Coupling dynamic decoupling water electrolysis electricity-hydrogen cogeneration system and method based on HATN-Zn double-effect battery

Abstract

The invention relates to an HATN-Zn double-effect battery coupling dynamic decoupling water electrolysis electricity-hydrogen co-production system and method, and the system comprises an HATN-Zn battery unit which is used for storing or releasing electric energy through the reversible oxidation-reduction reaction of HATN and Zn; the hydrogen production electrolytic tank is used for generating hydrogen through a hydrogen evolution reaction in an acid environment, performing oxidation regeneration on the HATN electrode in a reduction state, and charging the positive electrode of the HATN-Zn battery unit with energy; and the oxygen production electrolytic tank is used for generating oxygen through an oxygen evolution reaction in an alkaline environment, carrying out reduction regeneration on the Zn electrode in an oxidation state, and charging the negative electrode of the HATN-Zn battery unit with energy. By the adoption of the technical scheme, space-time decoupling of electric energy and hydrogen energy can be achieved through cooperation of dynamic decoupling water electrolysis and the double-effect battery so as to improve stability, dendritic crystals are avoided through combination of bipolar membrane regulation and control and electrolyte circulation, fluctuation new energy input is adapted, and therefore the overall energy conversion efficiency is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of new energy storage and conversion technology, in particular to a HATN-Zn dual-effect battery coupled dynamic decoupling water electrolysis and hydrogen co-production system and method. BACKGROUND

[0002] As a zero-carbon energy carrier, hydrogen energy can not only replace fossil fuels and be applied to difficult-to-abate fields such as steel smelting and chemical synthesis, but also can be used as a long-period energy storage medium to alleviate the temporal and spatial mismatch of new energy power generation such as photovoltaic and wind power generation, and the hydrogen co-production technology becomes a key path to realize the large-scale production of hydrogen energy.

[0003] In the prior art, traditional alkaline electrolytic tank hydrogen production technology, energy storage devices such as lithium ion batteries supporting electrolysis systems, and zinc-based battery energy storage technology are usually used to realize the coordinated operation of new energy power generation and hydrogen production; among them, the traditional alkaline electrolytic tank hydrogen production technology is rigidly coupled with hydrogen and oxygen production, which will be frequently started and stopped under fluctuating new energy input, resulting in poor stability and catalytic layer degradation; in the energy storage device such as lithium ion battery supporting electrolysis system, the coordination efficiency of the energy storage device such as lithium ion battery and the electrolytic tank is low, which is difficult to match the long-period operation demand; and the zinc-based battery cannot be stably matched with fluctuating input due to dendrite growth problems.

[0004] It should be noted that the information disclosed in the above background section is only used to strengthen the understanding of the background of the present disclosure, and therefore can include information that does not constitute prior art known to those of ordinary skill in the art. SUMMARY

[0005] In view of the above problems, the present application provides a HATN-Zn dual-effect battery coupled dynamic decoupling water electrolysis and hydrogen co-production system and method, which can dynamically decouple water electrolysis and dual-effect battery to realize the temporal and spatial decoupling of electric energy and hydrogen energy to improve stability.

[0006] To achieve the purpose of the present application, the present application provides the following technical solutions:

[0007] In a first aspect, the present application provides a HATN-Zn dual-effect battery coupled dynamic decoupling water electrolysis and hydrogen co-production system, comprising:

[0008] The HATN-Zn battery unit comprises a HATN electrode in an oxidation state, a Zn electrode in a reduction state, and an external power supply, and is used for storing or releasing electric energy through reversible oxidation and reduction reactions of HATN and Zn;

[0009] a hydrogen production electrolytic cell, comprising the HATN electrode in a reduced state, a hydrogen evolution Pt electrode and a first power source, for generating hydrogen by hydrogen evolution reaction in an acidic environment, and oxidizing the HATN electrode in a reduced state to regenerate it, to charge the HATN-Zn battery unit anode;

[0010] an oxygen production electrolytic cell, comprising the Zn electrode in an oxidized state, an oxygen evolution Ru / Ir electrode and a second power source, for generating oxygen by oxygen evolution reaction in an alkaline environment, and reducing the Zn electrode in an oxidized state to regenerate it, to charge the HATN-Zn battery unit cathode;

[0011] wherein the hydrogen production electrolytic cell and the oxygen production electrolytic cell are in communication and separated by a diaphragm.

