CN222261132U - Electrochemical device - Google Patents
Electrochemical device Download PDFInfo
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- CN222261132U CN222261132U CN202420389832.6U CN202420389832U CN222261132U CN 222261132 U CN222261132 U CN 222261132U CN 202420389832 U CN202420389832 U CN 202420389832U CN 222261132 U CN222261132 U CN 222261132U
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- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 311
- 239000001257 hydrogen Substances 0.000 claims abstract description 308
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 304
- 238000006243 chemical reaction Methods 0.000 claims abstract description 118
- 239000000463 material Substances 0.000 claims abstract description 115
- 239000012530 fluid Substances 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 230000036961 partial effect Effects 0.000 claims description 48
- 239000007787 solid Substances 0.000 claims description 35
- 239000000446 fuel Substances 0.000 claims description 32
- 238000007254 oxidation reaction Methods 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 abstract description 20
- 230000002829 reductive effect Effects 0.000 abstract description 9
- 230000001681 protective effect Effects 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 230000002427 irreversible effect Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003570 air Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000009545 invasion Effects 0.000 description 2
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
本实用新型公开了一种电化学装置，属于电化学技术领域。所述电化学装置括包括电化学堆及第一氢气生成装置，所述电化学堆具有第一反应区入口、第一反应区及第一反应区出口，所述第一反应区入口及第一反应区出口分别与所述第一反应区连通，所述电化学堆的第一反应区入口与第一氢气生成装置的出口连接，所述第一氢气生成装置内装填第一氢气生成材料。本实用新型利用第一氢气生成装置内装填的第一氢气生成材料与水蒸气反应，从而消耗水蒸气，同时反应产生的氢气，进入电化学堆作为保护气，可以保护电化学堆内的催化剂；被氧化的第一氢气生成材料可被所述还原性流体还原，从而使第一氢气生成材料可循环利用，使用寿命长，成本较低。
The utility model discloses an electrochemical device, which belongs to the field of electrochemical technology. The electrochemical device includes an electrochemical stack and a first hydrogen generating device. The electrochemical stack has a first reaction zone inlet, a first reaction zone and a first reaction zone outlet. The first reaction zone inlet and the first reaction zone outlet are respectively connected to the first reaction zone. The first reaction zone inlet of the electrochemical stack is connected to the outlet of the first hydrogen generating device. The first hydrogen generating device is filled with a first hydrogen generating material. The utility model utilizes the first hydrogen generating material filled in the first hydrogen generating device to react with water vapor, thereby consuming water vapor. At the same time, the hydrogen generated by the reaction enters the electrochemical stack as a protective gas, which can protect the catalyst in the electrochemical stack; the oxidized first hydrogen generating material can be reduced by the reducing fluid, so that the first hydrogen generating material can be recycled, with a long service life and low cost.
Description
Technical Field
The utility model relates to the technical field of electrochemistry, in particular to an electrochemical device.
Background
The conversion between electrical energy and chemical energy is accomplished by a wide variety of electrochemical devices, such as fuel cells, electrolytic cells, and the like. Common fuel cells include Alkaline Fuel Cells (AFC), phosphoric Acid Fuel Cells (PAFC), molten carbonate fuel cells (MCFF), proton Exchange Membrane Fuel Cells (PEMFC), direct Methanol Fuel Cells (DMFC), solid Oxide Fuel Cells (SOFC), etc., and common electrolytic cells include alkaline electrolytic cells (AWE), proton exchange membrane water electrolytic cells (PEMWE), anion exchange membrane water electrolytic cells (AEMWE), solid Oxide Electrolytic Cells (SOEC), etc. The Solid Oxide Fuel Cell (SOFC) and the Solid Oxide Electrolytic Cell (SOEC) can be collectively called as a Solid Oxide Cell (SOC), and the Solid Oxide Cell (SOC) is an advanced electrochemical energy conversion device, and has a wide application prospect in the fields of clean energy power generation and CO 2 conversion. A Solid Oxide Fuel Cell (SOFC) is an energy conversion device capable of directly converting chemical energy stored in fuel and oxidant into electric energy, and has a relatively high operating temperature, typically in the range of 700-1000 ℃, so that it can utilize its waste heat to realize cogeneration while generating electricity, and the energy utilization efficiency can be up to 90%. A Solid Oxide Electrolytic Cell (SOEC) is an electrochemical energy conversion device that converts electrical and thermal energy into chemical energy, the reaction of which is the reverse reaction of a solid oxide fuel cell. As one of the main technical routes for hydrogen production by water electrolysis today, SOEC is usually operated at 700-850 ℃ with an electrolysis efficiency as high as 85-95%. The solid oxide fuel cell and the solid oxide cell may react using the same electrochemical stack, except that the anode side of the solid oxide fuel cell is in the solid oxide cell as the cathode side, e.g., hydrogen molecules (H 2) are oxidized to H + under anode catalysis by loss of electrons (e -) at the anode side of the solid oxide fuel cell, and hydrogen ions (H +) are reduced to hydrogen (H 2) under cathode catalysis by the resulting electrons (e -) at the cathode side of the solid oxide cell.
