A bio-based glass polymer humidity power generation system and its preparation method

Abstract

The present invention provides a bio-based glass polymer humidity power generation system and its preparation method, which belongs to the field of green energy power generation technology. The present invention prepares a bio-based glass polymer material that can be used in conjunction with electrodes to generate electricity under conditions where a humidity gradient exists. The bio-based glass polymer is a solid formed by the polymerization reaction of tartaric acid, malic acid, or citric acid and 1,4-butanediol diglycidyl ether. When the bio-based glass polymer material is between the positive electrode material and the negative electrode material, efficient output of current can be achieved at room temperature under conditions where a humidity gradient exists. The material of the present invention has the advantages of low preparation cost, strong environmental resistance, stable energy output, reusability, and degradable recycling. It can generate electricity by absorbing water vapor in a natural environment, can be applied to the field of green energy, and has broad application prospects.

Description

Technical Field

[0001] The present invention belongs to the technical field of green energy power generation, and in particular relates to a bio-based glass polymer humidity power generation system and a preparation method thereof. Background Art

[0002] Electricity has become an indispensable part of human life. Faced with energy scarcity, the use of new energy sources is constantly being developed. In recent years, a range of materials have been used for wet and hydropower generation. However, these materials suffer from poor water resistance and mechanical properties. Their structures are susceptible to damage and decomposition in high-temperature and high-humidity environments, and they lack self-repair capabilities. Accidental damage can lead to loss of electrical performance, reducing their lifespan and practicality.

[0003] Glass-like polymers, due to their recyclability, weldability, reshapeability, chemical degradation, and biocompatibility, have shown promising application prospects in a variety of fields, including recyclable adhesives, self-healing coatings, and carbon fiber composites. The bio-based synthesis of glass-like polymers ensures a wide range of raw material sources.

[0004] The principle of the hygroscopic effect mainly involves the hygroscopic properties of biomass nanofiber materials. The surfaces of these materials are rich in hydrophilic groups, such as hydroxyl groups and carboxyl groups. When airflow with high humidity passes through these materials, the steam will be captured in the form of bound water and free water, forming a double electric layer, thereby generating a flow potential. In addition, groups such as carboxyl groups and amino groups in biomass nanofibers can dissociate into freely moving ions, forming ion transmission channels, further generating a potential difference, and thus generating current. According to the hygroscopic effect, in materials containing a large number of hydroxyl groups, moisture will react with the hydroxyl groups, causing the hydroxyl groups to generate carriers. The gradient distribution of functional groups allows the carriers to diffuse from a high concentration section to a low concentration section, thereby forming voltage and current, and realizing the output of electrical energy. Since the movement of carriers is completely spontaneous, this energy conversion method has a high efficiency. Summary of the Invention

[0005] The present invention aims to prepare a bio-based glass polymer wet gas power generation system, comprising a positive electrode material, a negative electrode material and a bio-based glass polymer material, wherein the bio-based glass polymer material is sandwiched between the positive electrode material and the negative electrode material; wherein the positive electrode material is a conductive metal or graphite, and the positive electrode material is provided with at least one opening, and the negative electrode material is a complete conductive metal or graphite sheet, and the bio-based glass polymer material is a solid obtained by polymerization reaction of tartaric acid, malic acid or citric acid and 1,4-butanediol diglycidyl ether; its general structural formula is shown in FIG. Figure 1 、 Figure 2 and Figure 3 shown.

[0006] A method for preparing a bio-based glass polymer humidity power generation system comprises the following steps: dissolving tartaric acid in water, preheating 1,4-butanediol diglycidyl ether at 90±5°C, mixing the tartaric acid aqueous solution and 1,4-butanediol diglycidyl ether, and stirring at 120-130°C to obtain a light yellow homogeneous solution; preheating the light yellow homogeneous solution on a flat plate vulcanizer at 150-170°C to obtain a viscous liquid, and after exhaust treatment, pressurizing and heat-insulating at 150-170°C to obtain the bio-based glass polymer material.