[0012] In a possible implementation, the HATN-Zn double-effect battery-based coupled dynamic decoupling water electrolysis-electricity hydrogen co-production system further comprises an oxygen-containing strong acid solution tank and a saturated ZnO alkali hydroxide solution tank; the oxygen-containing strong acid solution tank is in communication with the hydrogen production electrolytic cell through an acid liquid input pipeline and an acid liquid output pipeline, to form a circulation loop of the oxygen-containing strong acid solution; the saturated ZnO alkali hydroxide solution tank is in communication with the oxygen production electrolytic cell through an alkali liquid input pipeline and an alkali liquid output pipeline, to form a circulation loop of the saturated ZnO alkali hydroxide solution.

[0013] In a possible implementation, each of the acid liquid input pipeline, the acid liquid output pipeline, the alkali liquid input pipeline and the alkali liquid output pipeline is provided with a peristaltic pump.

[0014] In a possible implementation, the HATN-Zn double-effect battery-based coupled dynamic decoupling water electrolysis-electricity hydrogen co-production system further comprises a hydrogen storage tank and an oxygen storage tank, the hydrogen storage tank is in communication with the hydrogen production electrolytic cell through a hydrogen gas output pipeline, for storing hydrogen gas output by the hydrogen production electrolytic cell, and the oxygen storage tank is in communication with the oxygen production electrolytic cell through an oxygen gas output pipeline, for storing oxygen gas output by the oxygen production electrolytic cell.

[0015] In a possible implementation, the hydrogen storage tank and the oxygen storage tank are respectively connected to a gas purification device, and the gas purification device is any one or more of a desiccator and a particulate filter.

[0016] In a possible implementation, the oxygen-containing strong acid solution is sulfuric acid solution or nitric acid solution, and the hydrogen ion concentration ranges from 2.0 to 4.0 M.

[0017] In a possible implementation, the saturated ZnO alkali hydroxide solution is composed of ZnO and a sodium hydroxide solution or ZnO and a potassium hydroxide solution, the concentration of the sodium hydroxide solution and the potassium hydroxide solution ranges from 2.0 M to 4.0 M, and the saturated concentration of the ZnO ranges from 0.1 M to 0.3 M.

[0018] In a possible implementation, the hydrogen evolution Pt electrode is a porous titanium-based electrode coated with a platinum-carbon catalyst, and the oxygen evolution Ru / Ir electrode is a porous titanium-based electrode coated with an IrO2-RuO2 mixed oxide.

[0019] In a possible implementation, the HATN-Zn battery unit has a first switch, the hydrogen production electrolytic cell has a second switch, and the oxygen production electrolytic cell has a third switch, wherein the first switch is used to control the HATN electrode and the Zn electrode to be powered by the external power supply, the second switch is used to control the first power supply to power the HATN electrode and the hydrogen evolution Pt electrode, and the third switch is used to control the second power supply to power the Zn electrode and the oxygen evolution Ru / Ir electrode.

[0020] In a second aspect, the application further provides a dynamic decoupling water electrolysis and electricity hydrogen co-production method based on a HATN-Zn dual-effect battery coupling, which is used to control the dynamic decoupling water electrolysis and electricity hydrogen co-production system based on the HATN-Zn dual-effect battery coupling, and the method comprises the following steps:

[0021] The acid liquid input pipeline, the acid liquid output pipeline, the alkali liquid input pipeline, the alkali liquid output pipeline, the hydrogen output pipeline, and the oxygen output pipeline are closed, the second switch and the third switch are disconnected, the first switch is closed, and the HATN-Zn battery composed of the HATN electrode in the oxidation state and the Zn electrode in the reduction state supplies power to the external power supply;

[0022] The acid liquid input pipeline, the acid liquid output pipeline, and the hydrogen output pipeline are opened, the first switch is disconnected, the second switch is closed, the first power supply supplies power to the HATN electrode in the reduction state to perform an oxidation reaction and charges, and at the same time, the first power supply supplies power to the hydrogen evolution Pt electrode to generate a reduction reaction and generate hydrogen, and the hydrogen is input into the hydrogen storage tank through the hydrogen output pipeline;

[0023] The alkali liquid input pipeline, the alkali liquid output pipeline, and the oxygen output pipeline are opened, the first switch is disconnected, the third switch is closed, the second power supply supplies power to the Zn electrode in the oxidation state to perform a reduction reaction and charges, and at the same time, the second power supply supplies power to the oxygen evolution Ru / Ir electrode to generate an oxidation reaction and generate oxygen, and the oxygen is input into the hydrogen storage tank through the oxygen output pipeline.