In SOFCs, when a fuel other than hydrogen is used, the fuel is usually reformed by steam reforming, partial oxidation, catalytic cracking, or the like, and then enters the anode, and in SOECs, steam and hydrogen are supplied to the SOEC cathode together as a reaction gas. The catalyst in the SOFC anode and SOEC cathode is typically a metal or alloy (e.g., nickel) that is susceptible to oxidation, and is in a reduced state during normal operation of the electrochemical stack due to the presence of a reducing atmosphere (H 2), and when the system ceases to supply reducing fluid (where reducing fluid refers to fuel to the anode side of the SOFC and hydrogen to the cathode side of the SOEC, and the like) due to a sudden stop or failure, the catalyst in the electrochemical stack is inevitably subject to the intrusion of ambient air, resulting in a failure of the catalyst function. At present, the prior art generally adopts modes such as metal sacrificing, rapid cooling, inert gas passing and the like to avoid the catalyst function failure caused by the invasion of the external gas on the electrochemical stack, however, the prior art still has the problems that ① is complex to operate and high in cost, ② is not fully utilized with water vapor, ③ is not fully considered with the harm and influence of the water vapor, and the water vapor can cause certain invasion damage to the electrochemical stack, for example, oxidation of a catalyst on the anode side of an SOEC or a catalyst on the cathode side of the SOEC.
Therefore, it is necessary to develop an electrochemical device to fully utilize water vapor while avoiding catalyst failure caused by water vapor oxidation.
Disclosure of utility model
Based on the drawbacks of the prior art, an object of the present utility model is to provide an electrochemical device.
In order to achieve the above purpose, the utility model adopts the following technical scheme:
The electrochemical device comprises an electrochemical stack and a first hydrogen generation device, wherein the electrochemical stack is provided with a first reaction zone inlet, a first reaction zone and a first reaction zone outlet, the first reaction zone inlet and the first reaction zone outlet are respectively communicated with the first reaction zone, the first reaction zone inlet of the electrochemical stack is connected with the outlet of the first hydrogen generation device, the first hydrogen generation device is of a structure with hollow inside and two open ends, the inlet of the first hydrogen generation device is used for receiving reducing fluid and/or water vapor, the first hydrogen generation device is filled with a first hydrogen generation material, the material of the first hydrogen generation material is reducing metal or reducing alloy, and the first hydrogen generation material is used for reacting with the water vapor.
As a preferred embodiment of the present utility model, the first hydrogen generating material has a porous structure, and the first hydrogen generating material has a porosity of 10 to 300ppi.
As a preferred embodiment of the utility model, the thermodynamic equilibrium hydrogen partial pressure of the oxidation reaction of the first hydrogen generating material in the first hydrogen generating device is P 1, the thermodynamic equilibrium hydrogen partial pressure of the oxidation reaction of the catalyst in the first reaction zone is P 2, the hydrogen partial pressure in the first hydrogen generating device is P 3,P3＞P1 when the electrochemical device is operating normally, and the hydrogen partial pressure in the first reaction zone of the electrochemical stack is P 4,P4＞P2 when the inlet of the first hydrogen generating device does not receive the reducing fluid. If the electrochemical device is operating normally, P 3＜P1, the first hydrogen generating material in the first hydrogen generating device is oxidized, and when the inlet of the first hydrogen generating device does not receive the reducing fluid due to sudden stop or failure of the electrochemical device, the first hydrogen generating device does not have the capability of reacting with steam to generate hydrogen shielding gas, and if the inlet of the first hydrogen generating device does not receive the reducing fluid, P 4＜P2, the catalyst in the reaction zone of the electrochemical stack 1 is oxidized, so that irreversible damage is caused.
