CN119859810B - Membrane-free water electrolysis hydrogen production electrolytic tank based on chemical chain circulation and operation method - Google Patents
Membrane-free water electrolysis hydrogen production electrolytic tank based on chemical chain circulation and operation methodInfo
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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Abstract
Description
技术领域Technical Field
本发明涉及电解水制氢技术领域,尤其是一种基于化学链循环的无膜电解水制氢电解槽及运行方法。The present invention relates to the technical field of water electrolysis hydrogen production, and in particular to a membraneless water electrolysis hydrogen production electrolyzer based on chemical chain circulation and an operation method thereof.
背景技术Background Art
氢气由于其高能量密度及环境友好特性,被广泛视为一种理想的绿色能源载体。然而,目前全球90%以上的氢气生产依赖于化石燃料,这导致了大量二氧化碳的排放,不利于应对气候变化。为实现无碳经济,电解水制氢技术显得尤为关键,特别是在利用可再生能源如太阳能、风能、水能和地热能来提供电能的情况下。这种制氢方式不仅能够有效存储可再生能源的多余电力,还能解决可再生能源在时空分布上的不连续性问题,从而促进能源的可持续供应和分配。传统的有膜电解水制氢技术面临多重挑战,包括氢气与氧气混合带来的安全隐患、膜材料高昂的成本、膜电阻导致的效率损失等,上述问题限制了系统容量,阻碍了电解水制氢的大规模应用。尽管近年来国内外研究机构开发了数百种新型膜材料,但由于膜的离子传输活性和物理化学稳定性的限制,有膜电解水制氢技术始终难以突破安全性、大容量和低能耗之间的矛盾。Hydrogen, due to its high energy density and environmentally friendly properties, is widely considered an ideal green energy carrier. However, currently, over 90% of global hydrogen production relies on fossil fuels, resulting in significant carbon dioxide emissions and hindering climate change mitigation. To achieve a carbon-free economy, water electrolysis is crucial for hydrogen production, particularly when utilizing renewable energy sources such as solar, wind, hydro, and geothermal energy. This hydrogen production method not only effectively stores excess renewable energy but also addresses the spatial and temporal discontinuities of renewable energy, thereby promoting sustainable energy supply and distribution. Conventional membrane water electrolysis technology faces multiple challenges, including safety hazards associated with hydrogen and oxygen mixing, the high cost of membrane materials, and efficiency losses due to membrane resistance. These challenges limit system capacity and hinder the large-scale application of water electrolysis hydrogen production. Despite the recent development of hundreds of new membrane materials by research institutions both domestically and internationally, membrane water electrolysis technology has struggled to overcome the trade-off between safety, high capacity, and low energy consumption due to limitations in membrane ion transport activity and physicochemical stability.
针对此,无膜电解水技术应运而生,其通过载氧体的氧化还原循环(即化学链循环)实现析氢析氧反应的时空解耦,具有本征安全性和能耗等优势。但现有的无膜电解技术存在电解槽结构集成度低、制氢和制氧效率不高等问题。To address this issue, membraneless water electrolysis technology has emerged. It achieves spatiotemporal decoupling of the hydrogen and oxygen evolution reactions through the redox cycle of oxygen carriers (i.e., chemical chaining), offering advantages such as inherent safety and energy efficiency. However, existing membraneless electrolysis technologies suffer from low electrolyzer structural integration and low hydrogen and oxygen production efficiency.
发明内容Summary of the Invention
针对现有技术的不足,本发明提供一种基于化学链循环的无膜电解水制氢电解槽及运行方法,目的是提高电解槽结构的集成度,提高制氢效率。In view of the shortcomings of the existing technology, the present invention provides a membraneless water electrolysis hydrogen production electrolyzer based on chemical chain circulation and an operation method, the purpose of which is to improve the integration of the electrolyzer structure and improve the hydrogen production efficiency.
