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绿氢需求的快速增长对制氢电解槽提出了低成本、高电密以及适应低/变负载运行和快速/频繁启停的要求。碱性水电解制氢是当前低成本电解制氢的首选方法，但其电流密度低且设备庞大，难以适应可再生能源的电力波动性。碱性水电解的进一步发展面临着关键材料性能提升、电解槽优化设计和运行调控等方面的技术挑战。本文在介绍碱性水电解基本原理的基础上，梳理了限制碱性电解槽电流密度和负载运行范围的关键材料的研究进展。针对电解槽运行控制，阐述了反向电流对电极材料的影响与缓解策略，最后展望了碱性水电解制氢技术发展前景与挑战。
Abstract：With the rapid development of modern society and escalating energy demands, the widespread use of traditional non-renewable fossil fuels has exacerbated environmental pollution and the greenhouse effect worldwide. The ‘carbon peak, carbon neutral' goal propels wind power and photovoltaic-based renewable clean energy for power generation capacity in China. However, the intermittent and variable nature of renewable energy, along with a limited grid load regulation capacity, hinders the large-scale conversion or storage of intermittent power. Hydrogen serves as a sustainable fuel option due to its impressive high-energy potential at 140 MJ/kg and its capability for extensive, long-term storage, positioning it as a crucial element in transitioning towards a world underpinned by green, low-carbon energy sources. Generating green hydrogen through the electrolysis of water, powered by the variable outputs of renewable energy sources, becomes the most viable strategy for producing green hydrogen, while also leveraging the surplus energy from these renewables. At present, the widely adopted technique for hydrogen generation through water electrolysis is alkaline water electrolysis(AWE) with significant advantages of large single-unit size and low equipment cost, thus being a preferred technology route for large-scale hydrogen production. However, alkaline water electrolyzer is difficult to use for the new situation of fluctuating power supply to produce green hydrogen efficiently due to the problems of low current density, massive equipment, and poor dynamic operation capability. Alkaline water electrolysis has a problem of low current density. For electrode materials, the lower intrinsic catalytic activity of non-precious metal electrode materials makes the kinetics of the electrolytic water reaction, compared with precious metal catalysts such as platinum and iridium oxide. For the diaphragm materials, the typical thickness of PPS diaphragms offers a significant resistance to the movement of hydroxide ions and potential risks for gas crossover. Also, frequent stops and starts can induce reverse current, resulting in corroded electrodes and reduced lifespan. To confront these challenges, this review mainly summarized the research progress on transition metal catalysts and the development of industrial electrode technology. Alkaline water electrolysis electrode materials are mainly classified into three categories, i.e., precious metals, transition metals, and nonmetals. Among these, transition metal-based catalysts(i.e., Ni, Fe, Co, and Mol, and their compounds) have the advantages of low cost, simple preparation, and various structural compositions. They are considered as ideal materials to replace precious metal catalysts. The main types of these catalysts include single transition metals, sulfides, phosphides, and nitrides. They are often modified via electronic environment regulation, nanostructure optimization, and multi-component synergistic effects to enhance their intrinsic catalytic activity. For an efficient and reliable alkaline water electrolysis system, a high-performance diaphragm is also essential. The diaphragm separates the cathode and anode, prevents the mixing of hydrogen and oxygen, and transfers hydroxide ions. This review also represented the research progress on a new generation of composite diaphragms, and discussed the modifying industrial PPS diaphragms. Simple organic fiber diaphragms have a poor pore structure and a high ionic resistance, and their thickness and gas barrier properties are difficult to fully address. Applying an inorganic functional coating to the surface of PPS fabric to create an organic-inorganic composite diaphragm becomes the main aspect of diaphragm research. The inorganic functional coating on the surface of the composite diaphragm improves hydrophilicity and gas barrier properties and reduces the thickness and ionic resistance of the diaphragm. Alkaline electrolyzer downtime can produce a reverse current due to the potential difference between the conductive metal bipolar plate formed by the electronic pathway and the ionic pathway constituted by the alkaline circulation. This can cause a significant corrosion to the cathode material in the large volume intermediate compartment of the alkaline electrolyzer and creates a potential safety issue. Therefore, some studies addressing the mechanisms of reverse current formation and mitigation strategies are crucial for alkaline water electrolyzers for frequent shutdown and startup. Summary and prospects Alkaline water electrolysis is a highly mature, simple, and low-cost hydrogen production technology that is widely applied to a large-scale hydrogen production in China. In the future, the construction of new power systems will urgently need a large-scale wind power consumption capacity as well as a low-cost, green hydrogen supply in chemical and transportation industries. This requires electrolysis cells capable of adapting to fluctuating power sources, i.e., wind power. However, the existing industrial technology mainly focuses on a single-tank hydrogen production for incremental improvements. Limited progress is made to address some issues like a low current density and a poor dynamic performance. The emerging demand for green electricity to produce green hydrogen leads to higher requirements for the key materials and equipment technology of alkaline water electrolysis. The next generation of this technology can feature a high current density and a low energy consumption, operate across a wide and variable load, and have rapid start/stop capabilities to accommodate the fluctuating hydrogen production scenarios of renewable energy. The lab-research of AWE electrode catalysts should consider the needs of industrial applications. Simple organic fiber diaphragms have a poor pore structure and a high ionic resistance. Hence, thick membranes(typically >0.8 mm) are required to meet the gas barrier properties. Organic-inorganic composite diaphragms are promising for future industrial applications, although their long-term durability still requires a further verification. Moreover, there is a significant lack of research on the effect of fluctuating working conditions(i.e., variable loads and start-stop cycles) on the dissolution of electrode catalysts, detachment, and mechanical damage to the diaphragm. Beyond materials, further studies on system operation control and optimization are needed to improve dynamic performance(i.e., strategies to mitigate reverse current that limits the start-stop frequency of alkaline water electrolyzers.
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基本信息:
DOI：10.14062/j.issn.0454-5648.20230988
中图分类号:TQ116.2
引用信息:
[1]刁书楷,赵雄,郁章涛,等.碱性水电解槽关键材料研究进展[J].硅酸盐学报,2024,52(06):1841-1860.DOI:10.14062/j.issn.0454-5648.20230988.
基金信息:
国家自然科学基金项目(52202234); 北京市科协青年人才托举工程项目(BYESS2023073); 多场景规模化电解水制关键技术研究及应用示范项目资助(合同号:CTGTCI2023-LQ-04)
2023-12-24
2023
2024-05-14
2024-05-12
2024
1
2024-05-09
2024-05-09
2024-05-09