As a preferred embodiment of the present utility model, the electrochemical stack is a solid oxide fuel cell, the electrochemical device further comprises a reformer, and an outlet of the reformer, the first hydrogen generating device and an inlet of the first reaction zone of the electrochemical stack are sequentially connected.
As a preferred embodiment of the present utility model, the electrochemical stack is a solid oxide electrolytic cell, the electrochemical device further comprises a mixer, and an outlet of the mixer, the first hydrogen generating device and an inlet of the first reaction zone of the electrochemical stack are sequentially connected.
In a preferred embodiment of the present utility model, the outlet of the first reaction zone of the electrochemical stack is connected to a second hydrogen generating device, the second hydrogen generating device has a structure that is hollow inside and has two ends open, a second hydrogen generating material is disposed in the second hydrogen generating device, the second hydrogen generating material is made of a reducing metal or a reducing alloy, and the second hydrogen generating material is used for reacting with water vapor.
Further, the second hydrogen generating material is of a porous structure, and the porosity of the second hydrogen generating material is 10-300ppi.
Further, the electrochemical stack is a solid oxide fuel cell, the electrochemical device further comprises a combustor, and the outlet of the first reaction zone of the electrochemical stack, the second hydrogen generating device and the inlet of the combustor are sequentially connected.
Further, the thermodynamic equilibrium hydrogen partial pressure of the oxidation reaction of the second hydrogen generating material in the second hydrogen generating device is P 5, the thermodynamic equilibrium hydrogen partial pressure of the oxidation reaction of the catalyst in the first reaction zone is P 2, the hydrogen partial pressure in the second hydrogen generating device is P 6,P6＞P5 when the electrochemical device operates normally, and the hydrogen partial pressure in the first reaction zone of the electrochemical stack is P 4,P4＞P2 when the inlet of the first hydrogen generating device does not receive the hydrogen. If the electrochemical device is in normal operation, P 6＜P5, the second hydrogen generating material in the second hydrogen generating device is oxidized, and when the inlet of the first hydrogen generating device does not receive the reducing fluid due to sudden stop or failure of the electrochemical device, the refluxing water vapor cannot be consumed and sufficient hydrogen is provided, so that the protection effect on the electrochemical stack is lost, and if the inlet of the second hydrogen generating device does not receive the reducing fluid, P 4＜P2, the catalyst in the reaction zone of the electrochemical stack 1 is oxidized, so that irreversible damage is caused.
It will be appreciated that in the present utility model, the hydrogen partial pressure in the reactor zone and the hydrogen partial pressure at the hydrogen generating device are tested by electron bombardment mass spectrometry to obtain the concentration of hydrogen in the gas in the corresponding zone, and then the hydrogen partial pressure is calculated according to the following formula, hydrogen partial pressure = concentration of hydrogen =standard atmospheric pressure.
Compared with the prior art, the utility model has the beneficial effects that:
According to the utility model, the first hydrogen generating device is arranged at the inlet of the first reaction zone of the electrochemical pile, when the electrochemical device interrupts the supply of the reducing fluid, the first hydrogen generating material filled in the first hydrogen generating device is utilized to react with the water vapor to consume the water vapor, and meanwhile, the hydrogen generated by the reaction enters the electrochemical pile to be used as the protective gas, so that the catalyst in the electrochemical pile can be protected, and the water vapor is fully utilized while the catalyst failure caused by the oxidation of the water vapor is avoided. When the electrochemical device resumes the supply of the reducing fluid, the oxidized first hydrogen generating material can be reduced by the reducing fluid, so that the first hydrogen generating material can be recycled, the service life is long, and the cost is low.
Drawings
Fig. 1 is a schematic view illustrating a structure of an electrochemical device according to an embodiment of the present utility model;
Fig. 2 is a schematic structural view of an electrochemical device according to another embodiment of the present utility model;
Fig. 3 is a graph showing the voltage change of the fuel cell according to the present utility model before and after stopping the supply of the reducing fluid.
In the figure, 1-electrochemical stack, 2-first hydrogen generating device, 3-first hydrogen generating material, 4-reformer, 5-mixer, 6-second hydrogen generating device, 7-second hydrogen generating material, 8-burner, 9-pressurized storage system.