本发明采用的技术方案如下:The technical solution adopted in the present invention is as follows:
本发明提供一种基于化学链循环的无膜电解水制氢电解槽,所述电解槽包括分别与外部电源相连的第一端板、第二端板,所述第一端板与第二端板连接成整体,其内部设有至少一个双极板,两个端板和双极板之间、以及相邻两个双极板之间分别形成有电解小室;The present invention provides a membraneless water electrolysis hydrogen production electrolyzer based on chemical chaining cycle, the electrolyzer comprising a first end plate and a second end plate respectively connected to an external power supply, the first end plate and the second end plate being integrally connected, at least one bipolar plate being provided therein, and electrolysis chambers being formed between the two end plates and the bipolar plate, and between two adjacent bipolar plates;
每个所述电解小室内设有功能组件,所述功能组件包括依次贴合的双功能电极、多孔隔板和载氧体电极,所述双功能电极用于在第一工况下进行催化析氢、在第二工况下进行催化析氧;所述第一工况、第二工况下所述外部电源的极性相反;Each electrolysis cell is provided with a functional component, comprising a bifunctional electrode, a porous separator, and an oxygen carrier electrode bonded in sequence, wherein the bifunctional electrode is configured to catalyze hydrogen evolution under a first operating condition and catalyze oxygen evolution under a second operating condition; the polarity of the external power supply is opposite in the first and second operating conditions;
所述功能组件外侧套设有垫片;A gasket is provided on the outer side of the functional component;
除靠近所述第一端板的电解小室中所述功能组件外侧套设的垫片不设第一上通道,其余垫片的上部沿厚度方向均设有第一上通道;Except for the gasket sleeved on the outer side of the functional component in the electrolysis chamber close to the first end plate, which is not provided with the first upper channel, the upper parts of the remaining gaskets are provided with the first upper channel along the thickness direction;
所有垫片的下部均设有第一下通道;The lower part of all gaskets is provided with a first lower channel;
所述双极板两侧设有第一流道区,两侧的所述第一流道区通过其上分布的导电柱分别与所述载氧体电极和双功能电极电连接,使多个电解小室依次串联;The bipolar plate is provided with a first flow channel area on both sides, and the first flow channel areas on both sides are electrically connected to the oxygen carrier electrode and the bifunctional electrode respectively through the conductive columns distributed thereon, so that the multiple electrolysis chambers are connected in series in sequence;
双极板上部沿厚度方向设有第二上通道、下部沿厚度方向设有第二下通道,所述第一波流道区上部设有与所述第二上通道连通的第一导流道,所述第一流道区下部设有与所述第二下通道连通的第二导流道;A second upper channel is provided on the upper portion of the bipolar plate along the thickness direction, and a second lower channel is provided on the lower portion along the thickness direction. A first flow guide channel communicating with the second upper channel is provided on the upper portion of the first wave flow channel region, and a second flow guide channel communicating with the second lower channel is provided on the lower portion of the first flow channel region.
所述第一下通道、第二下通道依次交替连通形成电解液输入通道,所述电解液输入通道内的电解液经过所述第二导流道流入各电解小室;The first lower channel and the second lower channel are alternately connected in sequence to form an electrolyte input channel, and the electrolyte in the electrolyte input channel flows into each electrolytic chamber through the second flow guide channel;
所述第一上通道、第二上通道依次交替连通形成气液输出通道,各电解小室中的电解产物及电解液由所述第一导流道流出至所述气液输出通道;The first upper channel and the second upper channel are alternately connected in sequence to form a gas-liquid output channel, and the electrolysis products and electrolyte in each electrolysis chamber flow out from the first flow guide channel to the gas-liquid output channel;
所述第一端板内侧设有第二流道区,其通过导电柱与双功能电极连接,第一端板上沿厚度方向设有输入口;A second flow channel area is provided on the inner side of the first end plate, which is connected to the dual-function electrode through a conductive column, and an input port is provided on the upper thickness direction of the first end plate;
所述第二端板内侧设有第三流道区,其通过导电柱与载氧体电极连接,第二端板上沿厚度方向设有输出口;A third flow channel area is provided on the inner side of the second end plate, which is connected to the oxygen carrier electrode through a conductive column, and an output port is provided on the second end plate in the thickness direction;
所述第三流道区上部设有与所述输出口连通的第一导流道,The upper portion of the third flow channel area is provided with a first flow guide channel connected to the output port.
