Photocatalytic-thermochemical cell device for integration of offshore power generation and hydrogen energy

Abstract

The present application relates to a kind of photocatalysis-thermal chemical cell device for offshore power generation and hydrogen energy integration, the device is made of multiple photocatalysis-thermal chemical cell units connected in series, wherein each photocatalysis-thermal chemical cell unit includes polyacrylic hydrogel matrix as thermal chemical cell unit matrix, the polyacrylic hydrogel matrix contains potassium ferricyanide and potassium ferrocyanide, wherein the molar ratio of potassium ferricyanide and potassium ferrocyanide is 3:5~5:3, in addition, the content of FeCN 3‑ 0.1M~0.34M in 1000g PAA, oxygen production catalyst and hydrogen production catalyst are respectively introduced at the end close to light source and the end away from light source of the polyacrylic hydrogel matrix, 10g~40g oxygen production catalyst and 10g~35g hydrogen production catalyst are respectively introduced in 1000g polyacrylic hydrogel.The present application solves the expensive cost of current submarine power transmission system.

Description

Technical Field

[0001] This invention belongs to the fields of thermoelectricity and photocatalysis, and specifically relates to a photocatalytic-thermochemical battery device for integrated marine power generation and hydrogen energy. Background Technology

[0002] The motivation behind the field of solar energy conversion is to help us reduce our dependence on fossil fuels to meet our energy needs. While the use of fossil fuels has made invaluable contributions to the significant improvements in our living standards over the past two centuries, almost everyone now clearly recognizes the potentially serious consequences of continuing to burn fossil fuels and emit carbon dioxide into the atmosphere. Solar energy is a renewable, carbon-free energy source and is by far the most abundant energy source, accounting for over 99% of all renewable energy on Earth. However, the multi-stage utilization of solar energy is not yet fully developed. Meanwhile, in my country's current offshore energy supply architecture, off-site power supply still dominates, resulting in high transmission costs. Therefore, developing low-cost, green in-situ offshore energy supply devices is crucial. Summary of the Invention

[0003] In view of the above-mentioned limitations of the prior art, this invention proposes a photocatalytic-thermochemical battery device for integrated offshore power generation and hydrogen energy. The device of this invention can float on the sea surface and, under sunlight, can simultaneously generate electricity and hydrogen energy, thus solving the problem of the high cost of current submarine power transmission systems. Furthermore, it enables the simultaneous collection of hydrogen and electricity to power offshore equipment.

[0004] A photocatalytic-thermal chemical cell device for integrated offshore power generation and hydrogen energy is disclosed. The device comprises multiple photocatalytic-thermal chemical cell units connected in series by wires. Each photocatalytic-thermal chemical cell unit includes a polyacrylic acid hydrogel (PAA) matrix as the base material, the PAA matrix containing potassium ferricyanide (FeCN). 3- ) and potassium ferrocyanide (FeCN) 4- Redox couple, wherein the potassium ferricyanide (FeCN) 3- ) and potassium ferrocyanide (FeCN) 4- The molar ratio of FeCN in PAA is 3:5 to 5:3, preferably 1:1.15 to 1:1.45, and more preferably 1:1.3. Additionally, the FeCN content in 1000g PAA... 3-The content is 0.1M to 0.34M, preferably 0.26M. An oxygen-generating catalyst and a hydrogen-generating catalyst are introduced into the polyacrylic acid hydrogel matrix at the end near the light source (hot end or upper end) and the end away from the light source (cold end or lower end), respectively. 10g to 40g of the oxygen-generating catalyst and 10g to 35g of the hydrogen-generating catalyst are introduced into 1000g of PAA, preferably 27g and 22g, respectively. The oxygen-generating catalyst and the hydrogen-generating catalyst are preferably oxygen-deficient tungsten oxide (O₂). v -WO3) and sulfur-deficient zinc indium sulfide (S v -ZIS). In each photocatalytic-thermal chemical cell unit, a copper mesh serving as a hot-end electrode is fixed to the end of the polyacrylic acid hydrogel matrix near the light source using transparent conductive adhesive. At the end of the polyacrylic acid hydrogel matrix away from the light source in each photocatalytic-thermal chemical cell unit, a copper foil serving as a cold-end electrode is sealed with transparent epoxy resin. The hot-end and cold-end electrodes of the multiple photocatalytic-thermal chemical cell units are connected in series sequentially using copper tape.

