碳中和背景下高温固体氧化物电解制氢的过程建模与热力学分析

doi:10.12096/j.2096-4528.pgt.21010

摘要/Abstract

摘要：

电解制氢能够将不稳定的可再生能源转化为氢能，实现大规模、季节性储能，是助力实现我国碳中和目标的关键手段之一。对高温固体氧化物电解制氢技术进行了探讨与研究，介绍了高温固体氧化物电解的工作原理；针对其实际运行特性，建立了电解过程电化学模型与热力学模型，并通过与实验数据对比验证了模型的有效性；进一步地，分析了电流密度和操作温度对高温固体氧化物电解极化损失的影响，研究了高温电解过程热力学性能的变化情况。结果表明：在高温下对固体氧化物电解进行整体热集成与热管理，有利于减少电能消耗；若将高温电解过程与其他工业过程相结合，利用低品位的工业余热或废热，则能够进一步提升高温固体氧化物电解的整体能效。

关键词: 碳中和, 可再生能源, 电解制氢, 高温固体氧化物, 电化学模型, 热力学分析

Abstract:

Water electrolysis can transform unstable renewable energy into the hydrogen energy and realize large-scale and seasonal energy storage, which is one of the key means to achieve the goal of "carbon neutrality" in China. The technology of high temperature solid oxide electrolysis cell (SOEC) was discussed and studied, and the working principle of the high temperature solid oxide electrolysis was introduced. According to its actual operation characteristics, the electrochemical model and thermodynamic model of electrolysis process were established, and the models were verified by comparing with the experimental data. Furthermore, the effects of current density and operating temperature on the high temperature solid oxide electrolysis were analyzed, and the thermodynamic analysis was conducted. The results show that the thermal integration and management of SOEC at high temperature will be conducive to reduce the power consumption. If the high-temperature electrolysis process is combined with other industrial processes and utilized the low-grade industrial waste heat, the overall efficiency of high-temperature solid oxide electrolysis is expected to be further improved.

Key words: carbon neutrality, renewable energy, hydrogen production by electrolysis, high temperature solid oxide, electrochemical model, thermodynamic analysis

中图分类号:

TK91
TQ116.2

王丹丹, 李亚楼, 李芳, 孙璐. 碳中和背景下高温固体氧化物电解制氢的过程建模与热力学分析[J]. 发电技术, 2021, 42(5): 554-560.

Dandan WANG, Yalou LI, Fang LI, Lu SUN. Process Modelling and Thermodynamic Analysis of Hydrogen Production by High Temperature Solid Oxide Electrolysis Under the Background of Carbon Neutrality[J]. Power Generation Technology, 2021, 42(5): 554-560.

图/表 10

图1 高温固体氧化物电解过程

Fig.1 High temperature solid oxide electrolysis process

图2 SOEC所需能量、能斯特电压与温度的关系

Fig.2 Relationship between energy, Nernst voltage and temperature for SOEC

表1 电解模型的操作条件和结构参数

Tab. 1 Operating conditions and structural parameters of electrolysis model

操作条件和结构参数	数值
操作压力P/kPa	100
操作温度T/K	973
阴极入口成分及其体积分数	100%O₂
阳极入口成分及其体积分数	90%H₂O，10%H₂
电子转移数n	2
阴极厚度d_H₂/μm	312.5
阳极厚度d_O₂/μm	17.5
电解质厚度d_E/μm	12.5
阴极指前因子γ_c/(GA/m²)	0.39
阳极指前因子γ_a/(GA/m²)	1.39
阴极活化能ΔE_{act, c}/(MJ/mol)	0.1
阳极活化能ΔE_{act, a}/(MJ/mol)	0.12
孔隙曲度ξ	5
孔隙率ε	0.3
孔隙平均半径r/μm	0.5

表2 SOEC模型电压模拟值与实验值对比

Tab. 2 Comparison of voltage simulation values and experimental values of SOEC model

电流密度/(A/m²)	电压模拟值/V		电压实验值/V
电流密度/(A/m²)	923 K	973 K	923 K	973 K
0	0.934	0.915	0.895	0.880
1 000	1.131	1.033	1.064	0.972
2 000	1.249	1.122	1.236	1.077
3 000	1.337	1.193	1.385	1.178
4 000	1.410	1.252	1.510	1.277
5 000	1.474	1.303	1.580	1.360
6 000	1.532	1.350	1.620	1.420
7 000	1.586	1.392	1.655	1.466
8 000	1.636	1.432	1.680	1.510

图3 各类极化过电压分布情况

Fig.3 Distribution of various polarization overvoltage

图4 电流密度、温度对活化过电压的影响

Fig.4 Influence of current density and temperature on activation overvoltage

图5 电流密度、温度对欧姆过电压的影响

Fig.5 Influence of current density and temperature on ohmic overvoltage

图6 电流密度、温度对浓差过电压的影响

Fig.6 Influence of current density and temperature on concentration overvoltage

图7 电流密度、温度对SOEC所需热能的影响

Fig.7 Influence of current density and temperature on heat energy required by SOEC

图8 电流密度、温度对SOEC所需电能的影响

Fig.8 Influence of current density and temperature on power required by SOEC

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