第三流道区下部设有与所述电解液输入通道连通的第二导流道;A second flow channel communicating with the electrolyte input channel is provided at the lower portion of the third flow channel area;
所述电解液输入通道入口端与所述输入口连接,所述气液输出通道出口端与所述输出口连接。The inlet end of the electrolyte input channel is connected to the input port, and the outlet end of the gas-liquid output channel is connected to the output port.
进一步技术方案为:Further technical solutions are:
所述第一导流道和第二导流道位于双极板和第二端板的靠近载氧体电极侧。The first flow guide channel and the second flow guide channel are located on the side of the bipolar plate and the second end plate close to the oxygen carrier electrode.
第一导流道、第二导流道的深度均不大于双极板厚度的二分之一。The depth of the first flow guide channel and the second flow guide channel is no more than half the thickness of the bipolar plate.
所述双功能电极的材质包括金属磷化物、金属硫化物、金属碳化物、金属氮化物、金属氧化物中的一种。The material of the bifunctional electrode includes one of metal phosphide, metal sulfide, metal carbide, metal nitride and metal oxide.
所述双功能电极尺寸不大于所述载氧体电极尺寸。The size of the bifunctional electrode is no larger than that of the oxygen carrier electrode.
所述载氧体电极为以氢氧化镍为主要成分的电极。The oxygen carrier electrode is an electrode with nickel hydroxide as a main component.
所述多孔隔板为镂空或不镂空片状结构,由绝缘多孔材料制成。The porous partition is a hollow or non-hollow sheet structure and is made of insulating porous material.
本发明还提供一种所述基于化学链循环的无膜电解水制氢电解槽的运行方法,包括氢、氧分步式生产,其包括:The present invention also provides a method for operating the membraneless water electrolysis hydrogen production electrolyzer based on chemical looping cycle, including step-by-step production of hydrogen and oxygen, which comprises:
通过控制外部电源开关切换电解槽的运行工况,使至少一个所述电解槽在第一工况、第二工况下依次交替运行,实现同一空间内氢气、氧气的分步生产;By controlling an external power switch to switch the operating conditions of the electrolytic cells, at least one of the electrolytic cells is operated alternately in a first operating condition and a second operating condition, thereby realizing step-by-step production of hydrogen and oxygen in the same space;
所述第一工况为:在20-50℃电解液中,所述第一端板和第二端板分别连接外部电源负极和正极,通电后所述双功能电极促进电解水产氢,所述载氧体电极中的活性组分被氧化为氧化态载氧体,氢气从所述气液输出通道输出;The first operating condition is as follows: in an electrolyte at 20-50°C, the first end plate and the second end plate are connected to the negative electrode and the positive electrode of an external power supply, respectively. When powered on, the bifunctional electrode promotes the electrolysis of water to produce hydrogen, the active components in the oxygen carrier electrode are oxidized to oxidized oxygen carriers, and hydrogen is output from the gas-liquid output channel.
所述第二工况为:在50-100℃的电解液中,反转外部电源极性,即所述第一端板和第二端板分别连接外部电源正极和负极,通电后所述双功能电极促进电解水产氧,所述载氧体电极中的氧化态载氧体在温度场作用下被部分自发还原同时在电场的作用下被完全还原,氧气从所述气液输出通道输出。The second operating condition is: in an electrolyte at 50-100°C, the polarity of the external power supply is reversed, that is, the first end plate and the second end plate are respectively connected to the positive and negative electrodes of the external power supply. After power is turned on, the bifunctional electrode promotes the electrolysis of water to produce oxygen, and the oxidized oxygen carrier in the oxygen carrier electrode is partially spontaneously reduced under the action of the temperature field and is completely reduced under the action of the electric field, and oxygen is output from the gas-liquid output channel.