Detailed Description
The present utility model will be further described with reference to specific examples and comparative examples for better illustrating the objects, technical solutions and advantages of the present utility model, and the object of the present utility model is to be understood in detail, not to limit the present utility model. All other embodiments, which can be made by those skilled in the art without the inventive effort, are intended to be within the scope of the present utility model.
Referring to fig. 1-2, the electrochemical device provided by the utility model comprises an electrochemical stack 1, wherein the electrochemical stack 1 is provided with a first reaction zone inlet, a first reaction zone and a first reaction zone outlet, the first reaction zone inlet and the first reaction zone outlet are respectively communicated with the first reaction zone, the first hydrogen generating device 2 is of a structure with hollow inside and two open ends, the first reaction zone inlet of the electrochemical stack 1 is connected with the outlet of the first hydrogen generating device 2, the inlet of the first hydrogen generating device 2 is used for receiving reducing fluid and/or water vapor, and the reducing fluid and/or water vapor sequentially flows through the first hydrogen generating device 2 and the first reaction zone of the electrochemical stack and then flows out from the first reaction zone outlet. The first hydrogen generating apparatus 2 is filled with a first hydrogen generating material 3, the material of the first hydrogen generating material 3 is a reducing metal or a reducing alloy, and the first hydrogen generating material 3 can react with water vapor.
When the electrochemical device fails and the inlet of the first hydrogen generating device 2 does not receive the reducing fluid, the water vapor is not stopped timely, so that the water content in the fluid entering through the inlet of the first reaction zone of the electrochemical stack 1 is rapidly increased, and certain intrusion damage is caused to the electrochemical stack 1. The utility model is provided with a first hydrogen generating device 2 connected with a first reaction zone inlet of an electrochemical pile 1, and utilizes a first hydrogen generating material 3 filled in the first hydrogen generating device 2 to react with steam so as to consume the steam, wherein the reaction general formula is xJ +yH2 2O→JxOy+yH2, J represents the first hydrogen generating material 3, and hydrogen generated by the reaction enters the electrochemical pile 1 as a protective gas, so that a catalyst in the electrochemical pile 1 can be protected. When the electrochemical device resumes the supply of the reducing fluid, J xOy can be reduced by the reducing fluid, and the first hydrogen-generating material 3 can be recycled, and has a long life and a low cost.
In one embodiment, the first hydrogen-generating material 3 is porous, and the first hydrogen-generating material 3 has a porosity of 10 to 300ppi.
The inventors have found that the first hydrogen generating material 3 having a porous structure has a larger specific surface area, and the reaction rate of the first hydrogen generating material 3 with water vapor can be accelerated. If the porosity of the first hydrogen generating material 3 is less than 10ppi, the specific surface area of the first hydrogen generating material 3 is too small, the reaction rate of the first hydrogen generating material 3 and water vapor is too small, sufficient hydrogen cannot be generated, the protection effect on the electrochemical stack 1 is poor, and if the porosity of the first hydrogen generating material 3 is more than 300ppi, the pore path of the first hydrogen generating material 3 is tortuous and long, the pressure loss at the inlet of the first reaction zone of the electrochemical stack 1 is increased, the air supply difficulty at the inlet of the first reaction zone of the electrochemical stack 1 is increased, and the energy consumption of an air supply device is increased.
It should be understood that the reducing fluid of the present utility model may be hydrogen or a mixture of hydrogen and methane, the first reaction zone being an anode reaction zone if the electrochemical stack is a solid oxide fuel cell, or a cathode reaction zone if the electrochemical stack is a solid oxide electrolysis cell.
In one embodiment, the thermodynamic equilibrium hydrogen partial pressure of the oxidation reaction of the first hydrogen generating material 3 in the first hydrogen generating device 2 is P 1, the thermodynamic equilibrium hydrogen partial pressure of the oxidation reaction of the catalyst in the reaction zone of the electrochemical stack 1 is P 2, the hydrogen partial pressure in the first hydrogen generating device 2 is P 3,P3＞P1 when the electrochemical device is operating normally, and the hydrogen partial pressure in the first reaction zone of the electrochemical stack 1 is P 4,P4＞P2 when the reducing fluid is not received at the inlet of the first hydrogen generating device 2.
