Article(id=1239211866078105951, tenantId=1146029695717560320, journalId=1238823019242635269, issueId=1239211861397270994, articleNumber=null, orderNo=null, doi=10.12465/j.issn.0253-4339.2025.01.032, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1701792000000, receivedDateStr=2023-12-06, revisedDate=1704384000000, revisedDateStr=2024-01-05, acceptedDate=1705334400000, acceptedDateStr=2024-01-16, onlineDate=1773380732315, onlineDateStr=2026-03-13, pubDate=1739635200000, pubDateStr=2025-02-16, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773380732315, onlineIssueDateStr=2026-03-13, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773380732315, creator=13701087609, updateTime=1773380732315, updator=13701087609, issue=Issue{id=1239211861397270994, tenantId=1146029695717560320, journalId=1238823019242635269, year='2025', volume='46', issue='1', pageStart='1', pageEnd='166', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=0, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773380731200, creator=13701087609, updateTime=1773384112372, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1239226043106652319, tenantId=1146029695717560320, journalId=1238823019242635269, issueId=1239211861397270994, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1239226043106652320, tenantId=1146029695717560320, journalId=1238823019242635269, issueId=1239211861397270994, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=32, endPage=45, ext={EN=ArticleExt(id=1239211866292015457, articleId=1239211866078105951, tenantId=1146029695717560320, journalId=1238823019242635269, language=EN, title=Research Progress of Compression Heat Pump Coupled with Heat Storage of Phase Change Materials, columnId=null, journalTitle=Journal of Refrigeration, columnName=null, runingTitle=null, highlight=null, articleAbstract=

The application of latent thermal energy storage with heat pumps has been extensively studied in recent years. The combination of phase change heat storage and a heat pump can improve the performance of the heat pump and the utilization of renewable energy; however, further cost reduction and efficiency increase are required. Therefore, this study reviews the progress of heat pumps coupled with solid-liquid phase change materials and summarizes the applicable conditions and characterization methods for phase change materials applied to heat pumps. The optimization approaches for the performance of the heat pump system are summarized, including the selection and improvement of phase change materials, the optimal setting of the heat exchanger, and the dynamic optimization control strategy of the system. The outstanding performance of heat pumps with cascade heat storage in improving the supply-side comfort and utilization rate of renewable energy indicates the broad prospect of cascade heat storage being applied to heat pump energy storage systems. Herein, mixed, non-eutectic phase change materials are proposed as alternative materials for cascade heat storage. Notably, summarizing and developing new methods for adjusting the thermophysical properties of phase change materials for energy storage is necessary for adapting the selection and improvement of phase change materials to the optimization of the thermodynamic cycle of cascade heat storage devices and further improving the heating decarbonization ability of latent heat storage heat pumps.

, correspAuthors=null, authorNote=null, correspAuthorsNote=
