductivity and good processing performance, and the preparation method is simple and controllable, showing broad application prospects in the field of flexible electronic devices.

Description

Technical Field

[0001] This invention belongs to the field of organic semiconductor materials, and relates to an organic semiconductor material based on a one-dimensional organic conjugated coordination polymer, its preparation method, and its application in supercapacitors. Background Technology

[0002] Conjugated coordination polymers, a class of functional materials constructed from organic ligands and metal ions through coordination bonds, have shown broad application prospects in the field of energy storage and conversion in recent years. These materials, through the d-π hybridization between the metal center and the conjugated ligands, can form extended network structures that facilitate electron delocalization, providing a structural basis for efficient charge transport, and thus attracting widespread attention in the field of organic semiconductors.

[0003] However, due to the inherent rigid framework structure of conjugated coordination polymers, existing materials generally face the bottleneck of poor processability, making it difficult to simultaneously meet the dual requirements of high conductivity and good processability for electronic devices. Currently, a common improvement strategy is to composite or hybridize conjugated coordination polymers with flexible materials to improve their film-forming properties. However, these methods often introduce problems such as discontinuous conductive channels and poor interfacial contact, leading to a significant decrease in the intrinsic conductivity of the material. On the other hand, interfacial synthesis methods can achieve thin film preparation, but they have limitations such as strong substrate dependence and difficulty in large-scale preparation, making it difficult to meet the mass production requirements of high-quality thin film materials for practical applications.

[0004] Therefore, how to achieve controllable film formation and structural regulation of conjugated coordination polymers through reasonable molecular design and synthesis strategies, and obtain thin film materials with both intrinsic high conductivity and excellent processing performance, is of great significance for promoting the practical application of such materials in the field of flexible devices. Summary of the Invention

[0005] This invention aims to solve the technical challenge of existing conjugated coordination polymers in achieving both high conductivity and good processability. It provides a novel class of one-dimensional organic conjugated coordination polymers, their preparation methods, and applications in supercapacitors. Specifically, it provides a class of tetrathithyl-p-benzoquinone nickel organic semiconductor materials with the structure of Formula I, exhibiting both high electronic and ionic conductivity. A one-pot synthesis strategy is provided, which, by introducing an acetic acid-based regulator, allows for controllable preparation of the material's crystallinity, morphology, and macroscopic form (powder or self-supporting thin film). A flexible self-supporting thin film is also provided, maintaining structural and electrical stability under bending and folding conditions. Finally, the application of the above materials as binder-free independent electrodes in supercapacitors is provided to achieve high specific capacitance and excellent cycle stability.

[0006] The organic semiconductor material based on a one-dimensional organic conjugated coordination polymer provided by this invention has the structure shown in Formula I, namely Ni-TTBQ-A:

[0007]

[0008] Formula I In Equation I, m is 1-4, A + Li + Na + K + 、Rb + .

[0009] The organic semiconductor material of this invention can be a powder or a self-supporting thin film.

[0010] When the organic semiconductor material is in powder form, it exhibits mixed conductivity, with an electronic conductivity of 1 S·cm at 300 K. -1 The ionic conductivity reaches 10. -5 S·cm -1 .

[0011] When the organic semiconductor material is a self-supporting thin film, its electronic conductivity reaches 219 S·cm at 300 K. -1 It is also flexible.

[0012] The present invention also provides a method for preparing the organic semiconductor material, comprising the following steps: The organic semiconductor material is obtained by reacting 2,3,5,6-tetramercapto-1,4-hydroquinone (TTHQ) with nickel acetate tetrahydrate in an aqueous solution of acetic acid base.

[0013] Preferably, the acetic acid base is at least one selected from lithium acetate, sodium acetate, potassium acetate, and rubidium acetate; The reaction conditions are: temperature 60-80℃, time 12-24 hours.

[0014] Preferably, when preparing the powdered material, the reaction temperature is 60°C, the reaction time is 12 hours, and the molar ratio of the acetic acid base to the 2,3,5,6-tetramercapto-1,4-hydroquinone is: lithium acetate or sodium acetate 20:1, potassium acetate 30:1, and rubidium acetate 5:1.