According to the utility model, the filling position and the filling amount of the first hydrogen generating material 3 are regulated and controlled to ensure that the first hydrogen generating material 3 is kept in a reduced state during normal operation of the device, and when the inlet of the first hydrogen generating device 2 does not receive the reducing fluid due to sudden stop or failure of the electrochemical device, the first hydrogen generating material 3 can continuously react with water vapor to generate hydrogen protective gas. If the electrochemical device is operating normally, P 3＜P1, the first hydrogen generating material 3 in the first hydrogen generating device 2 is oxidized, and when the inlet of the first hydrogen generating device 2 does not receive the reducing fluid due to sudden stop or failure of the electrochemical device, the first hydrogen generating device no longer has the capability of reacting with water vapor to generate hydrogen shielding gas, and if the inlet of the first hydrogen generating device 2 does not receive the reducing fluid, P 4＜P2, the catalyst in the reaction zone of the electrochemical stack 1 is oxidized, resulting in irreversible damage.
In one embodiment, the electrochemical stack 1 is a solid oxide fuel cell, the electrochemical device further includes a reformer 4, and an outlet of the reformer 4, the first hydrogen generating device 2, and an inlet of the first reaction zone of the electrochemical stack 1 are sequentially connected.
If the electrochemical stack 1 is a solid oxide fuel cell, the inlet of the first reaction zone of the electrochemical stack 1 is an anode inlet, and the outlet of the first reaction zone of the electrochemical stack 1 is an anode outlet. The reactant gas in the reformer 4 generally includes steam and a reducing fluid, and once the electrochemical device is suddenly stopped or the inlet of the first hydrogen generating apparatus 2 does not receive the reducing fluid due to a fault, the steam in the reformer 4 directly flows to the anode of the solid oxide fuel cell, which may cause a certain damage to the anode structure of the fuel cell. According to the utility model, the first hydrogen generating device 2 is arranged between the outlet of the reformer 4 and the inlet of the first reaction zone of the electrochemical stack 1, when the electrochemical device is suddenly stopped or the inlet of the first hydrogen generating device 2 does not receive the reducing fluid due to faults, the first hydrogen generating material 3 can consume water vapor and generate hydrogen, and the generated hydrogen enters the anode of the gas battery, so that a good protection effect can be achieved.
In one embodiment, the electrochemical device is a solid oxide electrolytic cell, the electrochemical device further comprises a mixer 5, and an outlet of the mixer 5, the first hydrogen generating device 2 and an inlet of the first reaction zone of the electrochemical stack 1 are sequentially connected.
If the electrochemical pile 1 is a solid oxide electrolytic cell, the inlet of the first reaction zone of the electrochemical pile 1 is the cathode inlet of the solid oxide electrolytic cell, and the outlet of the first reaction zone of the electrochemical pile 1 is the cathode outlet of the solid oxide electrolytic cell. The reaction gas of the mixer 5 generally comprises water vapor and a reducing fluid, and once the electrochemical device is suddenly stopped or the inlet of the first hydrogen generating device 2 is stopped due to a fault, the reducing fluid is not received by the inlet of the first hydrogen generating device 2, and the water vapor in the mixer 5 flows to the cathode of the solid oxide electrolytic cell through the first hydrogen generating device 2, so that the cathode structure of the electrolytic cell is damaged to some extent. According to the utility model, the first hydrogen generating device 2 is arranged between the outlet of the mixer 5 and the inlet of the first reaction zone of the electrochemical reactor 1, when the electrochemical device is suddenly stopped or the inlet of the first hydrogen generating device 2 does not receive the reducing fluid due to faults, the first hydrogen generating material 3 can consume water vapor and generate hydrogen, and the generated hydrogen enters the cathode of the electrolytic cell, so that a good protection effect can be achieved.
Specifically, the electrochemical device further comprises a pressurized storage system 9, the outlet of the first reaction zone of the electrochemical stack 1, the second hydrogen generating device 6 and the inlet of the pressurized storage system 9 are sequentially connected, and the pressurized storage system 9 is used for storing the gas output by the second hydrogen generating device 6.
In an embodiment, the outlet of the first reaction zone of the electrochemical stack 1 is connected to a second hydrogen generating device 6, the second hydrogen generating device 6 is hollow and has two ends open, a second hydrogen generating material 7 is disposed in the second hydrogen generating device 6, the material of the second hydrogen generating material 7 is a reducing metal or a reducing alloy, and the second hydrogen generating material 7 can react with water vapor.