进一步技术方案的为:Further technical solutions are:
所述运行方法还包括氢、氧连续式生产,其包括:The operation method also includes continuous production of hydrogen and oxygen, which includes:
利用至少一个所述电解槽形成第一组电解槽、利用至少一个所述电解槽形成第二组电解槽;Using at least one of the electrolytic cells to form a first group of electrolytic cells, and using at least one of the electrolytic cells to form a second group of electrolytic cells;
通过控制外部电源开关切换电解槽的运行工况,使所述第一组电解槽在所述第一工况、第二工况下依次交替运行,同时,所述第二组电解槽在所述第二工况、第一工况下依次交替运行,实现不同空间下氢气和氧气的连续生产。By controlling the external power switch to switch the operating conditions of the electrolytic cells, the first group of electrolytic cells operates alternately under the first operating condition and the second operating condition. At the same time, the second group of electrolytic cells operates alternately under the second operating condition and the first operating condition, thereby realizing continuous production of hydrogen and oxygen in different spaces.
所述电解液为KOH或NaOH溶液。The electrolyte is KOH or NaOH solution.
本发明的有益效果如下:The beneficial effects of the present invention are as follows:
1、本发明在电解槽中引入了双功能电极,该电极不仅能够催化析氢反应,也能催化析氧反应,从而提高了电解槽系统的集成度。此外,避免了贵金属材料的使用,设备成本显著降低。1. The present invention introduces a bifunctional electrode into the electrolyzer, which catalyzes both the hydrogen evolution reaction and the oxygen evolution reaction, thereby improving the integration of the electrolyzer system. In addition, the use of precious metal materials is avoided, significantly reducing equipment costs.
2、本发明通过载氧体电极的氧化还原循环,在同一电解槽内实现了分步制氢、制氧。与双功能电极耦合后,可以在不同电压条件下制氢和制氧,极大地适应了可再生能源的功率波动性和间歇性,具备离网制氢的潜力。2. This invention achieves step-by-step hydrogen and oxygen production within the same electrolyzer through redox cycling of oxygen-carrier electrodes. Coupled with bifunctional electrodes, hydrogen and oxygen production can be achieved under different voltage conditions, significantly adapting to the power fluctuations and intermittency of renewable energy and demonstrating the potential for off-grid hydrogen production.
3、本发明通过温度场和电场的耦合向电解系统供能。在制氢阶段,载氧体在低温电场作用下被氧化,抑制竞争性析氧反应发生。在制氧阶段,氧化态载氧体在温度场和电场的共同作用下被还原,确保载氧体的完全再生,显著提升载氧体再生速率,解决了析氧反应的速率限制问题,大幅提高制氢循环效率。此外,由于温度场的作用,制氧电压大幅降低,显著降低了综合制氢成本。3. The present invention supplies energy to the electrolysis system through the coupling of temperature field and electric field. In the hydrogen production stage, the oxygen carrier is oxidized under the action of the low-temperature electric field, which inhibits the occurrence of competitive oxygen evolution reaction. In the oxygen production stage, the oxidized oxygen carrier is reduced under the combined action of the temperature field and the electric field, ensuring the complete regeneration of the oxygen carrier, significantly improving the regeneration rate of the oxygen carrier, solving the rate limitation problem of the oxygen evolution reaction, and greatly improving the hydrogen production cycle efficiency. In addition, due to the effect of the temperature field, the oxygen production voltage is greatly reduced, which significantly reduces the overall hydrogen production cost.
本发明的其它特征和优点将在随后的说明书中阐述,并且,部分地从说明书中变得显而易见,或者通过实施本发明而了解。Other features and advantages of the present invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the present invention.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为本发明实施例无膜电解水制氢的电解槽的结构示意图。FIG1 is a schematic structural diagram of an electrolytic cell for producing hydrogen by membraneless water electrolysis according to an embodiment of the present invention.
图2为本发明实施例的垫片的结构示意图。FIG2 is a schematic structural diagram of a gasket according to an embodiment of the present invention.
图3为本发明实施例的双极板的结构示意图。FIG3 is a schematic structural diagram of a bipolar plate according to an embodiment of the present invention.