[0015] Preferably, when preparing the self-supporting thin film material, the reaction temperature is 80°C, the reaction time is 24 hours, and the acetic acid base is lithium acetate or sodium acetate, the molar ratio of acetic acid base to TTHQ is 6:1, and the product is collected at the gas-liquid interface.

[0016] The organic semiconductor material provided by this invention can be used to prepare supercapacitor electrodes or organic semiconductor devices; the organic semiconductor material can be used as an independent electrode in symmetrical supercapacitors without the need to add binders and conductive additives.

[0017] In addition, the present invention also provides a supercapacitor comprising the above-mentioned organic semiconductor material as an electrode material.

[0018] This invention employs tetrathiol-p-phenol with different reactive substituents as ligand units to construct a one-dimensional coordination polymer with metallic nickel. Compared to traditional all-thiol ligand systems, this design significantly enriches the structural diversity of the material by introducing substituents with different reactivity. While ensuring the integrity of the conductive channels, it achieves synergistic effects of multiple functions, endowing the material with excellent redox activity, significantly improving processability, and providing an effective channel for ion transport, resulting in typical mixed conductivity behavior. At 300 K, the electronic conductivity of this material reaches 1 S·cm. -1 The ionic conductivity reaches 10. -5 S·cm -1 It exhibits excellent mixed conductivity properties.

[0019] In the synthesis strategy, acetic acid base was introduced as a regulator, which effectively improved the crystallinity of the one-dimensional product and enabled the control of the product growth process and microstructure. Through this design, the electronic conductivity and processing performance of the material were synergistically optimized. The prepared self-supporting film maintained stable electrical properties under bending, folding, and other deformation conditions. The Ni-TTBQ-Na film achieved an electronic conductivity of 219 S·cm at 300 K. -1 As a binder-free, additive-free, independent electrode, this material exhibits excellent electrochemical performance in supercapacitor devices. Taking Ni-TTBQ-Na as an example, at 0.3 A·g -1 At a current density of 249 F·g, its capacitance per unit volume reaches 249 F·g. -1 ; in 3A·g -1 After 5000 cycles, the capacity remained as high as 88%, demonstrating excellent cycle stability.

[0020] Furthermore, the preparation method provided by this invention is simple and can realize the preparation of large-area, high-quality thin films, which has broad application prospects in cutting-edge fields such as flexible energy storage and wearable electronics. Attached Figure Description

[0021] Figure 1 This is a schematic diagram of the synthesis of nickel tetramercapto-p-benzoquinone (Ni-TTBQ-A, where A is Li, Na, K, or Rb).

[0022] Figure 2 The image shows the powder X-ray diffraction (PXRD) pattern of nickel tetrathiomercapto-p-benzoquinone (Ni-TTBQ-K) prepared in Example 1 of this invention and its comparison with the theoretical pattern.

[0023] Figure 3The PXRD pattern of nickel tetrathio-p-benzoquinone (Ni-TTBQ-A, where A is Li, Na, K, or Rb) prepared in Example 1 of this invention is shown.

[0024] Figure 4 Infrared (IR) spectra of nickel tetrathiomercapto-p-benzoquinone (Ni-TTBQ-A, where A is Li, Na, K, or Rb) and 2,3,5,6-tetrathiomercapto-1,4-hydroquinone (TTHQ) prepared in Example 1 of this invention.

[0025] Figure 5 The image shows a scanning electron microscope (SEM) image of nickel tetrathiomercapto-p-benzoquinone (Ni-TTBQ-A, where A is Li, Na, K, or Rb) prepared in Example 1 of this invention.

[0026] Figure 6 The transmission electron microscope (TEM) image of nickel tetrathiomercapto-p-benzoquinone (Ni-TTBQ-A, where A is Li, Na, K, or Rb) prepared in Example 1 of this invention.

[0027] Figure 7 The conductivity of the tetrathiomercapto-p-benzoquinone nickel (Ni-TTBQ-A, where A is Li, Na, K, or Rb) prepared in Example 1 of this invention is shown as a function of temperature.

[0028] Figure 8 Electrochemical impedance spectroscopy (EIS) of nickel tetrathiomercapto-p-benzoquinone (Ni-TTBQ-A, where A is Li, Na, K, or Rb) prepared in Example 1 of this invention.

