热力学循环路径决定着热电转换工作过程与效率，热再生电化学循环（TREC）所有工作过程中均伴随着热量的变化（吸热或放热），对TREC热力学状态具有较大的影响，从而致使TREC热电转换特性与传统的埃里克森循环相比偏差较大。针对这一问题，本文对TREC进行了系统的热力学分析并针对有限时间、有限热源、无限时间、无限热源等多种实际情况建立了热力学过程描述和相应的数学模型，并深入探讨了实际运行过程与理想分析方法不协调所产生的性能数值偏差，及关键参数对系统性能的影响。 研究表明，当系统实际运行时间短于理想平衡所需时间时，应采用有限分析方法。若此时使用无限分析方法则会与实际情况产生偏差，偏差的大小与运行时间直接相关，而当运行时间达到平衡时间的80%时，这种偏差可控制在2%以下。 热源对系统运行阶段的影响主要体现在平衡时的温度和温度平衡速率上。 这种影响与热电容成正比，也与系统性能成正相关。 因此，为了提高系统性能，建议选择热容与系统热容比较高的高/低温热源，并且等压吸放热阶段的时间应略微超过系统平衡所需的时间。
FU Shen
,
TANG Xin
,
LIU Penghui
,
LI Guiqiang
. A Systematic Thermodynamic Analysis of the Thermally Regenerative Electrochemical Cycle[J]. 热科学学报, 2025
, 34(2)
: 389
-399
.
DOI: 10.1007/s11630-025-2094-5
Thermally regenerative electrochemical cycle (TREC) is a novel and effective heat-to-electricity technology for harvesting low-grade heat. Currently, reported TREC analyses have been based on the Stirling cycle of ideal infinite heat source and infinite time for heat transfer. However, this will lead to inaccuracy when the scenario deviates from the ideal case. In this study, a systematic thermodynamic analysis on TREC is performed to address this problem. Based on different heat transfer situations, the description of thermodynamic processes and the corresponding mathematical models are established. At the same time, the TREC system, with the solar collector as the high-temperature heat source and the environment as the low-temperature heat source, is employed as a case. And the study delved into discrepancies arising from incongruences between the practical operational process and the traditional ideal analytical methodologies, along with an investigation of the different thermal environment impact on system performance. The findings suggest that the finite analysis method should be used when the actual operating time of the system is shorter than the desired equilibrium period. On the contrary, the use of the infinite analysis method, in this case, produces an error, the magnitude of which is directly related to the operating time, whereas when the time reaches 80% of the equilibrium time the error can be controlled to less than 2%. The influence of the heat source on the operating phase of the system is mainly in the temperature equilibrium and the rate of temperature equilibrium. This effect is proportional to the thermal capacitance and is also positively related to the system performance. Therefore, to improve system performance, it is recommended that a high-temperature heat source with a high ratio of thermal capacitance to system thermal capacitance should be selected and that the response time should slightly exceed the system equilibrium duration.
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