[0007] At least two holes are made on the positive electrode material, and the bio-based glass polymer material is cut into blocks and placed between the positive electrode material and the negative electrode material to ensure that the bio-based glass polymer material touches and conducts electricity with the positive electrode material and the negative electrode material. The blocks are aligned and fixed to ensure that moisture can enter the bio-based glass polymer material, thereby obtaining a bio-based glass polymer moisture power generation system.

[0008] Wherein, the tartaric acid is either malic acid or citric acid.

[0009] Wherein, the molar ratio of the tartaric acid or malic acid or citric acid to 1,4-butanediol diglycidyl ether is 0.8 to 1.2.

[0010] The stirring treatment time is 6.5-7.5h, and the stirring speed is 200-250r / min.

[0011] Wherein, the preheating time is 40 to 80 minutes.

[0012] Among them, the exhaust treatment is to pressurize to 20~25Mpa, release the pressure after reaching the pressure requirement, and perform at least two exhaust operations in succession.

[0013] The pressurized heat preservation treatment time is 4 to 6 hours, and the pressure is 8 to 12 MPa.

[0014] Beneficial effects

[0015] The present invention involves a polyaddition reaction between L-(+)-tartaric acid and 1,4-butanediol diglycidyl ether to produce a cross-linked polymer network connected by ester and ether bonds. Under conditions of a humidity gradient, the material generates a voltage, thereby enabling the output of current.

[0016] The power generation principle of the wet gas power generation system prepared by the present invention is as follows: (1) Generally, room temperature is higher than the glass transition temperature of the power generation system material, that is, the polymer chain segments of the material are mobile in normal environments. (2) Because the chain segments contain a large number of carboxyl and hydroxyl groups, the carboxyl and hydroxyl groups interact with water molecules to release protons. After a large number of protons accumulate, an ion concentration gradient is formed within the material, which promotes the directional movement of protons, thereby generating an electric current. When the internal equilibrium is reached, the water molecules are desorbed again, causing the protons to move in the original direction, forming a secondary current. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 : A simplified structural diagram of the bio-based glass polymer prepared in Example 1 of the present invention.

[0018] Figure 2 : A simplified structural diagram of the bio-based glass polymer prepared in Example 4 of the present invention.

[0019] Figure 3 : A simplified structural diagram of the bio-based glass polymer prepared in Example 5 of the present invention.

[0020] Figure 4 : Schematic diagram of power generation principle of the present invention.

[0021] Figure 5 : Physical diagram of the matrix material structure of the present invention.

[0022] Figure 6 : Schematic diagram of the power generation state of the matrix material of the present invention. DETAILED DESCRIPTION

[0023] In the embodiment, the L-(+)-tartaric acid, D-(+)-tartaric acid, DL-(+)-tartaric acid, malic acid, citric acid, and 1,4-butanediol diglycidyl ether were all purchased from Anaiji Chemical, the wires, copper sheets, and aluminum sheets were all purchased from Taobao, and the multimeter was an OWON B41T model.

[0024] Example 1

[0025] This embodiment provides a method for preparing a bio-based glass polymer moisture power generation system. The bio-based glass polymer moisture power generation system comprises a bio-based glass polymer material, a positive electrode material, and a negative electrode material. The specific preparation method is as follows:

[0026] (1) Preparation method of bio-based glass polymer.

[0027] Weigh 24.25g of L-(+)-tartaric acid and dissolve it in 30mL of water. Weigh 38.88g of 1,4-butanediol diglycidyl ether (the molar ratio of tartaric acid to epoxy resin is 0.8) and preheat it in a 90℃ oil bath. Add L-(+)-tartaric acid aqueous solution dropwise to 1,4-butanediol diglycidyl ether and stir with a stirrer at a speed of 250r / min. Adjust the temperature of the oil bath to 120℃, heat and stir for 7.5h to obtain a light yellow homogeneous solution. Pour the light yellow homogeneous solution into a mold with release paper and preheat it on a 160℃ flat plate vulcanizer for 40min. After preheating, quickly pressurize the mold to 20Mpa for exhaust operation for 5 consecutive times. Finally, the material is cured at 160℃ for 5h. A light yellow transparent solid is obtained, which is a L-TA / BDE bio-based material. The structural formula of the light yellow transparent solid is shown in Figure 1 shown.

