A pluggable semi-metallic based non-sacrificial electrode and applications thereof

Abstract

The application discloses a kind of pluggable semi-metallic base non-sacrificial electrode and its application, the electrode is halogen atom doped semi-metallic base C3N4@C (CN) 3 as catalytic material, and is prepared by high-temperature copolymerization with catalytic material in situ attached to porous stainless steel conductive substrate.The semi-metallic base non-sacrificial electrode has strong acid and alkali corrosion resistance, thermal stability and carrier migration and separation capacity, by adjusting the type and proportion of halogen atom doping, the redox capacity of semi-metallic base non-sacrificial electrode catalytic material can be further optimized, can be applied to the oxidation and reduction of electrolyte in plant body and in vivo plant power generation and supply output.

Description

Technical Field

[0001] This invention belongs to the field of energy storage and energy conversion technology, specifically relating to an organic semi-metallic catalytic material and its pluggable electrode device. Technical Background

[0002] Technologies that generate electricity using clean energy, such as wind and solar power, generally feature energy conservation and environmental friendliness. However, these technologies and equipment are expensive, geographically dependent, and susceptible to climate change, requiring further improvement. The future demand for electricity in societal development can be summarized as "safe, efficient, sustainable, and low-cost," reflecting the enduring pursuit of energy development. Plant-based power generation technology uses plants as the primary generator, leveraging electrochemical methods and the plants' own physiological processes to directly or indirectly convert natural light, mechanical energy, and biomass energy into electricity. This green energy technology offers environmentally friendly, abundant, and long-lasting clean energy, showing significant application potential in numerous fields.

[0003] In recent years, researchers both domestically and internationally have conducted preliminary explorations in the field of plant-based power generation, including sacrificial electrode plant galvanic cell power generation technology, photosynthesis-like power generation technology, plant microbial fuel cell power generation technology, and plant-based regional ion concentration perturbation power generation technology. Energy can be extracted from the stems and leaves of lemons, potatoes, plantains, moss leaves, aloe vera, pineapples, tomatoes, lemons, Spartina alterniflora, money trees, and silver poplars, with a maximum output power reaching 100 mW / m². 2 These plant-based batteries can provide power for up to five months, with a maximum open-circuit voltage of 30.6V, a maximum current typically in the microamplitude range, and a load resistance of tens of ohms. However, current plant-based batteries and technologies offer relatively low output voltage and current, resulting in limited power supply capabilities. Their battery life and power density are insufficient for typical applications. In particular, current plant-based batteries use copper and zinc electrodes. During the electrode reaction, the electrode surface reacts with plant tissue fluid, gradually corroding the zinc electrode. Electrode consumption or surface passivation affects the sustainable and stable current output, and can even lead to no current output. Furthermore, zinc ions continuously dissolve and enter the plant during the electrode reaction. If zinc ions accumulate within the plant, it can cause poisoning, limiting their practical application.

[0004] Organic polymers possess advantages such as low toxicity, good biocompatibility, and ease of modification and regulation, demonstrating promising application potential in the biomedical field. As a typical organic polymer material, the half-metal C(CN)3 has been synthesized in recent years and used in photoelectrocatalysis. C(CN)3 has an odd number of valence electrons, resulting in spontaneous magnetization. The magnetic moment is distributed between three adjacent N atoms, and N atoms have smaller and more localized p orbitals than C atoms. The p orbitals of C atoms at molecular structural joints promote ferromagnetic coupling. Integer magnetic moments and ferromagnetism make C(CN)3, based on a triazine ring structure, an intrinsic half-metal. The narrow band gap determines the excellent electrical conductivity of C(CN)3; however, its intrinsic redox ability is suppressed. Therefore, it is necessary to regulate the band structure of C(CN)3 through heteroatom and heteroelement doping modification to optimize its catalytic performance. Summary of the Invention

[0005] The purpose of this invention is to provide a pluggable semi-metallic non-sacrificial electrode and its application in plant batteries. The fabrication process of this semi-metallic pluggable catalytic electrode is controllable, and it has strong resistance to acid and alkali corrosion and high thermal stability. In particular, its excellent redox ability and carrier separation and transport ability enable the electrode to generate electricity through catalysis in plants.