When the electrochemical device fails and the inlet of the first hydrogen generating device 2 does not receive the reducing fluid, the outlet of the first reaction zone of the electrochemical stack 1 is easy to generate water vapor backflow, and the water vapor backflow can cause certain invasive damage to the electrochemical stack 1. The second hydrogen generating device 6 is connected with the outlet of the first reaction zone of the electrochemical pile 1, and the second hydrogen generating material 7 filled in the second hydrogen generating device 6 is utilized to react with the water vapor in a reflux way to consume the water vapor and react with the water vapor to generate hydrogen protection gas, so that the water vapor is prevented from flowing back to the electrochemical pile 1, and the electrochemical pile 1 is prevented from being damaged.
Specifically, the second hydrogen generating material 7 has a porous structure, and the second hydrogen generating material 7 has a porosity of 10 to 300ppi.
The inventors have found that the second hydrogen generating material 7 having a porous structure has a larger specific surface area, and the reaction rate of the second hydrogen generating material 7 with water vapor can be accelerated. If the porosity of the second hydrogen generating material 7 is less than 10ppi, the specific surface area of the second hydrogen generating material 7 is too small, the reaction rate of the second hydrogen generating material 7 and water vapor is too small, the backflow water vapor is not consumed fast enough, sufficient hydrogen cannot be provided, the protection effect on the electrochemical stack 1 is poor, and if the porosity of the second hydrogen generating material 7 is more than 300ppi, the pore path of the second hydrogen generating material 7 is tortuous and long, the pressure loss at the outlet of the first reaction zone of the electrochemical stack 1 is increased, on one hand, the energy consumption of the gas supply device is increased, and on the other hand, the operation pressure of the electrochemical stack 1 is increased, and the sealing failure of the electrochemical stack 1 is easily caused.
Specifically, the electrochemical stack is a solid oxide fuel cell, the electrochemical device further comprises a combustor 8, and the outlet of the first reaction zone of the electrochemical stack 1, the second hydrogen generating device 6 and the inlet of the combustor 8 are sequentially connected.
Specifically, the thermodynamic equilibrium hydrogen partial pressure of the oxidation reaction of the second hydrogen generating material 7 in the second hydrogen generating device 6 is P 5, the thermodynamic equilibrium hydrogen partial pressure of the oxidation reaction of the catalyst in the reaction zone of the electrochemical stack 1 is P 2, the hydrogen partial pressure in the second hydrogen generating device 6 is P 6,P6＞P5 when the electrochemical device is operating normally, and the hydrogen partial pressure in the first reaction zone of the electrochemical stack 1 is P 4,P4＞P2 when the reducing fluid is not received at the inlet of the first hydrogen generating device 2.
According to the utility model, the filling position and the filling amount of the second hydrogen generating material 7 are regulated and controlled to ensure that the second hydrogen generating material 7 is kept in a reduced state during normal operation of the device, and when the inlet of the first hydrogen generating device 2 does not receive the reducing fluid, the second hydrogen generating material 7 can continuously react with water vapor to generate hydrogen shielding gas. If the electrochemical device is operating normally, P 6＜P5, the second hydrogen generating material 7 in the second hydrogen generating device 6 is oxidized, and when the inlet of the first hydrogen generating device 2 does not receive the reducing fluid due to sudden stop or failure of the electrochemical device, the refluxing water vapor cannot be consumed and sufficient hydrogen is provided, so that the protection effect of the electrochemical stack 1 is lost, and if the inlet of the second hydrogen generating device 6 does not receive the reducing fluid, P 4＜P2 oxidizes the catalyst in the reaction zone of the electrochemical stack 1, so that irreversible damage is caused.
In the present utility model, the reducing metal may be any one of iron, nickel, and cobalt, and the component of the reducing alloy includes at least two of iron, nickel, and cobalt.
The following examples and comparative examples are provided to facilitate an understanding of the present utility model. The examples are not provided to limit the scope of the claims. The experimental reagents and instruments involved in the practice of the present utility model are common reagents and instruments unless otherwise specified.
Example 1
The present embodiment provides an electrochemical device having a structure as shown in fig. 1.