[0028] (2) Preparation methods of positive and negative electrode materials.

[0029] In this embodiment, a 3.5 cm × 1.8 cm × 0.1 cm copper sheet is used as the positive electrode, and four small holes with a diameter of 2 mm are made on the top of the copper electrode. A seamless 3.5 cm × 1.8 cm × 0.1 cm copper sheet is used as the negative electrode.

[0030] (3) Assembly of bio-based glass polymer wet gas power generation system.

[0031] The L-TA / BDE bio-based material prepared in step (1) is cut into blocks of 3.5 cm × 1.8 cm × 0.1 cm and placed between the positive electrode and the negative electrode prepared in step (2), ensuring that the L-TA / BDE bio-based material touches the positive electrode material and the negative electrode material and is conductive, and aligned and fixed. The fixing method is to tighten the clips, and ensure that moisture can effectively enter the material to obtain a bio-based glass polymer wet gas power generation system.

[0032] (4) Measurement of the output voltage of the wet gas power generation system.

[0033] Connect the assembled wet gas power generation system to a multimeter, adjust the multimeter to V, and measure the output voltage. The data is shown in the table below.

[0034] Example 1 Output voltage of wet gas power generation system under copper electrode

[0035]

[0036]

[0037] Example 2

[0038] This embodiment provides a method for preparing a bio-based glass polymer moisture power generation system. The bio-based glass polymer moisture power generation system comprises a bio-based glass polymer material, a positive electrode material, and a negative electrode material. The specific preparation method is as follows:

[0039] (1) Preparation method of bio-based glass polymer.

[0040] Weigh 24.25g of D-(+)-tartaric acid and dissolve it in 30mL of water. Weigh 32.68g of 1,4-butanediol diglycidyl ether (molar ratio of tartaric acid to epoxy resin: 1) and preheat in an 85°C oil bath. Add 1,4-butanediol diglycidyl ether dropwise to the D-(+)-tartaric acid aqueous solution while stirring at 200 rpm. Adjust the oil bath temperature to 125°C and heat and stir for 6.5 hours to obtain a pale yellow homogeneous solution. Pour the pale yellow homogeneous solution into a mold lined with release paper and preheat on a flatbed vulcanizer at 170°C for 40 minutes. After preheating, rapidly pressurize the mold to 25 MPa and vent twice. Finally, cure the material at 170°C for 4 hours. The resulting pale yellow, transparent solid is the D-TA / BDE bio-based material.

[0041] (2) Preparation methods of positive and negative electrode materials.

[0042] In this embodiment, a 3.5 cm × 1.8 cm × 0.1 cm copper sheet is used as the positive electrode, and two small holes with a diameter of 2 mm are made on the top of the copper electrode. A seamless 3.5 cm × 1.8 cm × 0.1 cm aluminum sheet is used as the negative electrode.

[0043] (3) Assembly of bio-based glass polymer wet gas power generation system.

[0044] The D-TA / BDE bio-based material prepared in step (1) is cut into blocks of 3.5 cm × 1.8 cm × 0.1 cm and placed between the positive electrode and the negative electrode prepared in step (2), ensuring that the D-TA / BDE bio-based material touches the positive electrode material and the negative electrode material and is conductive, aligned and fixed, and the fixing method is to select a clip to tighten, and ensure that moisture can effectively enter the material to obtain a bio-based glass polymer moisture power generation system.

[0045] (4) Measurement of output voltage of wet gas power generation system

[0046] Connect the assembled wet gas power generation system to a multimeter, adjust the multimeter to V, and measure the output voltage. The data is shown in the table below.

[0047] Example 2 Output voltage of wet gas power generation system under aluminum electrode

[0048]

[0049]

[0050] Example 3

[0051] This embodiment provides a method for preparing a bio-based glass polymer moisture power generation system. The bio-based glass polymer moisture power generation system comprises a bio-based glass polymer material, a positive electrode material, and a negative electrode material. The specific preparation method is as follows:

[0052] (1) Preparation method of bio-based glass polymer.