Xiao Xin, male, associate professor, College of Environmental Science and Engineering, Donghua University, 86-18964749723, E-mail: . Research fields: latent thermal energy storage and flexible thermal management.
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近年来,潜热储能热管理在热泵中的应用受到广泛关注。将相变蓄热技术与热泵结合可提升热泵性能及对可再生能源的利用率,但仍需进一步降本增效。综述了近年来压缩式热泵与相变材料耦合储热的研究进展,分类概述了不同应用场景下相变材料相关热物性的适用条件及其表征方法。概括了热泵储能系统性能的优化途径,包括相变材料选取原则与改良方法、储热器的优化设置思路和相关原理、系统的动态优化控制策略等。梯级相变蓄热型热泵在提升供给侧舒适性和提高可再生能源利用率等方面的突出表现,表明了梯级蓄热应用于热泵储能系统中的广阔前景,提出非共晶混合相变材料作为梯级蓄热备选材料的观点。指出需要总结和开发储能相变材料热物性可调控的新方法,使相变材料的选取和改良技术与梯级蓄热装置的热力学理论优化研究相适应,进一步提升相变蓄热型热泵的供热脱碳能力。

, correspAuthors=null, authorNote=null, correspAuthorsNote=
肖鑫,男,副教授,东华大学环境科学与工程学院,18964749723,E-mail:。研究方向:相变蓄能及柔性热管理。
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Applied Thermal Engineering, 2017, 115: 393-405., articleTitle=Experimental performance study on a dual-mode CO2 heat pump system with thermal storage, refAbstract=null), Reference(id=1239224538479784058, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239211866078105951, doi=null, pmid=null, pmcid=null, year=2022, volume=42, issue=1, pageStart=196, pageEnd=211, url=null, language=null, rfNumber=[70], rfOrder=78, authorNames=杨鹤, 杜小泽, journalName=中国电机工程学报, refType=null, unstructuredReference=杨鹤, 杜小泽. 布雷顿循环热泵储能的性能分析与多目标优化[J]. 中国电机工程学报, 2022, 42(1): 196-211., articleTitle=布雷顿循环热泵储能的性能分析与多目标优化, refAbstract=null), Reference(id=1239224539951984764, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239211866078105951, doi=null, pmid=null, pmcid=null, year=2022, volume=42, issue=1, pageStart=196, pageEnd=211, url=null, language=null, rfNumber=[70], rfOrder=79, authorNames=YANG He, DU Xiaoze, journalName=Proceedings of the CSEE, refType=null, unstructuredReference=(YANG He, DU Xiaoze. Performance analysis and multi-objective optimization of brayton cycle pumped thermal energy storage[J]. 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1压缩机;2冷凝器;3液体接收器;4热能储存;5,6膨胀阀;7蒸发器;8,9感应器;V1-V4球阀;V5-V6单向阀;P1-P2压力传感器;T1-T10热电偶;FM流量计。

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类型相变材料相变温度/℃密度/(kg/m3导热系数/[W/(m·K)]相变潜热/(kJ/kg)
无机材料CaCl2·6H2O[33]29.91 7100.57190.0
石蜡类石蜡RT4[28]2.0~4.0880(s)/770(l)0.20180.0
石蜡[29]21.08500.20 
石蜡C21H44[30]40.08000.14220.0
石蜡RT-44HC[34]43.0860(s)/760(l)0.20255.0
石蜡(P-116)[35]44.08170.16226.0
石蜡[31]53.5810(s)/790(l)0.21266.0
有机材料正葵酸[36]31.6878 155.4
聚乙二醇6000[37]52.0~66.0   
硬脂酸[35]58.19650.29169.0
), ArticleFig(id=1239224524823130994, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239211866078105951, language=CN, label=表1, caption=用于热泵系统中的单一相变材料的热物理性质, figureFileSmall=null, figureFileBig=null, tableContent=
类型相变材料相变温度/℃密度/(kg/m3导热系数/[W/(m·K)]相变潜热/(kJ/kg)
无机材料CaCl2·6H2O[33]29.91 7100.57190.0
石蜡类石蜡RT4[28]2.0~4.0880(s)/770(l)0.20180.0
石蜡[29]21.08500.20 
石蜡C21H44[30]40.08000.14220.0
石蜡RT-44HC[34]43.0860(s)/760(l)0.20255.0
石蜡(P-116)[35]44.08170.16226.0
石蜡[31]53.5810(s)/790(l)0.21266.0
有机材料正葵酸[36]31.6878 155.4
聚乙二醇6000[37]52.0~66.0   
硬脂酸[35]58.19650.29169.0
), ArticleFig(id=1239224524919599990, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239211866078105951, language=EN, label=Tab.2, caption=Thermophysical properties of composite modified phase change materials used in heat pump systems, figureFileSmall=null, figureFileBig=null, tableContent=
复合相变材料相变温度/℃导热系数/[W/(m·K)]相变潜热/(kJ/kg)
35%月桂酸/65%癸酸[38]19.80.14133.2
60%癸酸/24%月桂酸/10%SiO2/6% EG[36] 1.53109.2
33.8%十二酸/41.1%十四醇/20.1%十六醇/5% EG[39]26.1 172.2