[0029] Figure 9 PXRD patterns in reflection and transmission modes of the nickel-tetrathio-p-benzoquinone thin film (Ni-TTBQ-Na) prepared in Example 2 of this invention.

[0030] Figure 10 The resistivity variation spectrum of the nickel-tetrathio-p-benzoquinone thin film (Ni-TTBQ-Na) prepared in Example 2 of this invention under different bending states.

[0031] Figure 11 The conductivity of the nickel-p-benzoquinone thin film (Ni-TTBQ-Na) prepared in Example 2 of this invention is shown as a function of temperature.

[0032] Figure 12 This is a schematic diagram of the device assembly when the tetrathio-p-benzoquinone nickel film (Ni-TTBQ-Na) prepared in Example 2 of the present invention is used as an independent electrode in a symmetrical supercapacitor.

[0033] Figure 13The galvanostatic charge-discharge curves (GCD) of the nickel-p-benzoquinone thin film (Ni-TTBQ-Na) prepared in Example 2 of this invention when used in a symmetrical supercapacitor device at different current densities.

[0034] Figure 14 Cyclic stability curves of the nickel tetrathio-p-benzoquinone thin film (Ni-TTBQ-Na) prepared in Example 2 of this invention when used in a symmetrical supercapacitor device, and images of the light-emitting diodes lit up. Detailed Implementation

[0035] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0036] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.

[0037] The conductivity of the material prepared by this invention was tested using the following method: The electronic conductivity of the material was tested using a KEITHLEY 2002 Multimeter instrument with a four-probe method: first, the powder sample was pressed into a 5×2 mm block, and then silver paste was used to connect it to four silver wires for testing.

[0038] The ionic conductivity of the material was obtained by measuring the electrochemical impedance spectroscopy (EIS) of the compressed sample using an electrochemical workstation (CHI 660E). First, the powder sample was compressed into a block, then silver wires were glued to both sides of the block using silver paste. The silver wires were then connected to the electrochemical workstation for testing. The ionic conductivity was calculated from the resistance of a sample of known size.

[0039] The electrochemical performance of the material prepared by this invention was tested on an electrochemical workstation (CHI 660E).

[0040] To address the technical bottleneck of existing conjugated coordination polymers in achieving both intrinsic high conductivity and good processability, this invention provides a nickel material (Ni-TTBQ-A, where A is an alkali metal ion) with a structure shown in Formula I. This material is prepared by reacting 2,3,5,6-tetramercapto-1,4-hydroquinone with a nickel source in an acetic acid-based aqueous solution. During the synthesis process, the ligand unit is oxidized from hydroquinone to a phenolic compound.

[0041] This invention introduces acetic acid as a reaction regulator, which on the one hand improves the crystallinity of the product, and on the other hand achieves effective control over the product growth process and microstructure. By controlling the reaction conditions (temperature, time, and amount of acetic acid), powdered products or flexible self-supporting films that can self-assemble at the gas-liquid interface can be obtained.

[0042] The material of this invention exhibits excellent mixed conductivity: an electronic conductivity of 1 S·cm at 300 K. -1 The ionic conductivity reaches 10. -5 S·cm -1 The Ni-TTBQ-Na thin film exhibits an electronic conductivity as high as 219 S·cm. -1 Furthermore, it maintains structural and electrical stability even after bending and folding.

[0043] When used as a binder-free, additive-free, independent electrode in a symmetrical supercapacitor, this material exhibits excellent electrochemical performance: at 0.3 A·g -1 The capacitance per unit current density reaches 249 F·g -1 3 A·g -1 After 5000 cycles, the capacity retention rate is as high as 88%.

[0044] This invention achieves synergistic optimization of material structure and performance through a one-pot synthesis method. The reaction process is simple and controllable, demonstrating the application prospects of one-dimensional organic conjugated coordination polymers as organic semiconductor materials in flexible electronic devices.

[0045] Example 1: Preparation of nickel tetrathiomercapto-p-benzoquinone (Ni-TTBQ-A, where A is Li, Na, K, or Rb) powder as shown in Formula I. Synthesis diagram as shown Figure 1 As shown.