图4为本发明实施例的第一端板结构示意图FIG4 is a schematic diagram of the first end plate structure according to an embodiment of the present invention
图5为本发明实施例的第二端板的结构示意图。FIG5 is a schematic structural diagram of a second end plate according to an embodiment of the present invention.
图6为本发明对比例和实施例2的单一电解小室测试所得槽电压曲线。FIG6 is a cell voltage curve obtained from the single electrolysis chamber test of the comparative example and Example 2 of the present invention.
图中:1、电解小室;2、双极板;3、电解液输入通道;4、气液输出通道;5、第一端板;6、第二端板;7、第一导流道;8、第二导流道;9、螺母;10、螺栓;101、双功能电极;102、多孔隔板;103、载氧体电极;104、垫片;201、第一流道区;301、第一下通道;302、第二下通道;401、第一上通道;402、第二上通道;501、第二流道区;601、第三流道区;3011、输入口;4021、输出口。In the figure: 1. electrolysis chamber; 2. bipolar plate; 3. electrolyte input channel; 4. gas-liquid output channel; 5. first end plate; 6. second end plate; 7. first flow channel; 8. second flow channel; 9. nut; 10. bolt; 101. bifunctional electrode; 102. porous partition; 103. oxygen carrier electrode; 104. gasket; 201. first flow channel area; 301. first lower channel; 302. second lower channel; 401. first upper channel; 402. second upper channel; 501. second flow channel area; 601. third flow channel area; 3011. input port; 4021. output port.
具体实施方式DETAILED DESCRIPTION
以下结合附图说明本发明的具体实施方式。The specific embodiments of the present invention are described below with reference to the accompanying drawings.
实施例1Example 1
如图1所示,本实施例的一种基于化学链循环的无膜电解水制氢电解槽,电解槽包括分别与外部电源相连的第一端板5、第二端板6,第一端板5、第二端板6连接形成整体,其内部设有一个或多个双极板2,两个端板和与之相邻的双极板2之间、以及相邻两个双极板2之间分别形成有电解小室1;As shown in FIG1 , a membraneless water electrolysis hydrogen production electrolyzer based on a chemical chaining cycle in this embodiment includes a first end plate 5 and a second end plate 6, each of which is connected to an external power source. The first end plate 5 and the second end plate 6 are connected to form a whole, and one or more bipolar plates 2 are provided therein. Electrolysis chambers 1 are formed between two end plates and adjacent bipolar plates 2, and between two adjacent bipolar plates 2.
每个电解小室内设有功能组件,功能组件包括依次贴合的双功能电极101、多孔隔板102和载氧体电极103,双功能电极101用于在第一工况下进行催化析氢、在第二工况下进行催化析氧;所述第一工况、第二工况下外部电源的极性相反;Each electrolysis cell is provided with a functional component, which includes a bifunctional electrode 101, a porous separator 102, and an oxygen carrier electrode 103, which are sequentially bonded. The bifunctional electrode 101 is used to catalyze hydrogen evolution under a first operating condition and catalyze oxygen evolution under a second operating condition. The polarity of the external power supply is opposite in the first and second operating conditions.
所述功能组件外侧套设有垫片104;A gasket 104 is provided on the outside of the functional component;
参见图1和图2,除靠近所述第一端板5的电解小室1中所述功能组件外侧套设的垫片104不设第一上通道401,其余垫片104的上部沿厚度方向均设有第一上通道401;所有垫片104的下部均设有第一下通道301;1 and 2 , except for the gasket 104 sleeved on the outside of the functional component in the electrolysis chamber 1 near the first end plate 5, which does not have the first upper channel 401, the upper portions of the remaining gaskets 104 are provided with the first upper channel 401 along the thickness direction; the lower portions of all gaskets 104 are provided with the first lower channel 301;
双极板2两侧分别与相邻两个电解小室的载氧体电极103和双功能电极101连接并形成流道,使多个电解小室1依次串联。Both sides of the bipolar plate 2 are respectively connected to the oxygen carrier electrodes 103 and the bifunctional electrodes 101 of two adjacent electrolysis chambers to form flow channels, so that multiple electrolysis chambers 1 are sequentially connected in series.