[0005] The photocatalytic-thermochemical cell unit described above can be prepared in the following ways:

[0006] (a) Preparation of FeCN 3- and FeCN 4- FeCN with a molar ratio of 3:5 to 5:3 4- / FeCN 3- Electrolyte solution;

[0007] (b) FeCN 4- / FeCN 3- Electrolyte solution, acrylic acid, and 2-hydroxyethyl methacrylate (HEMA) were mixed thoroughly. Then, ethylene glycol dimethacrylate (EDGMA), 5 wt% ammonium persulfate (APS) solution, and N,N,N',N'-tetramethylethylenediamine (TMEDA) were added and mixed thoroughly to obtain PAA-FeCN. 3- / 4- Mixed solution, in which 1 mL of FeCN 3- / FeCN 4- For the electrolyte solution, the amounts of acrylic acid, HEMA, EDGMA, APS solution and TMEDA are 0.3-0.5g, 2-4g, 20-40mg, 0.2-0.4mL and 0.2-0.4mL, respectively.

[0008] (c) FeCN containing an oxygen-generating catalyst dispersed therein 4- / FeCN 3-Acrylic acid, 2-hydroxyethyl methacrylate (HEMA), ethylene glycol dimethacrylate (EDGMA), 5 wt% ammonium persulfate (APS) solution, and N,N,N',N'-tetramethylethylenediamine (TMEDA) were added to the electrolyte solution and mixed thoroughly to obtain the oxygen-generating catalyst / PAA-FeCN. 3- / 4- Mixed solution, in which 1 mL of FeCN 4- / FeCN 3- In the electrolyte solution, the amounts of oxygen-generating catalyst, acrylic acid, HEMA, EDGMA, APS solution, and TMEDA are 10mg–40mg: 0.3–0.5g: 2–4g: 20–40mg: 0.2–0.4mL: 0.2–0.4mL, respectively.

[0009] (d) FeCN containing a hydrogen production catalyst dispersed therein 4- / FeCN 3- Acrylic acid, 2-hydroxyethyl methacrylate (HEMA), ethylene glycol dimethacrylate (EDGMA), 5 wt% ammonium persulfate solution (APS), and N,N,N',N'-tetramethylethylenediamine (TMEDA) were added to the electrolyte solution and mixed thoroughly to obtain PAA-FeCN. 3- / 4 / Hydrogen production catalyst mixed solution, wherein 1 mL of FeCN 4- / FeCN 3- Based on the electrolyte solution, the amounts of hydrogen-producing catalyst, acrylic acid, HEMA, EDGMA, APS solution, and TMEDA are 10mg–35mg: 0.3–0.5g: 2–4g: 20–40mg: 0.2–0.4mL: 0.2–0.4mL, respectively.

[0010] (e) Transfer the mixed solution from step (d) into a mold and polymerize it at a temperature of 313K to 323K for a time of 10 to 20 minutes. Then transfer the mixed solution from step (b) into a mold and polymerize it at a temperature of 313K to 323K for a time of 10 to 20 minutes. Finally, transfer the mixed solution from step (c) into a mold and polymerize it at a temperature of 313K to 323K for a time of 2 to 3 hours.

[0011] The photocatalytic-thermochemical battery device of the present invention, which integrates offshore power generation and hydrogen energy, solves the problem of the high cost of current submarine power transmission systems. Furthermore, it enables the simultaneous collection of hydrogen and electrical energy to power offshore equipment. Attached Figure Description

[0012] Figure 1 This is a mechanism diagram of the photocatalytic-thermochemical battery unit of the present invention.

[0013] Figure 2 The O in the photocatalytic-thermochemical cell unit of this invention v- WO3 / PAA-FeCN 3- / 4- / S v -ZIS diagram.

[0014] Figure 3 This is a diagram of the device for the large-area photocatalytic-thermochemical cell of the present invention.

[0015] Figure 4 The voltage, solar intensity, and amount of hydrogen and oxygen produced by the photocatalytic-thermochemical cell device of the present invention are shown under natural light conditions. Detailed Implementation

[0016] To better understand the purpose, technical solution, and advantages of the present invention, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments.

[0017] This invention, based on the design and synthesis of photocatalytic-thermochemical battery units, connects them in series using wires (copper wires) to construct a large-area photocatalytic-thermochemical battery device. Under illumination, the device generates a photothermal effect. Under a temperature difference field, the electrolyte redox couple in the system undergoes redox reactions at the hot and cold ends, respectively, thereby generating voltage, which can power small marine equipment. Simultaneously, the photocatalyst in the system undergoes hydrogen and oxygen production reactions, and the hydrogen and oxygen are further collected as stored clean energy to power other equipment. Figure 1 A mechanism diagram of the photocatalytic-thermochemical cell unit of the present invention is shown.