[0046] Under an argon atmosphere, TTHQ (0.2 mmol, 47.7 mg), deionized water (20 mL), and additives (acetate: lithium acetate / sodium acetate / potassium acetate / rubidium acetate, with molar ratios relative to the ligands of 20, 20, 30, and 5, respectively) were added to a 100 mL two-necked flask. After sonication, a pale yellow transparent solution was obtained, followed by the addition of nickel acetate tetrahydrate (0.2 mmol, 49.8 mg). The reaction system was continued at 60 °C for 12 h. After the reaction was complete, the product was collected by filtration and washed several times successively with water, ethanol, and acetone, then dried under vacuum in a 60 °C oven for 24 h to obtain nickel tetrathiomercapto-p-benzoquinone powder as shown in Formula I, labeled as Ni-TTBQ-A (A being Li, Na, K, or Rb), where m is 2 when A is Li or Na, and m is 1 when A is K or Rb.

[0047] Example 2: Preparation of nickel tetrathio-p-benzoquinone (Ni-TTBQ-A, where A is Li or Na) thin film as shown in Formula I Under argon protection, TTHQ (0.2 mmol, 47.7 mg), deionized water (20 mL), and additives (lithium acetate or sodium acetate, molar ratio to ligand 6:1) were added to a 100 mL two-necked flask. The mixture was sonicated to obtain a light yellow solution, followed by the addition of nickel acetate tetrahydrate (0.2 mmol, 49.8 mg). The reaction system temperature was raised to 80 °C, the argon protection was removed, and the reaction was carried out with gentle stirring for 24 h. Finally, the black thin film product formed at the gas-liquid interface was collected and washed several times with water, ethanol, and acetone. The product was flattened and vacuum dried in a 60 °C oven for 24 h to obtain a nickel tetrathio-p-benzoquinone film as shown in Formula I, labeled Ni-TTBQ-AF (A is Li, Na), where m is 2-4, varying with ambient humidity.

[0048] Elemental analysis was performed on the series of Ni-TTBQ-A materials: the relative content of the elements Ni:S was about 1:1, indicating that the obtained materials were all one-dimensional products.

[0049] Figure 2 The image shows the powder X-ray diffraction (PXRD) pattern of nickel tetrathio-p-benzoquinone (Ni-TTBQ-K) prepared in Example 1 of this invention and its comparison with the theoretical pattern. As can be seen from the image, the experimentally obtained XRD is highly consistent with the simulated XRD and exhibits excellent crystallinity.

[0050] Figure 3 The PXRD pattern of nickel tetrathio-p-benzoquinone (Ni-TTBQ-A, where A is Li, Na, K, or Rb) prepared in Example 1 of this invention is shown in the figure. As can be seen from the figure, the materials obtained under different weak base salts have similar PXRD patterns, indicating that their crystal structures have certain similarities.

[0051] Figure 4 The infrared (IR) spectra of nickel tetrathiomercapto-1,4-hydroquinone (Ni-TTBQ-A, where A is Li, Na, K, or Rb) and 2,3,5,6-tetrathiomercapto-1,4-hydroquinone (TTHQ) prepared in Example 1 of this invention are shown at 1620 cm⁻¹. -1 A distinct C=O vibrational signal was observed, indicating that the phenolic unit in the ligand structure was oxidized to a benzoquinone structure during the synthesis process.

[0052] Figure 5 and Figure 6 The SEM and TEM images of the tetrathithyl-p-benzoquinone nickel (Ni-TTBQ-A, where A is Li, Na, K, or Rb) prepared in Example 1 of this invention show that the cation has a regulatory effect on the morphology of the product.

[0053] Figure 7 and Figure 8The electrical conductivity versus temperature and electrochemical impedance spectroscopy (EIS) spectra of the tetrathiomercapto-p-benzoquinone nickel (Ni-TTBQ-A, where A is Li, Na, K, or Rb) prepared in Example 1 of this invention are shown, indicating that this type of material exhibits mixed conductivity behavior. At 300 K, the electronic conductivity reaches 1 S·cm. -1 The ionic conductivity reaches 10. -5 S·cm -1 It exhibits excellent mixed conductivity properties.

[0054] Figure 9 The PXRD patterns in reflection and transmission modes of the nickel-tetrathioquinone thin film (Ni-TTBQ-Na) prepared in Example 2 of this invention show that the thin film sample has good crystallinity and high orientation.