具体的,参见图1和图3,双极板2两侧设有第一波浪形导流面201,两侧的所述第一波浪形导流面201通过其上分布的导电柱分别与所述载氧体电极103和双功能电极101电连接,使多个电解小室1依次串联。Specifically, referring to Figures 1 and 3, a first wavy guide surface 201 is provided on both sides of the bipolar plate 2. The first wavy guide surfaces 201 on both sides are electrically connected to the oxygen carrier electrode 103 and the bifunctional electrode 101 through conductive columns distributed thereon, so that multiple electrolysis chambers 1 are connected in series in sequence.
双极板2上部沿厚度方向设有第二上通道402、下部沿厚度方向设有第二下通道302,所述第一波浪形导流面201上部设有与所述第二上通道402连通的第一导流道7,所述第一波浪形导流面201下部设有与所述第二下通道302连通的第二导流道8;The bipolar plate 2 has a second upper channel 402 formed on its upper portion along the thickness direction, and a second lower channel 302 formed on its lower portion along the thickness direction. The first wavy guide surface 201 has a first guide channel 7 in communication with the second upper channel 402 formed on its upper portion, and a second guide channel 8 in communication with the second lower channel 302 formed on its lower portion.
如图1所示,所述第一下通道301、第二下通道302依次交替连通形成电解液输入通道3,所述电解液输入通道3内的电解液经过所述第二导流道8流入各电解小室1;所述第一上通道401、第二上通道402依次交替连通形成气液输出通道4,各电解小室1中电解后反应物由所述第一导流道7流出至所述气液输出通道4。As shown in Figure 1, the first lower channel 301 and the second lower channel 302 are alternately connected in sequence to form an electrolyte input channel 3, and the electrolyte in the electrolyte input channel 3 flows into each electrolysis chamber 1 through the second guide channel 8; the first upper channel 401 and the second upper channel 402 are alternately connected in sequence to form a gas-liquid output channel 4, and the reactants after electrolysis in each electrolysis chamber 1 flow out from the first guide channel 7 to the gas-liquid output channel 4.
参见图4和图5,第一端板5内侧设有第二波浪形导流面501,其通过导电柱与双功能电极101连接,第一端板5上沿厚度方向设有输入口3011。第二端板6内侧设有第三波浪形导流面601,其通过导电柱与载氧体电极103连接,第二端板6上沿厚度方向设有输出口4021;第三波浪形导流面601上部设有与所述输出口4021连通的第一导流道7,第三波浪形导流面601下部设有与所述电解液输入通道3连通的第二导流道8。Referring to Figures 4 and 5 , a second wavy guide surface 501 is provided on the inner side of the first end plate 5, which is connected to the dual-function electrode 101 via a conductive post. An input port 3011 is provided along the thickness of the first end plate 5. A third wavy guide surface 601 is provided on the inner side of the second end plate 6, which is connected to the oxygen carrier electrode 103 via a conductive post. An output port 4021 is provided along the thickness of the second end plate 6. A first guide channel 7 communicating with the output port 4021 is provided on the upper portion of the third wavy guide surface 601, and a second guide channel 8 communicating with the electrolyte input channel 3 is provided on the lower portion of the third wavy guide surface 601.
电解液输入通道3入口端与所述输入口3011连接,用于向电解槽内部输送电解液。气液输出通道4出口端与所述输出口4021连接,用于向外输出电解后的氢气或氧气产物和电解液。The inlet of the electrolyte input channel 3 is connected to the input port 3011 for delivering electrolyte to the electrolytic cell. The outlet of the gas-liquid output channel 4 is connected to the output port 4021 for outputting hydrogen or oxygen products and electrolyte after electrolysis.
第一端板5、第二端板6上还设有电源接线柱和螺栓孔。作为具体实施方式,可采用螺母9和螺栓10将第一端板5、第二端板6端板固定连接,进而将各垫片104、双极板2压紧,使各电解小室被固定。Power terminals and bolt holes are also provided on the first and second end plates 5, 6. In a specific embodiment, nuts 9 and bolts 10 can be used to securely connect the first and second end plates 5, 6, thereby compressing the gaskets 104 and bipolar plates 2 to secure the electrolysis cells.