[0024] The technical solution provided in the application can have the following beneficial effects:

[0025] By the HATN-Zn double-effect battery coupling dynamic decoupling water electrolysis electric hydrogen cogeneration system and method provided in the application, through the dynamic decoupling water electrolysis and the collaborative operation of the HATN-Zn double-effect battery, a three-step cogeneration architecture is constructed, the time-space decoupling of the electric energy output and the water electrolysis hydrogen production is realized, the frequent start-stop of the electrolytic cell is reduced to improve the stability; and through the reversible oxidation-reduction reaction of HATN and Zn and the offline storage design of the hydrogen storage tank and the oxygen storage tank, the time-space limitation of the electric energy and the hydrogen energy production is avoided, the long-period operation demand is matched; meanwhile, through the reversible oxidation-reduction reaction of HATN and Zn and the ion regulation of the bipolar membrane diaphragm, the dendrite problem of the zinc-based electrode is inhibited, the efficient adaptation to the fluctuating new energy input such as photovoltaic and wind power is realized, and the overall energy conversion efficiency is improved.

[0026] It should be understood that the foregoing general description and the following detailed description are only exemplary and explanatory, and cannot limit the present disclosure. BRIEF DESCRIPTION OF DRAWINGS

[0027] The accompanying drawings are used to provide a further understanding of the present application, and constitute a part of the specification, and are used to explain the present application together with embodiments of the present application, and do not constitute a limitation of the present application. Obviously, the drawings in the following description are only some embodiments of the present disclosure, and other drawings can be obtained by those skilled in the art without creative labor on the basis of these drawings.

[0028] Figure 1 The structure schematic diagram of the HATN-Zn double-effect battery coupling dynamic decoupling water electrolysis electric hydrogen cogeneration system provided for the embodiments of the present application is shown in the figure;

[0029] Figure 2 The chemical structural formula schematic diagram of HATN in the HATN-Zn double-effect battery coupling dynamic decoupling water electrolysis electric hydrogen cogeneration system provided for the embodiments of the present application is shown in the figure;

[0030] Figure 3 The mechanism schematic diagram of HATN being reduced to 6H-HATN and 6H-HATN being oxidized to HATN in the HATN-Zn double-effect battery coupling dynamic decoupling water electrolysis electric hydrogen cogeneration system provided for the embodiments of the present application is shown in the figure;

[0031] Figure 4 The step-by-step water electrolysis hydrogen production and HATN-Zn double-effect battery discharge curve schematic diagram in the HATN-Zn double-effect battery coupling dynamic decoupling water electrolysis electric hydrogen cogeneration system provided for the embodiments of the present application is shown in the figure.

[0032] Reference signs:

[0033] 10, HATN-Zn battery unit; 20, hydrogen production electrolyzer; 30, oxygen production electrolyzer; 40, HATN electrode; 50, Zn electrode; 60, hydrogen evolution Pt electrode; 70, oxygen evolution Ru / Ir electrode; 81, first power supply; 82, second power supply; 91, first switch; 92, second switch; 93, third switch; 100, external power supply; 110, diaphragm; 120, strong acid solution tank containing oxygen, 121, acid solution input pipeline, 122, acid solution output pipeline; 130, saturated ZnO alkali hydroxide solution tank, 131, alkali solution input pipeline, 132, alkali solution output pipeline; 140, hydrogen storage tank, 141, hydrogen gas output pipeline; 150, oxygen storage tank, 151, oxygen gas output pipeline; 160, peristaltic pump. DETAILED DESCRIPTION

[0034] Example implementations will now be described more fully with reference to the accompanying drawings. Example implementations, however, can be implemented in many different forms and should not be construed as limited to the examples set forth herein; rather, these implementations are provided so that this disclosure will be thorough and complete, and will fully convey the concept of example implementations to those skilled in the art. The described features, structures, or characteristics can be combined in one or more implementations.