[0055] Figure 10 and Figure 11 The resistivity and conductivity versus temperature spectra of the nickel tetrathiomercapto-p-benzoquinone thin film (Ni-TTBQ-Na) prepared in Example 2 of this invention under different bending states are shown respectively. This indicates that the thin film material maintains stable electrical properties under bending, folding, and other deformation conditions. It can be seen that the electronic conductivity of the Ni-TTBQ-Na thin film reaches 219 S·cm at 300 K. -1 .

[0056] Figure 12 This is a schematic diagram of the device assembly when the nickel tetrathio-p-benzoquinone film (Ni-TTBQ-Na) prepared in Example 2 of the present invention is used as an independent electrode in a symmetrical supercapacitor. The device is assembled using a sandwich-like structure, in which carbon-based graphite paper is used as the current collector, the nickel tetrathio-p-benzoquinone film (Ni-TTBQ-Na) is used as an independent electrode, and PAM hydrogel immersed in 1M KCl solution is used as the separator and electrolyte carrier.

[0057] Figure 13 and Figure 14 The nickel tetrathiomercapto-p-benzoquinone thin film (Ni-TTBQ-Na) prepared in Example 2 of this invention, when used in a symmetrical supercapacitor device, exhibits galvanostatic charge-discharge (GCD) curves and cycle stability curves at different current densities, demonstrating that this material displays excellent electrochemical performance and superior stability in supercapacitor devices. The Ni-TTBQ-Na thin film, at 0.3 A·g... -1 At a current density of 249 F·g, its capacitance per unit volume reaches 249 F·g. -1 ; in 3 A·g -1 After 5000 cycles, the capacity remains as high as 88%.

[0058] Comparative Example 1: Synthesis Attempt Without Acetate Additives Following the steps of Example 1, but without adding any acetate additives, TTHQ and nickel acetate tetrahydrate were simply mixed in deionized water and reacted at 60°C for 12 h.

[0059] Results: The product obtained in the reaction system was uneven in color and contained a large number of unreacted ligands. PXRD characterization showed that the characteristic diffraction peaks of the product were weak in intensity and few in number. Conductivity tests showed that its electronic conductivity was 4.06 S·cm. -1 The yield and crystallinity of this product were significantly lower than those prepared in Example 1. This indicates that acetate additives are crucial for promoting the reaction and improving product yield.

[0060] Comparative Example 2: Using an inorganic base instead of acetate Following the steps of Example 1, the acetate was replaced with an equimolar amount of sodium hydroxide (NaOH), while other conditions remained unchanged (TTHQ 0.2 mmol, nickel acetate tetrahydrate 0.2 mmol, deionized water 20 mL, reaction at 60°C for 12 h).

[0061] Results: The reaction occurred rapidly. PXRD characterization showed that the product was amorphous and had no characteristic diffraction peaks. Conductivity testing showed that its electronic conductivity was less than 10. -8 S·cm -1 The concentration of the product was significantly lower than that of the crystalline product prepared in Example 1. This indicates that a weakly alkaline environment for acetate is key to obtaining ordered crystals and excellent electrical conductivity; an excessively alkaline environment can lead to disordered product structure due to excessively rapid reaction, thereby affecting electrical properties.

[0062] Comparative Example 3: Using other metal sources to replace nickel acetate Following the preparation steps of Ni-TTBQ-Na in Example 1, nickel acetate tetrahydrate was replaced in equal molar amounts with nickel chloride (NiCl2), nickel sulfate (NiSO4), and nickel nitrate (Ni(NO3)2).

[0063] Results: Under the above three conditions, after 24 h of reaction, the product obtained was heterogeneous in color and contained a large number of unreacted ligands. PXRD characterization showed that the product was amorphous and had no characteristic diffraction peaks. Conductivity tests showed that its electronic conductivity was below 10. -8 S·cm - ¹, significantly lower than the crystalline product prepared in Example 1. This indicates that the acetate anion may participate in the coordination or regulation process, and nickel acetate is the preferred nickel source in this synthetic system.

[0064] Comparative Example 4: Preparation of Thin Films by Changing the Reaction Temperature Following the preparation steps of Ni-TTBQ-Na-F in Example 2, the reaction temperatures were changed to 60℃ (same as the powder preparation conditions) and 100℃, respectively.