The electrochemical device comprises an electrochemical pile 1, a first hydrogen generating device 2, a reformer 4, a second hydrogen generating device 6 and a combustor 8, wherein the electrochemical pile 1 is provided with a first reaction zone inlet, a first reaction zone and a first reaction zone outlet, the first reaction zone inlet and the first reaction zone outlet are respectively communicated with the first reaction zone, the electrochemical pile 1 is a solid oxide fuel cell, the first reaction zone is an anode reaction zone, the first hydrogen generating device 2 is of a structure with hollow inside and two open ends, the second hydrogen generating device 6 is of a structure with hollow inside and two open ends, the outlet of the reformer 4, the first hydrogen generating device 2 and the first reaction zone inlet of the electrochemical pile 1 are sequentially connected, the first reaction zone outlet of the electrochemical pile 1, the second hydrogen generating device 6 and the inlet of the combustor 8 are sequentially connected, the first hydrogen generating device 2 is filled with a first hydrogen generating material 3, and the second hydrogen generating device 6 is filled with a second hydrogen generating material 7.
The thermodynamic equilibrium hydrogen partial pressure of the oxidation reaction of the first hydrogen generating material 3 in the first hydrogen generating device 2 is P 1, the thermodynamic equilibrium hydrogen partial pressure of the oxidation reaction of the catalyst in the reaction zone of the electrochemical pile 1 is P 2, the hydrogen partial pressure in the first hydrogen generating device 2 is P 3,P3＞P1 when the electrochemical device is in normal operation, and the hydrogen partial pressure in the first reaction zone of the electrochemical pile 1 is P 4,P4＞P2 when the inlet of the first hydrogen generating device 2 does not receive the reducing fluid.
The thermodynamic equilibrium hydrogen partial pressure of the oxidation reaction of the second hydrogen generating material 7 in the second hydrogen generating device 6 is P 5, the hydrogen partial pressure in the second hydrogen generating device 6 is P 6,P6＞P5 when the electrochemical device is operating normally, and the hydrogen partial pressure in the first reaction zone of the electrochemical stack 1 is P 4,P4＞P2 when the reducing fluid is not received at the inlet of the first hydrogen generating device 2.
The first hydrogen generating material 3 was made of iron, the first hydrogen generating material 3 had a porosity of 110ppi, the second hydrogen generating material 7 was made of iron, and the second hydrogen generating material 7 had a porosity of 110ppi.
Example 2
The present embodiment provides an electrochemical device having a structure as shown in fig. 2.
The electrochemical device comprises an electrochemical pile 1, a first hydrogen generating device 2, a mixer 5, a second hydrogen generating device 6 and a pressurized storage system 9, wherein the electrochemical pile 1 is provided with a first reaction zone inlet, a first reaction zone and a first reaction zone outlet, the first reaction zone inlet and the first reaction zone outlet are respectively communicated with the first reaction zone, the electrochemical pile 1 is a solid oxide electrolytic cell, the first reaction zone is a cathode reaction zone, the first hydrogen generating device 2 is of a structure with hollow inside and open ends, the second hydrogen generating device 6 is of a structure with hollow inside and open ends, the outlet of the mixer 5, the first hydrogen generating device 2 and the first reaction zone inlet of the electrochemical pile 1 are sequentially connected, the first hydrogen generating device 2 is filled with a first hydrogen generating material 3, and the second hydrogen generating device 6 is filled with a second hydrogen generating material 7.
The thermodynamic equilibrium hydrogen partial pressure of the oxidation reaction of the first hydrogen generating material 3 in the first hydrogen generating device 2 is P 1, the thermodynamic equilibrium hydrogen partial pressure of the oxidation reaction of the catalyst in the reaction zone of the electrochemical pile 1 is P 2, the hydrogen partial pressure in the first hydrogen generating device 2 is P 3,P3＞P1 when the electrochemical device is in normal operation, and the hydrogen partial pressure in the first reaction zone of the electrochemical pile 1 is P 4,P4＞P2 when the inlet of the first hydrogen generating device 2 does not receive the reducing fluid.
The thermodynamic equilibrium hydrogen partial pressure of the oxidation reaction of the second hydrogen generating material 7 in the second hydrogen generating device 6 is P 5, the hydrogen partial pressure in the second hydrogen generating device 6 is P 6,P6＞P5 when the electrochemical device is operating normally, and the hydrogen partial pressure in the first reaction zone of the electrochemical stack 1 is P 4,P4＞P2 when the reducing fluid is not received at the inlet of the first hydrogen generating device 2.