[0018] Preparation of photocatalytic-thermochemical cell units

[0019] 0.042 grams of FeCN 4- and 0.028 grams of FeCN 3- Dispersed in 0.33 mL of deionized water, 0.33 mL of 0.34 M / 0.26 M FeCN was prepared. 4- / FeCN 3- Electrolyte solution.

[0020] The photocatalyst for sulfur-deficient zinc indium sulfide (S) v -ZIS) powder (2.5mg) and oxygen-deficient tungsten oxide (O v -WO3) powder (3 mg) was dispersed in 0.11 mL of 0.34 M / 0.26 M FeCN. 4- / FeCN 3-The electrolyte solution was ultrasonically stirred for 30 min, then 0.046 g acrylic acid (AA), 0.33 g 2-hydroxyethyl methacrylate (HEMA), 3.7 mg ethylene glycol dimethacrylate (EDGMA), 0.03 mL (5 wt%) of ammonium persulfate (APS) solution, and 0.03 mL of N,N,N',N'-tetramethylethylenediamine (TMEDA) were added and mixed thoroughly to obtain PAA-FeCN. 3- / 4 / S v -ZIS and O v -WO3 / PAA-FeCN 3- / 4- A mixed solution.

[0021] In 0.11 mL of 0.34 M / 0.26 M FeCN 4- / FeCN 3- 0.046 g acrylic acid (AA), 0.33 g 2-hydroxyethyl methacrylate (HEMA), 3.7 mg ethylene glycol dimethacrylate (EDGMA), 0.03 mL 5 wt% ammonium persulfate (APS) solution, and 0.03 mL N,N,N',N'-tetramethylethylenediamine (TMEDA) were added to the electrolyte solution and mixed thoroughly to obtain PAA-FeCN. 3- / 4 A mixed solution.

[0022] Then the corresponding PAA-FeCN 3- / 4 / S v -ZIS、PAA-FeCN 3- / 4- and O v -WO3 / PAA-FeCN 3- / 4- The mixed solution was sequentially transferred into a cylindrical mold (diameter: 20 mm, height: 9 mm), and polymerized at 323 K for 10 min, 10 min, and 3 hours respectively. Finally, O was obtained. v- WO3 / PAA-FeCN 3- / 4- / S v -ZIS photocatalytic-thermochemical cell unit.

[0023] Figure 2 The O in the photocatalytic-thermochemical cell unit of this invention v- WO3 / PAA-FeCN 3- / 4- / S v The diagram of -ZIS shows a cylindrical shape with a diameter of 20 mm and a height of 9 mm. The battery cell structure consists of an oxygen-generating catalyst O at the top. v -WO3, with hydrogen production catalyst S at the bottom. v -ZIS hydrogel polyacrylic acid (PAA-FeCN) containing redox electrolyte 3- / 4-The battery consists of a copper mesh as the hot end electrode, which is fixed to the hot end (or near the light source or at the top) of each battery cell using transparent conductive adhesive, and a copper foil as the cold end electrode, which is sealed to the cold end (or away from the light source or at the bottom) of each battery cell using transparent epoxy resin.

[0024] Larger area O v- WO3 / PAA-FeCN 3- / 4- / S v Preparation of -ZIS photocatalytic-thermochemical cell device: In the synthesis of O v -WO3 / PAA-FeCN 3- / 4- / S v Based on the ZIS photocatalytic-thermochemical cell unit, a large-area photocatalytic enhanced thermochemical cell device was gradually fabricated by using a transparent copper mesh as the hot electrode and copper foil as the cold electrode, connecting each sample in series with copper wire. First, we prepared a 9-unit reaction module (90mm × 90mm) made of polymethyl methacrylate (PMMA). Each unit was a cylindrical mold (diameter: 20mm, height: 9mm). Nine O v -WO3 / PAA-FeCN 3- / 4- / S v The ZIS system is connected in series via copper wire. Finally, the four isolated PMMA reaction modules are connected in series to form a large-area system of 36 elements (see [link]). Figure 3 In addition, we installed a gas collection bag on the PMMA reactor to collect the hydrogen and oxygen produced by the overall photocatalytic water splitting.