[0065] Results: After reacting at 60℃ for 24 h, only a few fragmented films were formed at the gas-liquid interface, failing to form a complete self-supporting film; most of the product precipitated at the bottom of the flask. After reacting at 100℃ for 24 h, although a film was formed, it was brittle and easily broken, and its conductivity was only 24 S·cm. -1 The temperature is lower than that of the film prepared at 80°C in Example 2. This indicates that 80°C is the preferred temperature for forming high-quality, highly conductive self-supporting films.

[0066] Comparative Example 5: Using other transition metals to replace nickel Following the preparation steps of Ni-TTBQ in Example 1, nickel acetate tetrahydrate was replaced in equal molar amounts with cobalt acetate tetrahydrate (Co(OAc)2·4H2O) and copper acetate monohydrate (Cu(OAc)2·H2O).

[0067] Results: Both reactions produced precipitates. However, PXRD showed poor crystallinity of the products, and conductivity tests showed that the electronic conductivity of the Co-based product was approximately 1.10 S·cm at 300 K. -1 Cu-based products are approximately 10 -3 S·cm -1 The conductivity is generally lower than that of Ni-based products. This indicates that the d-π conjugated system formed by nickel ions and TTHQ ligands has a unique advantage in achieving high conductivity.

[0068] As can be seen from the above examples and comparative examples, this invention successfully achieved the controllable preparation of highly crystalline, highly conductive one-dimensional organic conjugated coordination polymers by introducing an acetic acid base as a reaction regulator. The comparative examples demonstrate that factors such as the type and amount of acetate, reaction temperature, and selection of the metal source all significantly influence the structure, morphology, and properties of the product. The preferred technical solutions of this invention (Examples 1-2) exhibit significant advantages in terms of material conductivity, film-forming properties, mechanical flexibility, and electrochemical energy storage performance, and have important application value.

Claims

1. An organic semiconductor material based on a one-dimensional organic conjugated coordination polymer, having the structure shown in Formula I: Formula I In Equation I, m is 1-4, A + Li + Na + K + 、Rb + .

2. The organic semiconductor material according to claim 1, characterized in that: The organic semiconductor material is a powder or a self-supporting thin film.

3. The organic semiconductor material according to claim 2, characterized in that: When the organic semiconductor material is in powder form, it exhibits mixed conductivity, with an electronic conductivity of 1 S·cm at 300 K. -1 The ionic conductivity reaches 10. -5 S·cm -1 .

4. The organic semiconductor material according to claim 2, characterized in that: When the organic semiconductor material is a self-supporting thin film, its electronic conductivity reaches 219 S·cm at 300 K. -1 It is also flexible.

5. A method for preparing the organic semiconductor material according to any one of claims 1-4, comprising the following steps: The organic semiconductor material is obtained by reacting 2,3,5,6-tetramercapto-1,4-hydroquinone with nickel acetate tetrahydrate in an aqueous solution of acetic acid base.

6. The preparation method according to claim 5, characterized in that: The acetic acid base is at least one of lithium acetate, sodium acetate, potassium acetate, and rubidium acetate; The reaction conditions are: temperature 60-80℃, time 12-24 hours.

7. The preparation method according to claim 6, characterized in that: When preparing the powdered material, the reaction temperature is 60°C, the reaction time is 12 hours, and the molar ratio of the acetic acid base to the 2,3,5,6-tetramercapto-1,4-hydroquinone is: lithium acetate or sodium acetate 20:1, potassium acetate 30:1, and rubidium acetate 5:

1.

8. The preparation method according to claim 6, characterized in that: When preparing the self-supporting thin film material, the reaction temperature is 80℃, the reaction time is 24 hours, and the acetic acid base is lithium acetate or sodium acetate. The molar ratio of acetic acid base to TTHQ is 6:1, and the product is collected at the gas-liquid interface.

9. The use of the organic semiconductor material according to any one of claims 1-4 in the fabrication of supercapacitor electrodes or organic semiconductor devices; The organic semiconductor material is used as an independent electrode in a symmetrical supercapacitor.

10. A supercapacitor comprising the organic semiconductor material of any one of claims 1-4 as an electrode material.

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