[0035] In the present example implementation, a dynamic decoupling water electrolysis-electricity hydrogen co-production system based on HATN-Zn double-effect battery coupling is first provided. Referring to FIG. 1, the dynamic decoupling water electrolysis-electricity hydrogen co-production system based on HATN-Zn double-effect battery coupling includes a HATN-Zn battery unit 10, a hydrogen production electrolyzer 20, and an oxygen production electrolyzer 30; wherein: Figure 1

[0036] The HATN-Zn battery unit 10 includes a HATN electrode 40 in an oxidation state, a Zn electrode 50 in a reduction state, and an external power supply 100, for storing or releasing electric energy through reversible oxidation-reduction reaction of HATN and Zn;

[0037] The hydrogen production electrolyzer 20 includes the HATN electrode 40 in a reduction state, a hydrogen evolution Pt electrode 60, and a first power supply 81, for generating hydrogen through hydrogen evolution reaction in an acidic environment, and regenerating the HATN electrode 40 in a reduction state by oxidation, to charge the positive electrode of the HATN-Zn battery unit 10;

[0038] The oxygen production electrolyzer 30 includes the Zn electrode 50 in an oxidation state, an oxygen evolution Ru / Ir electrode, and a second power supply 82, for generating oxygen through oxygen evolution reaction in an alkaline environment, and regenerating the Zn electrode 50 in an oxidation state by reduction, to charge the negative electrode of the HATN-Zn battery unit 10;

[0039] ​The hydrogen-producing electrolyzer 20 and the oxygen-producing electrolyzer 30 are in communication and separated by a diaphragm 110.

[0040] It can be understood that the HATN material of the HATN electrode 40 is diquinoxalino[2,3-a:2',3'-c]phenazine, the structure of which is as shown in the following formula (I): Figure 2 The HATN material is reduced to 6H-HATN in the reduced state and oxidized to HATN in the oxidized state, and the mechanism of the reduction of HATN to 6H-HATN and the oxidation of 6H-HATN to HATN is as shown in the following formula (II): Figure 3

[0041] Further, the HATN electrode is prepared by a dry solid-state electrolyte film forming process, specifically, the HATN material synthesized by acid catalyzed stepwise condensation cyclization reaction and polytetrafluoroethylene dispersion liquid (PTFE) and acetylene black are pressed on the current collector in a certain proportion to obtain.

[0042] The preparation method of the HATN material can be specifically as follows:

[0043] In an argon environment, a mixture of 1,2-phenylenediamine (1356 mg, 12.0 mmol) and anhydrous hexa-π-cyclohexane (168 mg, 1.0 mmol, prepared by vacuum dehydration of hexa-π-cyclohexane octahydrate at 120°C for 2 h) was loaded into a three-necked flask. Glacial acetic acid (20 mL) and concentrated sulfuric acid (0.1 mL, 95 wt%, 1.8 mmol) were added as solvent and catalyst, respectively. The reaction mixture was heated to 115°C under vigorous stirring for 36 h to promote the initial condensation step, during which water was removed through a Dean-Stark trap. Subsequently, the temperature was increased to 140°C at a rate of 2°C / min, and the reaction was allowed to continue for 24 h to promote cyclization and final dehydration. The resulting deep yellow precipitate was collected by hot filtration and washed with methanol and acetone in sequence to remove unreacted starting materials and oligomer byproducts. Finally, the target product was collected and dried.

[0044] The preparation method of the HATN electrode can be specifically as follows:

[0045] The active material (70 wt% HATN), conductive additive (20 wt% Ketjenblack EC-300J), and polymeric binder (10 wt% PTFE) were pre-mixed. Subsequently, the mixture was compacted into a self-standing thin film using a roll compactor (5 cycles, 10 MPa roll pressure). Prior to lamination, the titanium mesh current collector (100 mesh) was surface pretreated by ultrasonic cleaning in ethanol for 30 min. The composite thin film was then pressed onto the pretreated titanium mesh using a hydraulic press under controlled parameters (22 MPa, 120 s) to precisely control the active mass loading of 3.0 ± 0.15 mg cm -2 .​

[0046] In one possible implementation, the external power supply 100 can be any one or more of an external load and an energy storage battery, wherein energy storage is performed by storing power into the energy storage battery, and energy release is performed by releasing power into the external load.

[0047] Furthermore, the energy storage battery or load includes a DC-DC conversion module, i.e., a DC-DC converter module.

[0048] In one possible implementation, the diaphragm 110 is a bipolar membrane (BPM).