[0006] The technical solution to achieve the purpose of this invention is:

[0007] In a first aspect, the present invention provides a pluggable half-metal-based non-sacrificial electrode, which is formed by in-situ polymerization of a halogen-doped C3N4@C(CN)3-based catalyst on a porous stainless steel substrate. The catalyst contains 0.08-2 wt% halogen atoms, and the catalyst loading on the porous stainless steel substrate is 0.5-5 mg / cm³. 2 .

[0008] Secondly, the present invention also provides a method for preparing the pluggable half-metal-based non-sacrificial electrode described in the first aspect, the specific steps of which are as follows:

[0009] Step a) Disperse tricyanomethanized imidazole ionic liquid, dicyandiamide and ammonium halide as raw materials in deionized water, sonicate for 10-30 min, soak in a porous stainless steel substrate for 0.5-2 h, evaporate the aqueous phase, and obtain a stainless steel electrode with catalyst precursor attached.

[0010] Step b) The stainless steel electrode with the catalyst precursor obtained in step a) is heated to 400-450°C in a tube furnace at a certain heating rate and maintained for 1-2 hours. Then it is heated to 500-550°C for 2-4 hours. After natural cooling to room temperature, it is washed with deionized water and vacuum dried to obtain a pluggable half-metal-based non-sacrificial electrode.

[0011] Furthermore, the tricyanomethanized imidazole ionic liquid is one of 1-ethyl-3-methylimidazolium tricyanomethanized, 1-propyl-3-methylimidazolium tricyanomethanized, 1-butyl-3-methylimidazolium tricyanomethanized, and 1-pentyl-3-methylimidazolium tricyanomethanized.

[0012] Furthermore, the ammonium halide salt is one of ammonium bromide or ammonium iodide.

[0013] Furthermore, the molar ratio of the tricyanomethanized imidazole ionic liquid to dicyandiamide is 1:10 to 1:30.

[0014] Furthermore, the molar ratio of the tricyanomethanized imidazole ionic liquid to the ammonium halide salt is 1:1 to 1:5.

[0015] Furthermore, the heating rate is 2℃ / min to 5℃ / min.

[0016] Thirdly, the present invention also provides the application of the pluggable semi-metallic non-sacrificial electrode described in the first aspect in plant batteries.

[0017] Compared with the prior art, the beneficial effects of the present invention are:

[0018] (1) Unlike traditional sacrificial electrodes for in vivo plant power generation such as Cu and Zn, this invention uses the redox capability of carbon-based catalytic materials to drive the redox reaction of electrolyte ions in the plant to generate electricity for the load. The semi-metallic catalytic material does not decompose during the power generation process, which significantly improves the stability and lifespan of sacrificial electrode type plant batteries.

[0019] (2) Organic half-metal C(CN)3 materials not only have high electrical conductivity and large delocalized electron density, which is conducive to carrier transport, but C(CN)3 also has good catalytic ability, which can promote the redox reaction of electrolytes in plants and generate electricity externally.

[0020] (3) C3N4 and C(CN)3 have similar structures, excellent compatibility and bonding, and outstanding interfacial performance. They can effectively reduce the resistance to charge transport between the two materials and improve the separation ability of photogenerated electrons and holes. Halogen atoms are embedded in the conjugated system composed of C(CN)3 and C3N4 through covalent bonds. Halogen atom doping can further adjust the band structure and conductivity of the half-metal material and improve the catalytic power generation capability of the non-sacrificial electrode.

[0021] The present invention will now be described in further detail with reference to the accompanying drawings. Attached Figure Description

[0022] Figure 1This is a flowchart illustrating the preparation process of a halogen-doped C3N4@C(CN)3 catalytic electrode.