第一导流道7和第二导流道8位于双极板2和第二端板6的靠近载氧体电极103侧,第一导流道7和第二导流道8的深度不大于双极板2厚度的二分之一。The first flow channel 7 and the second flow channel 8 are located on the side of the bipolar plate 2 and the second end plate 6 close to the oxygen carrier electrode 103 . The depth of the first flow channel 7 and the second flow channel 8 is no more than half the thickness of the bipolar plate 2 .
本实施例的双功能电极101的材质包括金属磷化物、金属硫化物、金属碳化物、金属氮化物、金属氧化物中的一种。具体的,双功能电极101为在泡沫镍上原位电沉积的CoFeNiPOx。The material of the dual-function electrode 101 of this embodiment includes one of metal phosphide, metal sulfide, metal carbide, metal nitride, and metal oxide. Specifically, the dual-function electrode 101 is CoFeNiPOx in-situ electrodeposited on nickel foam.
本实施例的双功能电极101尺寸不大于载氧体电极103尺寸。双功能电极101尺寸具体为载氧体电极103尺寸的三分之一。The size of the dual-function electrode 101 in this embodiment is not larger than that of the oxygen carrier electrode 103. Specifically, the size of the dual-function electrode 101 is one-third of that of the oxygen carrier electrode 103.
本实施例的多孔隔板102由绝缘多孔材料制成,用于防止双功能电极101和载氧体电极103短路。具体的,多孔隔板102为玻璃纤维隔板。The porous separator 102 of this embodiment is made of an insulating porous material and is used to prevent short circuit between the dual-function electrode 101 and the oxygen carrier electrode 103. Specifically, the porous separator 102 is a glass fiber separator.
本实施例的载氧体电极103采用氢氧化镍为活性组分的电极,具体为泡沫镍负载的Ni0.9Co0.1(OH)2。The oxygen carrier electrode 103 of this embodiment uses nickel hydroxide as an active component, specifically Ni 0.9 Co 0.1 (OH) 2 supported by nickel foam.
作为优选实施方式,双功能电极101和载氧体电极103截面为圆形,双极板2的截面为圆形,多孔隔板102为圆环、全尺寸圆形和镂空圆形的一种。As a preferred embodiment, the bifunctional electrode 101 and the oxygen carrier electrode 103 have circular cross-sections, the bipolar plate 2 has a circular cross-section, and the porous separator 102 is a ring, a full-size circle, or a hollow circle.
实施例2Example 2
本实施例提供一种实施例1所述基于化学链循环的无膜电解水制氢电解槽的运行方法,包括氢、氧分步式生产。This embodiment provides a method for operating the membraneless water electrolysis hydrogen production electrolyzer based on chemical looping cycle described in Example 1, including step-by-step production of hydrogen and oxygen.
所述氢、氧分步式生产,具体包括:The step-by-step production of hydrogen and oxygen specifically includes:
通过控制外部电源开关切换电解槽的运行工况,使至少一个电解槽在第一工况、第二工况下依次交替运行,实现同一空间中氢气、氧气的分步生产;By controlling an external power switch to switch the operating conditions of the electrolytic cells, at least one electrolytic cell is operated alternately in a first operating condition and a second operating condition, thereby realizing step-by-step production of hydrogen and oxygen in the same space;
第一工况为:在25℃的5M KOH电解液中,第一端板5和第二端板6分别连接外部电源负极和正极,通电后双功能电极101促进电解水产氢,载氧体电极103中的活性组分被氧化为氧化态载氧体,氢气从气液输出通道4输出;The first operating condition is: in a 5M KOH electrolyte at 25°C, the first end plate 5 and the second end plate 6 are connected to the negative and positive electrodes of an external power supply, respectively. After power is applied, the bifunctional electrode 101 promotes the electrolysis of water to produce hydrogen, and the active components in the oxygen carrier electrode 103 are oxidized to oxidized oxygen carriers, and hydrogen is output from the gas-liquid output channel 4.