[0025] O of photocatalytic-thermochemical cell device v- WO3 / PAA-FeCN 3- / 4- / S v -ZIS Thermoelectric Performance Testing

[0026] Each battery cell uses a copper mesh as the hot-end electrode and copper foil as the cold-end electrode, with the bottom wrapped in epoxy resin. A large-area device with 36 battery cells connected in series was placed on the surface of a flowing river to simulate a marine environment. On July 7, 2022, from 10:00 to 16:00 at Northwestern Polytechnical University in Xi'an, under natural light conditions, a photocatalytic reaction and photothermal effect were induced to generate voltage. The system voltage was monitored using a voltmeter, and the highest voltage reached was 4.4V. (See [link to documentation]). Figure 4 .

[0027] O thermoelectric-photocatalytic device v -WO3 / PAA-FeCN 3- / 4- / S v -ZIS photocatalytic performance test

[0028] We connected gas collection bags to each reactor module (90mm × 90mm). A large-area device with 36 battery cells connected in series was placed on the surface of a flowing river to simulate a marine environment. On July 7, 2022, from 10:00 to 16:00 at Northwestern Polytechnical University in Xi'an, photocatalytic generation of H2 and O2 was triggered under natural light conditions. Samples were taken every hour and injected into a chromatogram for testing. Offline gas chromatography was used to monitor the amount of H2 and O2 produced. After 6 hours of light exposure, the hydrogen production reached 0.5 mmol and the oxygen production reached 0.24 mmol. (See [link to relevant documentation]). Figure 4 .

[0029] This invention provides a large-area photocatalytic-thermochemical cell device integrating power generation and hydrogen energy for marine applications. Each photocatalytic-thermochemical cell is connected in series with wires to form a large-area device capable of storing 36 samples. Placed on a flowing river, under real sunlight, the voltage of the large-area device can reach 4.4V. Simultaneously, the system exhibits excellent photocatalytic hydrogen and oxygen production performance, producing 0.5 mmol of hydrogen and 0.24 mmol of oxygen. This device solves the problem of off-site power supply required for current small-scale marine equipment, reducing costs. Furthermore, the device generates clean hydrogen energy, which can be stored as a fuel source for other marine equipment.

Claims

1. A photocatalytic-thermochemical cell device for integrated offshore power generation and hydrogen energy, the device comprising multiple photocatalytic-thermochemical cell units connected in series, wherein each photocatalytic-thermochemical cell unit includes a polyacrylic acid hydrogel matrix as the cell matrix, the polyacrylic acid hydrogel matrix containing potassium ferrocyanide and potassium ferrocyanide, wherein the molar ratio of potassium ferrocyanide to potassium ferrocyanide is 3:5 to 5:3, and furthermore, 1000g PAA contains FeCN 3- The content is 0.1M to 0.34M. An oxygen-generating catalyst and a hydrogen-generating catalyst are introduced into the polyacrylic acid hydrogel matrix at the end near the light source and the end away from the light source, respectively. 10g to 40g of oxygen-generating catalyst and 10g to 35g of hydrogen-generating catalyst are introduced into 1000g of polyacrylic acid hydrogel.

2. The photocatalytic-thermochemical cell device according to claim 1, wherein the potassium ferricyanide (FeCN) 3- and potassium ferrocyanide (FeCN) 4- The molar ratio is 1:1.15 to 1:1.

45.

3. The photocatalytic-thermochemical cell device according to claim 1, wherein the potassium ferricyanide (FeCN) 3- and potassium ferrocyanide (FeCN) 4- The molar ratio is 1:1.

3.

4. The photocatalytic-thermochemical cell device according to claim 1, wherein 1000g of polyacrylic acid hydrogel contains potassium ferricyanide (FeCN). 3- The content is 0.26M.

5. The photocatalytic-thermochemical cell device according to claim 1, wherein 27g and 22g of oxygen-producing catalyst and hydrogen-producing catalyst are respectively introduced into 1000g of polyacrylic acid hydrogel.

6. The photocatalytic-thermochemical cell device according to claim 1, wherein the oxygen-producing catalyst and the hydrogen-producing catalyst are oxygen-deficient tungsten oxide and sulfur-deficient zinc indium sulfide, respectively.

7. The photocatalytic-thermal chemical cell device according to claim 1, wherein a copper mesh serving as a hot-end electrode is fixed to the end of the polyacrylic acid hydrogel matrix of each photocatalytic-thermal chemical cell unit near the light source by a transparent conductive adhesive, and a copper foil serving as a cold-end electrode is sealed to the end of the polyacrylic acid hydrogel matrix of each photocatalytic-thermal chemical cell unit away from the light source by a transparent epoxy resin, and the hot-end electrodes and cold-end electrodes of the plurality of photocatalytic-thermal chemical cell units are connected in series.

Images