The first hydrogen generating material 3 is made of iron-nickel alloy (iron-nickel ratio 1:1), the first hydrogen generating material 3 has a porosity of 60ppi, the second hydrogen generating material 7 is made of iron-nickel alloy (iron-nickel ratio 1:1), and the second hydrogen generating material 7 has a porosity of 60ppi.
Comparative example 1
The present comparative example is different from example 1 in that the first hydrogen generating apparatus 2 was not filled with the first hydrogen generating material, and the second hydrogen generating apparatus 6 was not filled with the second hydrogen generating material.
The operation of the first hydrogen generator 2 and the second hydrogen generator 6 in the electrochemical devices of example 1 and comparative example 1 was verified, and the electrochemical device was applied to a Solid Oxide Fuel Cell (SOFC) system before verification, and the verification procedure was as follows:
The SOFC system is in a heat preservation state (660 ℃) of normal operation, the supply reducing fluid is natural gas and steam, the corresponding molar flow ratio is 1:3, and the outlet temperature of the reformer is 440 ℃. The internal temperature of the first hydrogen generating apparatus 2 was 790 ℃, the corresponding composition of the internal fluid was H 2O(54.24％)、CH4(15.55％)、H2(23.94％)、CO2 (5.95%), CO (0.31%), i.e. the hydrogen partial pressure P 3 in the first hydrogen generating apparatus 2 was 0.24bar, while the thermodynamic equilibrium hydrogen partial pressure P 1 at which the oxidation reaction of the first hydrogen generating material 3 took place was 0.03bar, P 3＞P1, which indicates that the first hydrogen generating material 3 was in a reduced state.
And sending an emergency stop command to the SOFC system, automatically cutting off the reducing fluid, and detecting the open-circuit voltage of the electrochemical stack 1 by adopting a DC-DC converter when the system is in a natural cooling state. The test results are shown in FIG. 3.
As can be seen from fig. 3, the voltage value of example 1 is significantly greater than that of comparative example 1 after stopping the supply of the reducing fluid, since the open circuit voltage is directly related to the hydrogen partial pressure of the reaction zone, and at the same temperature, the higher the open circuit voltage, the higher the hydrogen partial pressure. From this, it is understood that the hydrogen generated by the reaction of the first hydrogen generating material 3 and the water vapor in example 1 enters the anode of the fuel cell, so that the hydrogen partial pressure of the anode is high, and the function of protecting the anode structure of the electrochemical stack 1 is achieved.
The following tests were performed on the devices of examples 1-2 above:
1. Installing a first hydrogen generating device filled with a first hydrogen generating material or a second hydrogen generating device filled with a second hydrogen generating material in a hearth, connecting the first hydrogen generating device or the second hydrogen generating device with the second hydrogen generating material on an air supply pipeline with a humidifying function, setting the temperature of the hearth to 800 ℃, introducing 2L/min dry H 2 for 2 hours, switching the gas into 2L/min dry hydrogen-nitrogen mixed gas (4% H 2), cooling the hearth to room temperature, taking out the first hydrogen generating material or the second hydrogen generating material, and weighing to obtain the initial quality of the first hydrogen generating material or the second hydrogen generating material;
2. Reinstalling the removed first or second hydrogen generating material into the furnace, and raising the furnace temperature to 800 ℃ under an atmosphere of 2L/min dry hydrogen-nitrogen mixture (4% H 2);
3. The gas is switched to 2L/minN 2 (20% humidification) for 2 hours to perform forced oxidation on the first hydrogen generating material or the second hydrogen generating material;
4. The gas is switched to 2L/min for drying H 2, and the first hydrogen generating material or the second hydrogen generating material is reduced for 2 hours;
5. And (3) sequentially repeating the steps 3 and 4 for 20 times, switching the gas into 2L/min dry hydrogen-ammonia mixed gas (4% H 2), cooling the hearth to room temperature, taking out the first hydrogen generating material or the second hydrogen generating material, and weighing to obtain the termination quality.
The test results show that the mass loss of both the first hydrogen-generating material and the second hydrogen-generating material after 20 repetitions of steps 3 and 4 (i.e., 20 cuts off and resumes the supply of the reducing fluid) was 1% or less.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present utility model and not for limiting the scope of the present utility model, and although the present utility model has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present utility model may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present utility model.
Claims (10)
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