[0049] It should be noted that the hydrogen-producing electrolysis cell and the oxygen-producing electrolysis cell are physically separated by a BPM membrane, forming independent acid / base electrolysis environments. The oxygen-producing electrolysis cell side is filled with 4 mol L... -1 A saturated ZnO solution containing KOH was used, and the hydrogen-producing electrolytic cell was filled with 2 mol L of KOH. -1 H2SO4. The BPM membrane not only achieves physical isolation between the acidic environment of the hydrogen-producing electrolyzer and the alkaline environment of the oxygen-producing electrolyzer, but also generates H2SO4 through water dissociation. + It migrates in a directional manner with OH-, providing ionic support for the electrolytic reactions on both sides and maintaining charge balance.

[0050] In one possible implementation, the HATN-Zn dual-effect battery-coupled dynamic decoupled water electrolysis and hydrogen cogeneration system further includes an oxygen-containing strong acid solution tank 120 and a saturated ZnO alkali metal hydroxide solution tank 130. The oxygen-containing strong acid solution tank 120 is connected to the hydrogen-producing electrolysis cell 20 through an acid inlet pipe 121 and an acid outlet pipe 122, forming a circulation loop for the oxygen-containing strong acid solution. The saturated ZnO alkali metal hydroxide solution tank 130 is connected to the oxygen-producing electrolysis cell through an alkali inlet pipe 131 and an alkali outlet pipe 132, forming a circulation loop for the saturated ZnO alkali metal hydroxide solution.

[0051] It is understandable that the combination of the oxygen-containing strong acid solution circulation loop and the saturated ZnO alkali metal hydroxide solution circulation loop can continuously replenish the H+ and Zn consumed in the reaction. 2 + Timely removal of byproducts ensures the stability of the electrolysis environment and maintains efficient reaction.

[0052] Furthermore, the acid inlet pipe 121, acid outlet pipe 122, alkali inlet pipe 131, and alkali outlet pipe 132 are all equipped with peristaltic pumps 160.

[0053] Understandably, 2 mol / L is optional. -1H2SO4 from the oxygen-containing strong acid solution tank 120 is driven by a peristaltic pump 160, and is transported to the hydrogen production electrolytic cell 20 through the acid liquid input pipeline 121. The waste liquid is returned to the oxygen-containing strong acid solution tank 120 through the acid liquid output pipeline 122 to form a closed loop. The concentration of H2SO4 is 4 mol / L -1 The saturated ZnO solution of KOH is driven by another peristaltic pump 160 from the saturated ZnO alkali metal hydroxide solution tank 130, and is transported to the oxygen production electrolytic cell 30 through the alkali liquid input pipeline 131. The waste liquid is returned through the alkali liquid output pipeline 132. The peristaltic pump can not only ensure sufficient supply of reactants on the electrode surface, but also avoid the increase of energy consumption caused by too fast flow rate, so as to balance the mass transfer efficiency and energy consumption.

[0054] In one possible implementation, the HATN-Zn dual-effect battery-based dynamic decoupling water electrolysis hydrogen production cogeneration system further comprises a hydrogen storage tank 140 and an oxygen storage tank 150. The hydrogen storage tank 140 is connected to the hydrogen production electrolytic cell 20 through a hydrogen output pipeline 141, and is used to store the hydrogen output by the hydrogen production electrolytic cell 20. The oxygen storage tank 150 is connected to the oxygen production electrolytic cell 30 through an oxygen output pipeline 151, and is used to store the oxygen output by the oxygen production electrolytic cell 30.

[0055] It can be understood that, optionally, the hydrogen generated by the hydrogen production electrolytic cell 20 is transported to the hydrogen storage tank 140 through the hydrogen output pipeline 141; and the oxygen generated by the oxygen production electrolytic cell is transported to the oxygen storage tank 150 through the oxygen output pipeline 151.

[0056] Further, the hydrogen storage tank 140 and the oxygen storage tank 150 are respectively connected to a gas purification device. The gas purification device is any one or more of a dryer and a particulate filter.

[0057] It can be understood that, by drying and filtering, the gas purification device can improve the purity of hydrogen and oxygen to more than 99.9%, meeting the requirements of fuel cells, precision chemical industry and other scenarios for high-purity gas.

[0058] In one possible implementation, the oxygen-containing strong acid solution is a sulfuric acid solution or a nitric acid solution, and the hydrogen ion concentration ranges from 2.0 to 4.0 M.

[0059] In one possible implementation, the saturated ZnO alkali metal hydroxide solution is composed of ZnO and sodium hydroxide solution or ZnO and potassium hydroxide solution. The concentration of the sodium hydroxide solution and the potassium hydroxide solution ranges from 2.0 to 4.0 M, and the saturated concentration of the ZnO ranges from 0.1 to 0.3 M.