[0053] Weigh 24.71 g of DL-(+)-tartaric acid and dissolve it in 30 mL of hot water. Weigh 27.65 g of 1,4-butanediol diglycidyl ether (molar ratio of tartaric acid to epoxy resin: 1.2) and preheat in a 95°C oil bath. Add 1,4-butanediol diglycidyl ether dropwise to the DL-(+)-tartaric acid aqueous solution while stirring at 250 rpm. Adjust the oil bath temperature to 120°C and heat and stir for 7.5 hours to obtain a pale yellow homogeneous solution. Pour the pale yellow homogeneous solution into a mold lined with release paper and preheat on a flatbed vulcanizer at 150°C for 80 minutes. After preheating, rapidly pressurize the mold to 25 MPa and vent it five times. Finally, cure the material at 150°C for 6 hours. The resulting pale yellow, transparent solid is the DL-TA / BDE bio-based material.

[0054] (2) Preparation methods of positive and negative electrode materials.

[0055] In this embodiment, a 3.5 cm × 1.8 cm × 0.1 cm graphite sheet is used as the positive electrode, and 8 small holes with a diameter of 1.5 mm are made on the top of the graphite electrode. A seamless 3.5 cm × 1.8 cm × 0.1 cm aluminum sheet is used as the negative electrode.

[0056] (3) Assembly of bio-based glass polymer wet gas power generation system.

[0057] The DL-TA / BDE bio-based material prepared in step (1) is cut into blocks of 3.5 cm × 1.8 cm × 0.1 cm and placed between the positive electrode and the negative electrode prepared in step (2), ensuring that the DL-TA / BDE bio-based material touches the positive electrode material and the negative electrode material and is conductive, and aligned and fixed. The fixing method is to tighten the clips, and ensure that moisture can effectively enter the material to obtain a bio-based glass polymer wet gas power generation system.

[0058] (4) Measurement of output voltage of wet gas power generation system

[0059] Connect the assembled wet gas power generation system to a multimeter, adjust the multimeter to V, and measure the output voltage. The data is shown in the table below.

[0060] Example 3 Output voltage of wet gas power generation system under graphite aluminum electrode

[0061]

[0062]

[0063] Example 4

[0064] This embodiment provides a method for preparing a bio-based glass polymer moisture power generation system. The bio-based glass polymer moisture power generation system comprises a bio-based glass polymer material, a positive electrode material, and a negative electrode material. The specific preparation method is as follows:

[0065] (1) Preparation method of bio-based glass polymer.

[0066] Weigh 24.25g of hydrated citric acid and dissolve it in 30mL of hot water to obtain a citric acid solution. Weigh 21.41g of 1,4-butanediol diglycidyl ether (the molar ratio of hydrated citric acid to epoxy resin is 1) and preheat it in a 90°C oil bath. Add citric acid aqueous solution dropwise to 1,4-butanediol diglycidyl ether and stir with a stirrer at a speed of 250r / min. Adjust the temperature of the oil bath to 120°C, heat and stir for 7.5h to obtain a light yellow homogeneous solution. Pour the light yellow homogeneous solution into a mold with release paper and preheat it on a 160°C flat plate vulcanizer for 40min. After preheating, quickly pressurize the mold to 20Mpa for exhaust operation for 5 consecutive times. Finally, the material is cured, and the curing process is 160°C for 5h. A light yellow transparent solid is obtained, which is a CA / BDE bio-based material. The structural formula of the light yellow transparent solid is shown in Figure 2 shown.

[0067] (2) Preparation methods of positive and negative electrode materials.

[0068] In this embodiment, the positive electrode is a 3.5cm×1.8cm×0.1cm aluminum sheet, and four small holes with a diameter of 2mm are made on the top of the copper electrode. The negative electrode is a seamless 3.5cm×1.8cm×0.1cm copper sheet.

[0069] (3) Assembly of bio-based glass polymer wet gas power generation system.

[0070] The CA / BDE bio-based material prepared in step (1) is cut into blocks of 3.5 cm × 1.8 cm × 0.1 cm and placed between the positive electrode and the negative electrode prepared in step (2), ensuring that the CA / BDE bio-based material touches the positive electrode material and the negative electrode material and is conductive, aligned and fixed, using tape as the fixing method, and ensuring that moisture can effectively enter the material to obtain a bio-based glass polymer moisture power generation system.