第二工况为:在90℃的5M KOH电解液中,反转外部电源极性,即第一端板5和第二端板6分别连接外部电源正极和负极,通电后双功能电极101促进电解水产氧,载氧体电极103中的氧化态载氧体在温度场作用下被部分自发还原同时在电场的作用下被完全还原,氧气从气液输出通道4输出。The second operating condition is: in a 5M KOH electrolyte at 90°C, the polarity of the external power supply is reversed, that is, the first end plate 5 and the second end plate 6 are connected to the positive and negative electrodes of the external power supply respectively. After power is turned on, the bifunctional electrode 101 promotes the electrolysis of water to produce oxygen, and the oxidized oxygen carrier in the oxygen carrier electrode 103 is partially spontaneously reduced under the action of the temperature field and is completely reduced under the action of the electric field, and oxygen is output from the gas-liquid output channel 4.
对比例Comparative Example
本对比例提供一种实施例1所述基于化学链循环的无膜电解水制氢电解槽的运行方法,和实施例2的区别是:电解液温度为25℃,即电解过程仅依赖电场供能。This comparative example provides an operating method of the membraneless water electrolysis hydrogen production electrolyzer based on chemical chain circulation described in Example 1. The difference from Example 2 is that the electrolyte temperature is 25°C, that is, the electrolysis process relies solely on electric field energy supply.
在100mA cm-2的制氢电流密度下,测试对比例和实施例2的单一电解小室,所得槽电压数据分别如图6中(a)、(b)所示。At a hydrogen production current density of 100 mA cm −2 , the single electrolysis cells of the comparative example and Example 2 were tested, and the cell voltage data obtained are shown in FIG6 (a) and (b) respectively.
与仅依赖电场供能的对比例相比,实施例2温度场与电场的共同作用显著降低了制氧电压。同时由于温度场作用下载氧体发生自发还原,加快了载氧体的再生速率,制氢效率显著高于仅电场供能条件。因此,温度场与电场的耦合供能显著提升了制氢循环效率。Compared to the comparative example relying solely on electric field power supply, the combined effects of the temperature field and electric field in Example 2 significantly reduced the oxygen production voltage. Furthermore, the temperature field activated the spontaneous reduction of the oxygen carrier, accelerating its regeneration rate, resulting in significantly higher hydrogen production efficiency than the electric field alone. Therefore, the coupled energy supply of the temperature field and electric field significantly improved the efficiency of the hydrogen production cycle.
实施例3Example 3
本实施例提供一种实施例1所述基于化学链循环的无膜电解水制氢电解槽的运行方法,包括氢、氧连续式生产。This embodiment provides a method for operating the membraneless water electrolysis hydrogen production electrolyzer based on chemical looping cycle described in Example 1, including continuous production of hydrogen and oxygen.
所述氢、氧连续式生产,包括:The continuous production of hydrogen and oxygen includes:
利用至少一个电解槽形成第一组电解槽、利用至少一个电解槽形成第二组电解槽;forming a first group of electrolytic cells using at least one electrolytic cell and forming a second group of electrolytic cells using at least one electrolytic cell;
通过控制外部电源开关切换电解槽的运行工况,使第一组电解槽在第一工况、第二工况下依次交替运行,同时,第二组电解槽在第二工况、第一工况下依次交替运行,实现不同空间下氢气和氧气的连续生产。By controlling the external power switch to switch the operating conditions of the electrolytic cells, the first group of electrolytic cells operates alternately under the first operating condition and the second operating condition. At the same time, the second group of electrolytic cells operates alternately under the second operating condition and the first operating condition, thereby realizing the continuous production of hydrogen and oxygen in different spaces.
本领域普通技术人员可以理解:以上所述仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例记载的技术方案进行修改,或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。Those skilled in the art will understand that the foregoing descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will be able to modify the technical solutions described in the foregoing embodiments or substitute equivalents for some of the technical features. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.
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