[0060] In one possible implementation, the hydrogen evolution Pt electrode 60 is a porous titanium-based electrode coated with a platinum-carbon catalyst; and the oxygen evolution Ru / Ir electrode 70 is a porous titanium-based electrode coated with a mixed oxide of IrO2-RuO2.

[0061] It can be understood that the special coating design of the hydrogen evolution Pt electrode and the oxygen evolution Ru / Ir electrode respectively reduces the overpotential of the hydrogen evolution and oxygen evolution reactions, and the porous titanium-based carrier enhances the electrode conductivity and mechanical durability.

[0062] In one possible implementation, the HATN-Zn battery unit 10 has a first switch 91, the hydrogen production electrolytic cell 20 has a second switch 92, and the oxygen production electrolytic cell 30 has a third switch 93; wherein the first switch 91 is used to control the HATN electrode 40 and the Zn electrode 50 to be powered by the external power supply 100, the second switch 92 is used to control the first power supply 81 to power the HATN electrode 40 and the hydrogen evolution Pt electrode 60, and the third switch 93 is used to control the second power supply 82 to power the Zn electrode 50 and the oxygen evolution Ru / Ir electrode 70.

[0063] It can be understood that the independent control of the three switches strictly separates the battery discharge and electrolytic charging modes, avoids energy loss caused by cross-powering, and ensures the specificity and efficiency of the electrode reactions in each step.

[0064] Further, the HATN-Zn dual-effect battery coupled dynamic decoupling water electrolysis and hydrogen production system based on the present application was tested for hydrogen and electricity co-production, as shown in Figure 4 The chronopotentiometry method was used:

[0065] HATN-Zn battery discharge step: connect the HATN electrode sheet to the working electrode of the electrochemical workstation, connect the Zn electrode sheet polished with sandpaper to the counter electrode of the electrochemical workstation, use the Ag / AgCl electrode as the reference electrode, and apply a cathode current of 10 mA cm -2 to the battery unit, and obtain the HATN-Zn battery unit discharge curve as shown in the left half of Figure 4 (Step 1), the discharge capacity is 3 mAh cm -2 , and the average voltage of the battery discharge is about 1.65 V. The discharge process is driven by the chemical potential difference of the electrodes, and after the release of the stored electrical energy, the HATN electrode is converted into the reduced HATN electrode, i.e., 6H-HATN.

[0066] Hydrogen-generating coupled positive electrode charging steps: Connect the reduced HATN electrode sheet to the counter electrode of the electrochemical workstation, connect the platinum-plated titanium mesh to the working electrode of the electrochemical workstation, use the Ag / AgCl electrode as the reference electrode, and apply 100 mA / cm² to the hydrogen-generating electrolyzer unit. -2 The discharge curve of the HATN-Zn battery cell obtained by determining the anode current is shown below. Figure 4 The middle section shown in Step 2 has a discharge capacity of 3 mAh cm⁻¹. -2 The required average voltage is approximately 1.49V. Water molecules are electrochemically reduced to hydrogen gas on the platinum electrode surface. Simultaneously, the HATN electrode (positive electrode) serves as a redox medium electrode, where an oxidation reaction occurs, simultaneously charging the battery's positive electrode.

[0067] Oxygen-generating coupled negative electrode charging steps: Connect the Ru / Ir electrode to the working electrode of the electrochemical workstation, connect the Zn electrode to the counter electrode of the electrochemical workstation, use the Ag / AgCl electrode as the reference electrode, and apply 100 mA cm⁻¹ to the oxygen-generating electrolyzer unit. -2 The discharge curve of the HATN-Zn battery cell obtained by determining the anode current is shown below. Figure 4 The right half of the area is shown (Step 3), with a discharge capacity of 3 mAh cm⁻¹. -2 The required average voltage is approximately 2.21V. Water molecules are electrochemically oxidized to generate oxygen on the Ru / Ir electrode surface, while a Zn electrode is used as a redox medium electrode, where the oxidation reaction occurs and the negative electrode of the battery is charged simultaneously.