[0023] Figure 2 The images show SEM and EDS elemental analysis of the C3N4@C(CN)3@Br composite catalyst obtained in Example 2.

[0024] Figure 3 The XRD diffraction pattern of the C3N4@C(CN)3@Br composite catalyst obtained in Example 2 is shown.

[0025] Figure 4 The acid-base stability of the C3N4@C(CN)3@Br-based non-sacrificial electrode obtained in Example 2 was evaluated.

[0026] Figure 5 The in vivo plant battery with C3N4@C(CN)3@Br-based non-sacrificial electrode obtained in Example 2.

[0027] Figure 6 The power density curve of the C3N4@C(CN)3@Br-based non-sacrificial electrode obtained in Example 2 is shown.

[0028] Figure 7 The power density curve of the parallel connection of the C3N4@C(CN)3@Br-based non-sacrificial electrode obtained in Example 2. Detailed Implementation

[0029] The following embodiments will enable those skilled in the art to gain a more comprehensive understanding of the present invention.

[0030] Example 1

[0031] Add 0.21 g (2.5 mmol) dicyandiamide, 0.046 g (0.2 mmol) 1-ethyl-3-methylimidazole tricyanomethanylate, and 0.02 g (0.2 mmol) NH4Br to 10 ml of deionized water, sonicate, and stir for 30 min to mix thoroughly. Add a pre-cut porous stainless steel substrate (~0.5 cm). 2 After soaking for 0.5 h, the aqueous phase was evaporated to obtain a stainless steel electrode with the catalyst precursor attached. This catalyst precursor-supported stainless steel electrode was heated to 400 °C at 2 °C / min in a tube furnace, held for 1 h, then heated to 550 °C and held for 2 h. It was then naturally cooled to room temperature, washed with deionized water, and vacuum dried to obtain a pluggable half-metallic non-sacrificial electrode. The preparation process is described in [link to preparation process]. Figure 1 .

[0032] When three pairs of C3N4@C(CN)3@Br electrodes prepared in Example 1 are inserted into the taro plant and connected in series, the maximum power density achievable with an external load resistance of 6kΩ is 15.53mW / m². 2When connected in parallel, the maximum power density achievable with an external load resistance of 5kΩ is 32.36mW / m². 2 .

[0033] Example 2

[0034] 0.21 g (2.5 mmol) of dicyandiamide, 0.046 g (0.2 mmol) of 1-ethyl-3-methylimidazole tricyanomethanyl, and 0.04 g (0.4 mmol) of NH4Br were added to 10 ml of deionized water, sonicated, and stirred for 30 min to mix evenly. A pre-cut porous stainless steel substrate was added and soaked for 0.5 h. The aqueous phase was evaporated to obtain a stainless steel electrode with the catalyst precursor attached. The stainless steel electrode with the catalyst precursor was heated to 400 °C at 2 °C / min in a tube furnace and held for 1 h, then heated to 550 °C and held for 2 h. After natural cooling to room temperature, it was washed with deionized water and vacuum dried to obtain a pluggable half-metallic non-sacrificial electrode.

[0035] Figure 2 The images show the SEM and EDS elemental distribution of the C3N4@C(CN)3@Br electrode catalyst in Example 2. It can be seen that the material has a two-dimensional nanosheet structure, and the carbon, nitrogen, oxygen and bromine elements are relatively uniformly distributed.

[0036] Figure 3 The XRD diffraction pattern of the C3N4@C(CN)3@Br electrode catalyst in Example 2 shows two diffraction peaks at 12.8° and 27.6°, which are attributed to its (100) and (002) crystal planes, respectively. The diffraction peaks of the composite material after different proportions of Br doping are basically consistent with those of the undoped C3N4@C(CN)3, proving that the doping of halogen atoms did not change the crystal structure of the material, but rather replaced some of the organic framework atoms.