[0071] (4) Measurement of output voltage of wet gas power generation system

[0072] Connect the assembled wet gas power generation system to a multimeter, adjust the multimeter to V, and measure the output voltage. The data is shown in the table below.

[0073] Example 4 Output voltage of wet gas power generation system under copper-aluminum electrodes

[0074]

[0075]

[0076] Example 5

[0077] This embodiment provides a method for preparing a bio-based glass polymer moisture power generation system. The bio-based glass polymer moisture power generation system comprises a bio-based glass polymer material, a positive electrode material, and a negative electrode material. The specific preparation method is as follows:

[0078] (1) Preparation method of bio-based glass polymer.

[0079] Weigh 24.25g of malic acid and dissolve it in 30mL of water to obtain a malic acid aqueous solution. Weigh 33.56g of 1,4-butanediol diglycidyl ether (the molar ratio of malic acid to epoxy resin is 1.1) and preheat it in a 90℃ oil bath. Add malic acid aqueous solution dropwise to 1,4-butanediol diglycidyl ether and stir with a stirrer at a speed of 250r / min. Adjust the temperature of the oil bath to 120℃, heat and stir for 7.5h to obtain a light yellow homogeneous solution. Pour the light yellow homogeneous solution into a mold with release paper and preheat it on a 160℃ flat plate vulcanizer for 40min. After preheating, quickly pressurize the mold to 20Mpa for exhaust operation for 5 consecutive times. Finally, the material is cured, and the curing process is 160℃ for 5h. A light yellow transparent solid is obtained, which is a MA / BDE bio-based material. The structural formula of the light yellow transparent solid is shown in Figure 3 shown.

[0080] (2) Preparation methods of positive and negative electrode materials.

[0081] In this embodiment, a 3.5 cm × 1.8 cm × 0.1 cm copper sheet is used as the positive electrode, and four small holes with a diameter of 2 mm are made on the top of the copper electrode. A seamless 3.5 cm × 1.8 cm × 0.1 cm copper sheet is used as the negative electrode.

[0082] (3) Assembly of bio-based glass polymer wet gas power generation system.

[0083] The MA / BDE bio-based material prepared in step (1) is cut into blocks of 3.5 cm × 1.8 cm × 0.1 cm and placed between the positive electrode and the negative electrode prepared in step (2), ensuring that the MA / BDE bio-based material touches the positive electrode material and the negative electrode material and is conductive, and aligned and fixed. The fixing method is to use a rubber band to tie it, and ensure that moisture can effectively enter the material to obtain a bio-based glass polymer moisture power generation system.

[0084] (4) Measurement of output voltage of wet gas power generation system

[0085] Connect the assembled wet gas power generation system to a multimeter, adjust the multimeter to V, and measure the output voltage. The data is shown in the table below.

[0086] Example 1 Output voltage of wet gas power generation system under copper electrode

[0087]

[0088]

[0089] Example 6

[0090] (1) Preparation method of bio-based glass polymer.

[0091] Weigh 24.25g of L-(+)-tartaric acid and dissolve it in 30mL of hot water. Weigh 38.88g of 1,4-butanediol diglycidyl ether and preheat in a 90°C oil bath (molar ratio of tartaric acid to epoxy resin: 0.8). Add 1,4-butanediol diglycidyl ether dropwise to the L-(+)-tartaric acid aqueous solution while stirring with a stirrer at 250 rpm. Adjust the oil bath temperature to 120°C and heat and stir for 7.5 hours to obtain a pale yellow homogeneous solution. Pour the pale yellow homogeneous solution into a mold lined with release paper and preheat on a flatbed vulcanizer at 160°C for 40 minutes. After preheating, rapidly pressurize the mold to 20 MPa and vent it five times. Finally, cure the material at 160°C for 5 hours to obtain a pale yellow, transparent solid.

[0092] (2) Preparation methods of positive and negative electrode materials.