[0068] Furthermore, in this example embodiment, a method for co-producing hydrogen via water electrolysis based on a HATN-Zn dual-effect battery with dynamic decoupling is also provided, for controlling the aforementioned co-producing hydrogen via water electrolysis based on a HATN-Zn dual-effect battery. The method may include:

[0069] In step S100, the acid inlet pipe 121, acid outlet pipe 122, alkali inlet pipe 131, alkali outlet pipe 132, hydrogen outlet pipe 141, and oxygen outlet pipe 151 are closed. The second switch 92 and the third switch 93 are disconnected, and the first switch 91 is closed. The HATN-Zn battery, composed of the HATN electrode 40 in the oxidized state and the Zn electrode 50 in the reduced state, supplies power to the external power supply 100.

[0070] Step S200, the acid liquid input pipeline 121, the acid liquid output pipeline 122 and the hydrogen output pipeline 141 are opened, the first switch 91 is disconnected, the second switch 92 is closed, the first power supply 81 supplies power to the HATN electrode 40 in the reduction state to perform the oxidation reaction charging, at the same time, supplies power to the hydrogen evolution Pt electrode 60 to generate hydrogen by reduction reaction, and the hydrogen is input into the hydrogen storage tank 140 through the hydrogen output pipeline 141.

[0071] Step S300, the alkali liquid input pipeline 131, the alkali liquid output pipeline 132 and the oxygen output pipeline 151 are opened, the first switch 91 is disconnected, the third switch 93 is closed, the second power supply 82 supplies power to the Zn electrode 50 in the oxidation state to perform the reduction reaction charging, at the same time, supplies power to the oxygen evolution Ru / Ir electrode to generate oxygen by oxidation reaction, and the oxygen is input into the hydrogen storage tank 150 through the oxygen output pipeline 151.

[0072] It should be noted that the hydrogen production coupled with the positive electrode charging and the oxygen production coupled with the negative electrode charging are performed synchronously, which can improve the system integration degree, shorten the overall cycle time, and further improve the efficiency of the electricity and hydrogen co-production by sharing the energy of the external power supply.

[0073] Other embodiments of the present disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the application disclosed herein. This application is intended to cover any variations, uses or adaptations of the application following, in general, the principles of the application and including such departures from the present disclosure as come within known or customary practice in the art to which the application pertains. It is intended that the specification and examples be considered as exemplary only, with the true scope and spirit of the application being indicated by the following claims.

[0074] The above embodiments are only used to illustrate the technical solutions of the present application, but not limit them. The present application is not limited to the exact structure as shown in the above description and the accompanying drawings, and the specific implementation of the present application should not be considered as limited to these descriptions. Various changes and modifications made by those skilled in the art without departing from the concept of the present application should be considered as falling within the scope of the present application.

Claims

1. A water electrolysis and hydrogen cogeneration system based on a HATN-Zn dual-effect battery coupling and dynamic decoupling, characterized in that, include: The HATN-Zn battery cell includes an oxidized HATN electrode, a reduced Zn electrode, and an external power supply, used for storing or releasing electrical energy through the reversible redox reaction between HATN and Zn. The hydrogen-producing electrolyzer includes the HATN electrode in a reduced state, the hydrogen evolution Pt electrode, and a first power source. It is used to generate hydrogen gas through a hydrogen evolution reaction in an acidic environment and to oxidize and regenerate the HATN electrode in a reduced state to charge the positive electrode of the HATN-Zn battery cell. The oxygen-generating electrolytic cell includes the Zn electrode in an oxidized state, the oxygen-evolving Ru / Ir electrode, and a second power source. It is used to generate oxygen through an oxygen evolution reaction in an alkaline environment and to reduce and regenerate the Zn electrode in an oxidized state to charge the negative electrode of the HATN-Zn battery cell. The hydrogen-producing electrolytic cell is connected to the oxygen-producing electrolytic cell and separated by a diaphragm.

2. The HATN-Zn dual-effect battery-based dynamic decoupling water electrolysis and hydrogen cogeneration system according to claim 1, characterized in that, It also includes a tank containing an oxygen-containing strong acid solution and a tank containing a saturated ZnO alkali metal hydroxide solution; the tank containing the oxygen-containing strong acid solution is connected to the hydrogen-producing electrolytic cell through an acid inlet pipeline and an acid outlet pipeline, forming a circulation loop for the oxygen-containing strong acid solution; the tank containing the saturated ZnO alkali metal hydroxide solution is connected to the oxygen-producing electrolytic cell through an alkali inlet pipeline and an alkali outlet pipeline, forming a circulation loop for the saturated ZnO alkali metal hydroxide solution.