[0037] Figure 4 For the acid-base stability evaluation of the C3N4@C(CN)3@Br electrode in Example 2, it can be seen from the figure that after the electrode was soaked in 1M sodium hydroxide and 1M hydrochloric acid for 6 hours, there was no catalytic material detached from the solution, and the catalyst could still be stably attached to the electrode.

[0038] Figure 5 This is an in vivo plant battery for Taroa alopecuroides based on the C3N4@C(CN)3@Br electrode of Example 2.

[0039] Figure 6To investigate the power density of plants with three pairs of C3N4@C(CN)3@Br electrodes from Example 2 inserted in series, under different external resistances, the following data was obtained. As shown in the figure, the power density gradually increases with increasing external resistance, reaching a maximum of 19.53 mW / m² when the external load resistance is 6 kΩ. 2 It then decreased to 9.21 mW / m 2 about.

[0040] Figure 7 To investigate the power density of plants with three pairs of C3N4@C(CN)3@Br electrodes from Example 2 inserted in parallel, under different external resistances, the following data was obtained. As shown in the figure, the power density gradually increases with increasing external resistance, reaching a maximum of 35.35 mW / m² when the external load resistance is 2 kΩ. 2 It then decreased to 6.47 mW / m 2 about.

[0041] Example 3

[0042] 0.21 g (2.5 mmol) of dicyandiamide, 0.046 g (0.2 mmol) of 1-ethyl-3-methylimidazole tricyanomethanyl, and 0.029 g (0.2 mmol) of NH4I were added to 10 ml of deionized water, sonicated, and stirred for 30 min to mix evenly. A pre-cut porous stainless steel substrate was added and soaked for 0.5 h. The aqueous phase was evaporated to obtain a stainless steel electrode with the catalyst precursor attached. The stainless steel electrode with the catalyst precursor was heated to 400 °C at 5 °C / min in a tube furnace and held for 1 h, then heated to 550 °C and held for 2 h. After natural cooling to room temperature, it was washed with deionized water and vacuum dried to obtain a pluggable half-metallic non-sacrificial electrode.

[0043] When three pairs of C3N4@C(CN)3@Br electrodes prepared in Example 3 are inserted into succulent plants and connected in series, the maximum power density achievable with an external load resistance of 2kΩ is 60.32mW / m². 2 When connected in parallel, the maximum power density achievable with an external load resistance of 4kΩ is 50.25mW / m². 2 .

[0044] Example 4

[0045] 0.21 g (2.5 mmol) of dicyandiamide, 0.046 g (0.2 mmol) of 1-ethyl-3-methylimidazole tricyanomethanyl, and 0.04 g (0.4 mmol) of NH4Br were added to 10 ml of deionized water, sonicated, and stirred for 30 min to mix evenly. A pre-cut porous stainless steel substrate was added and soaked for 2 h. The aqueous phase was evaporated to obtain a stainless steel electrode with the catalyst precursor attached. The stainless steel electrode with the catalyst precursor was heated to 400 °C at 2 °C / min in a tube furnace and held for 2 h, then heated to 550 °C and held for 2 h. After natural cooling to room temperature, it was washed with deionized water and vacuum dried to obtain a pluggable half-metallic non-sacrificial electrode.

[0046] When three pairs of C3N4@C(CN)3@Br electrodes prepared in Example 4 are inserted into succulent plants and connected in series, the maximum power density achievable with an external load resistance of 1kΩ is 95.25mW / m². 2 When connected in parallel, the maximum power density achievable with an external load resistance of 1kΩ is 126.28mW / m². 2 .