[0093] In this embodiment, the positive electrode is a 3.5cm×1.8cm×0.1cm iron sheet, and four small holes with a diameter of 2mm are made on the top of the iron electrode. The negative electrode is a seamless 3.5cm×1.8cm×0.1cm iron sheet.

[0094] (3) Assembly of bio-based glass polymer wet gas power generation system.

[0095] The MA / BDE bio-based material prepared in step (1) is cut into blocks of 3.5 cm × 1.8 cm × 0.2 cm and placed between the positive electrode and the negative electrode prepared in step (2), ensuring that the TA / BDE bio-based material touches the positive electrode material and the negative electrode material and is conductive, and aligned and fixed. The fixing method is to use a rubber band to tie it, and ensure that moisture can effectively enter the material to obtain a bio-based glass polymer moisture power generation system.

[0096] (3) Use a bio-based glass polymer moisture power generation system to light up a small light bulb.

[0097] Connect the positive and negative poles of the assembled moisture power generation system to the positive and negative poles of the small light bulb respectively. When there is moisture, the light bulb will light up.

[0098] Obviously, the present invention proposes a bio-based glass polymer moisture power generation system, the size of its positive and negative electrode materials and bio-based glass polymer materials will not affect the operation of its power generation system. The larger the material, the greater the power generation.

Claims

1. A bio-based glass polymer humidity power generation system, characterized by: The bio-based glass polymer humidity power generation system includes a positive electrode material, a negative electrode material, and a bio-based glass polymer material, wherein the bio-based glass polymer material is sandwiched between the positive electrode material and the negative electrode material; wherein the positive electrode material is a conductive metal or graphite, and the positive electrode material is provided with at least one opening; the negative electrode material is a complete conductive metal or graphite sheet; the bio-based glass polymer material is a solid formed by the polymerization reaction of L-(+)-tartaric acid, malic acid, or lemonade and 1,4-butanediol diglycidyl ether; and its general structural formula is as follows: ； and 。 2. A method for preparing the bio-based glass polymer humidity power generation system according to claim 1, characterized in that: The preparation method of the bio-based glass polymer material comprises the following steps: dissolving L-(+)-tartaric acid in water, preheating 1,4-butanediol diglycidyl ether at 90±5° C., mixing the aqueous solution of L-(+)-tartaric acid and 1,4-butanediol diglycidyl ether, and stirring at 120-130° C. to obtain a light yellow homogeneous solution; preheating the light yellow homogeneous solution on a flat plate vulcanizer at 150-170° C. to obtain a viscous liquid, and after degassing, pressurizing and heat-insulating at 150-170° C. to obtain the bio-based glass polymer material; At least two holes are made on the positive electrode material, and the bio-based glass polymer material is cut into blocks and placed between the positive electrode material and the negative electrode material to ensure that the bio-based glass polymer material touches and conducts electricity with the positive electrode material and the negative electrode material. The blocks are aligned and fixed to ensure that moisture can enter the bio-based glass polymer material, thereby obtaining a bio-based glass polymer moisture power generation system.

3. The method for preparing the bio-based glass polymer humidity power generation system according to claim 2, characterized in that: The L-(+)-tartaric acid is either malic acid or citric acid.

4. The method for preparing the bio-based glass polymer humidity power generation system according to claim 3, characterized in that: The molar ratio of the L-(+)-tartaric acid, malic acid or citric acid to 1,4-butanediol diglycidyl ether is 0.8 to 1.

2.

5. The method for preparing the bio-based glass polymer humidity power generation system according to claim 3, wherein: The stirring treatment time is 6.5-7.5 h, and the stirring speed is 200-250 r / min.

6. The method for preparing the bio-based glass polymer humidity power generation system according to claim 3, wherein: The preheating time is 40 to 80 minutes.

7. The method for preparing a bio-based glass polymer humidity power generation system according to claim 3, wherein: The exhaust treatment is to pressurize to 20 ~ 25 MPa, release the pressure after reaching the pressure requirement, and perform the exhaust operation at least twice in succession.

8. The method for preparing a bio-based glass polymer humidity power generation system according to claim 3, wherein: The pressurized heat preservation treatment time is 4 to 6 hours, and the pressure is 8 to 12 MPa.

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