3. The HATN-Zn dual-effect battery-based dynamic decoupling water electrolysis and hydrogen cogeneration system according to claim 2, characterized in that, The acid inlet pipeline, acid outlet pipeline, alkali inlet pipeline, and alkali outlet pipeline are all equipped with peristaltic pumps.

4. The HATN-Zn dual-effect battery-based dynamic decoupling water electrolysis and hydrogen co-production system according to claim 2, characterized in that, It also includes a hydrogen storage tank and an oxygen storage tank. The hydrogen storage tank is connected to the hydrogen-producing electrolyzer via a hydrogen output pipeline and is used to store the hydrogen output from the hydrogen-producing electrolyzer. The oxygen storage tank is connected to the oxygen-producing electrolyzer via an oxygen output pipeline and is used to store the oxygen output from the oxygen-producing electrolyzer.

5. The HATN-Zn dual-effect battery-based dynamic decoupling water electrolysis and hydrogen cogeneration system according to claim 4, characterized in that, The hydrogen storage tank and the oxygen storage tank are respectively connected to a gas purification device, which is any one or more of a dryer and a particulate filter.

6. The HATN-Zn dual-effect battery-based dynamic decoupling water electrolysis and hydrogen co-production system according to claim 2, characterized in that, The oxygen-containing strong acid solution is a sulfuric acid solution or a nitric acid solution, with a hydrogen ion concentration range of 2.0-4.0 M.

7. The HATN-Zn dual-effect battery-based dynamic decoupling water electrolysis and hydrogen cogeneration system according to claim 2, characterized in that, The saturated ZnO alkali metal hydroxide solution is composed of ZnO and sodium hydroxide solution or ZnO and potassium hydroxide solution, wherein the concentration range of the sodium hydroxide solution and the potassium hydroxide solution is 2.0-4.0M, and the saturated concentration range of ZnO is 0.1-0.3M.

8. The HATN-Zn dual-effect battery-coupled dynamic decoupling water electrolysis and hydrogen co-production system according to claim 1, characterized in that, The hydrogen evolution Pt electrode is a porous titanium-based electrode coated with a platinum-carbon catalyst; the oxygen evolution Ru / Ir electrode is a porous titanium-based electrode coated with a mixed oxide of IrO2-RuO2.

9. The HATN-Zn dual-effect battery-coupled dynamic decoupling water electrolysis and hydrogen cogeneration system according to claim 4, characterized in that, The HATN-Zn battery cell has a first switch, the hydrogen-producing electrolyzer has a second switch, and the oxygen-producing electrolyzer has a third switch; wherein, the first switch is used to control the HATN electrode and the Zn electrode to supply power to the external power source, the second switch is used to control the first power source to supply power to the HATN electrode and the hydrogen evolution Pt electrode, and the third switch is used to control the second power source to supply power to the Zn electrode and the oxygen evolution Ru / Ir electrode.

10. A method for co-producing hydrogen from water electrolysis based on a HATN-Zn dual-effect battery with dynamic decoupling, characterized in that, The method is used to control the HATN-Zn dual-effect battery-based dynamic decoupling water electrolysis and hydrogen cogeneration system as described in claim 9, including: The acid inlet pipeline, acid outlet pipeline, alkali inlet pipeline, alkali outlet pipeline, hydrogen outlet pipeline and oxygen outlet pipeline are closed, the second switch and the third switch are disconnected, the first switch is closed, and the HATN-Zn battery composed of the HATN electrode in the oxidized state and the Zn electrode in the reduced state supplies power to the external power source. When the acid inlet pipeline, acid outlet pipeline, and hydrogen outlet pipeline are opened, the first switch is disconnected, the second switch is closed, the first power supply supplies power to the HATN electrode in the reduced state to charge the oxidation reaction, and at the same time supplies power to the hydrogen evolution Pt electrode to generate hydrogen through the reduction reaction. The hydrogen is then fed into the hydrogen storage tank through the hydrogen outlet pipeline. The alkaline solution input pipeline, alkaline solution output pipeline, and oxygen output pipeline are opened. The first switch is disconnected, and the third switch is closed. The second power supply supplies power to the Zn electrode in the oxidized state to charge it for the reduction reaction. At the same time, it supplies power to the oxygen evolution Ru / Ir electrode to generate oxygen through the oxidation reaction. The oxygen is then input into the hydrogen storage tank through the oxygen output pipeline.

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