[0047] Example 5

[0048] 0.21 g (2.5 mmol) of dicyandiamide, 0.046 g (0.2 mmol) of 1-ethyl-3-methylimidazole tricyanomethanyl, and 0.029 g (0.2 mmol) of NH4I were added to 10 ml of deionized water, sonicated, and stirred for 30 min to mix evenly. A pre-cut porous stainless steel substrate was added and soaked for 0.5 h. The aqueous phase was evaporated to obtain a stainless steel electrode with the catalyst precursor attached. The stainless steel electrode with the catalyst precursor was heated to 420 °C at 5 °C / min in a tube furnace and held for 1 h, then heated to 500 °C and held for 2 h. After natural cooling to room temperature, it was washed with deionized water and vacuum dried to obtain a pluggable half-metallic non-sacrificial electrode.

[0049] When three pairs of C3N4@C(CN)3@Br electrodes prepared in Example 5 are inserted into the pointed-tail taro and connected in series, the maximum power density that can be achieved with an external load resistance of 2kΩ is 105.23mW / m². 2 When connected in parallel, the maximum power density achievable with an external load resistance of 5kΩ is 146.25mW / m². 2 .

Claims

1. A pluggable semi-metal based non-sacrificial electrode, characterized in that, The electrode is formed by in-situ polymerization loading of a C3N4@C(CN)3-based catalyst doped with halogen atoms on a porous stainless steel substrate, wherein the content of halogen atoms in the catalyst is 0.08-2wt%, and the loading amount of the catalyst on the porous stainless steel substrate is 0.5-5mg / cm 2 ; The preparation steps are: Step a), tricyanomethanide imidazole ionic liquid, dicyandiamide and ammonium halide salt are dispersed in deionized water as raw materials, ultrasonic treatment for 10-30 min, add porous stainless steel substrate and soak for 0.5-2 h, evaporate the water phase to obtain a stainless steel electrode with catalyst precursor attached; Step b), the stainless steel electrode with catalyst precursor attached obtained in step a) is heated to 400-450 DEG C at a certain heating rate in a tube furnace, maintained for 1-2 h, then raised to 500-550 DEG C, heated for 2-4 h, naturally cooled to room temperature, washed with deionized water and vacuum dried to obtain a pluggable semi-metal-based non-sacrificial electrode; The ammonium halide salt is one of ammonium bromide and ammonium iodide. The molar ratio of tricyanomethanide imidazole ionic liquid to dicyandiamide is 1:10-1:

30.

2. The method of claim 1, wherein the method further comprises: The specific steps are: Step a), tricyanomethanide imidazole ionic liquid, dicyandiamide and ammonium halide salt are dispersed in deionized water as raw materials, ultrasonic treatment for 10-30 min, add porous stainless steel substrate and soak for 0.5-2 h, evaporate the water phase to obtain a stainless steel electrode with catalyst precursor attached; Step b), the stainless steel electrode with catalyst precursor attached obtained in step a) is heated to 400-450 DEG C at a certain heating rate in a tube furnace, maintained for 1-2 h, then raised to 500-550 DEG C, heated for 2-4 h, naturally cooled to room temperature, washed with deionized water and vacuum dried to obtain a pluggable semi-metal-based non-sacrificial electrode.

3. The method of claim 2, wherein, The tricyanomethanide imidazole ionic liquid is one of tricyanomethanide 1-ethyl-3-methylimidazole, tricyanomethanide 1-propyl-3-methylimidazole, tricyanomethanide 1-butyl-3-methylimidazole and tricyanomethanide 1-pentyl-3-methylimidazole.

4. The method of claim 2, wherein, The ammonium halide salt is one of ammonium bromide and ammonium iodide.

5. The method of claim 2, wherein, The molar ratio of tricyanomethanide imidazole ionic liquid to dicyandiamide is 1:10-1:

30.

6. The method of claim 2, wherein, The molar ratio of tricyanomethanide imidazole ionic liquid to ammonium halide salt is 1:1-1:

5.

7. The method of claim 2, wherein, The heating rate is 2 DEG C / min-5 DEG C / min.

8. The pluggable semi-metal-based non-sacrificial electrode of claim 1 is applied in a plant cell.

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