80%石蜡/20% EG[40]27.39.80156.6
FCA/环氧烷[26]33.9~35.80.48~0.53211.7
SAT/AC复合物[15]47.8 219.8
SAT/KCl复合物[24]47.8 242.0
10%癸酸/90%62#石蜡[41]29.6~59.0 192.5
75%石蜡/25% EG[32]52.0~54.05.38140.0
36%硬脂酸/64%棕榈酸[12]52.30.28181.7
41%MgCl2·(H2O)6/59%Mg(NO32·(H2 O)6[42]40.0~65.00.60 
), ArticleFig(id=1239224525083177854, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239211866078105951, language=CN, label=表2, caption=用于热泵系统中的复合改良相变材料的热物理性质, figureFileSmall=null, figureFileBig=null, tableContent=
复合相变材料相变温度/℃导热系数/[W/(m·K)]相变潜热/(kJ/kg)
35%月桂酸/65%癸酸[38]19.80.14133.2
60%癸酸/24%月桂酸/10%SiO2/6% EG[36] 1.53109.2
33.8%十二酸/41.1%十四醇/20.1%十六醇/5% EG[39]26.1 172.2
80%石蜡/20% EG[40]27.39.80156.6
FCA/环氧烷[26]33.9~35.80.48~0.53211.7
SAT/AC复合物[15]47.8 219.8
SAT/KCl复合物[24]47.8 242.0
10%癸酸/90%62#石蜡[41]29.6~59.0 192.5
75%石蜡/25% EG[32]52.0~54.05.38140.0
36%硬脂酸/64%棕榈酸[12]52.30.28181.7
41%MgCl2·(H2O)6/59%Mg(NO32·(H2 O)6[42]40.0~65.00.60 
), ArticleFig(id=1239224526517629829, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239211866078105951, language=EN, label=Tab.3, caption=Methods for controlling the supercooling and melting temperature of phase change materials in heat pump systems, figureFileSmall=null, figureFileBig=null, tableContent=
作者材料组成、熔点和过冷度过冷度改善方法及材料相变点改性方法及材料调控效果
Jin Xin等[15]SAT4%十二水磷酸氢二钠作成核剂10%的乙酰胺非共晶混合相变点从53.1 ℃降至42.8 ℃,200次冷热循环过冷度近乎消除
58.0 ℃
>30.0 ℃
刘旋等[33]CaCl2·6H2O10%EG、2%SrCl2·6H2O 过冷度降至2 ℃以内
29.9 ℃
21.1 ℃
胡小东等[40]石蜡 20%EG相变点降至27.3 ℃,过冷度降低0.6 ℃
28.4 ℃
1.5 ℃
Li Minqi等[51]SAT1.5%十二水磷酸二钠作成核剂8%KCl和3%尿素为熔点改性材料相变点为47.8 ℃过冷度降至2.8 ℃
58.0 ℃
>30.0 ℃
G. Baran等[12]64.2%棕榈酸/35.8%硬脂酸 二元体系共晶共晶相变点52.3 ℃
C. Kutlu等[52]SAT采用电触发装置利用过冷度特性 电触发结晶20 s内温度从20.0 ℃升至56.4 ℃
58.0 ℃
>30.0 ℃
杜文清等[53]81%癸酸/19%石蜡 二元体系共晶共晶相变点27.4 ℃
), ArticleFig(id=1239224526635070346, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239211866078105951, language=CN, label=表3, caption=用于热泵系统中的相变材料的过冷度和熔点调控方法, figureFileSmall=null, figureFileBig=null, tableContent=
作者材料组成、熔点和过冷度过冷度改善方法及材料相变点改性方法及材料调控效果
Jin Xin等[15]SAT4%十二水磷酸氢二钠作成核剂10%的乙酰胺非共晶混合相变点从53.1 ℃降至42.8 ℃,200次冷热循环过冷度近乎消除
58.0 ℃
>30.0 ℃
刘旋等[33]CaCl2·6H2O10%EG、2%SrCl2·6H2O 过冷度降至2 ℃以内
29.9 ℃
21.1 ℃
胡小东等[40]石蜡 20%EG相变点降至27.3 ℃,过冷度降低0.6 ℃
28.4 ℃
1.5 ℃
Li Minqi等[51]SAT1.5%十二水磷酸二钠作成核剂8%KCl和3%尿素为熔点改性材料相变点为47.8 ℃过冷度降至2.8 ℃
58.0 ℃
>30.0 ℃
G. Baran等[12]64.2%棕榈酸/35.8%硬脂酸 二元体系共晶共晶相变点52.3 ℃
C. Kutlu等[52]SAT采用电触发装置利用过冷度特性 电触发结晶20 s内温度从20.0 ℃升至56.4 ℃
58.0 ℃
>30.0 ℃
杜文清等[53]81%癸酸/19%石蜡 二元体系共晶共晶相变点27.4 ℃
), ArticleFig(id=1239224526811231119, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239211866078105951, language=EN, label=Tab.4, caption=Simulation and experimental methods of cascade heat pump energy storage system, figureFileSmall=null, figureFileBig=null, tableContent=
研究类型作者系统用途TES模拟或实验方法热泵系统模拟或实验方法
数值模拟R. Hirmi等[22]转移供暖系统负荷TRNSYS中(修改的Type4a)混合水-PCM水箱TRNSYS中Type927组件单级水-水热泵模型
实验、模拟Zhu Chuanhui等[23]建筑采暖,峰谷电能利用TRNSYS中Type1270模型TRNSYS系统仿真
数值模拟C. Kutlu等[52]太阳能热泵供暖基于MATLAB建立的PCM储热罐数值模型使用REFPROP获取制冷剂的热物理特性
实验Yu Zhibin[59]回收离开冷凝器制冷剂中的显热除霜采用水箱搭建热泵实验台
数值模拟Huang Haotian等[68]太阳能供热系统源侧热管理基于MATLAB建立的PCM蓄热单元数值模型通过Type155实现数值模型和基于TRNSYS搭建的系统的联合仿真
), ArticleFig(id=1239224526958031764, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239211866078105951, language=CN, label=表4, caption=梯级热泵储能系统的模拟和实验方法, figureFileSmall=null, figureFileBig=null, tableContent=
研究类型作者系统用途TES模拟或实验方法热泵系统模拟或实验方法
数值模拟R. Hirmi等[22]转移供暖系统负荷TRNSYS中(修改的Type4a)混合水-PCM水箱TRNSYS中Type927组件单级水-水热泵模型
实验、模拟Zhu Chuanhui等[23]建筑采暖,峰谷电能利用TRNSYS中Type1270模型TRNSYS系统仿真
数值模拟C. Kutlu等[52]太阳能热泵供暖基于MATLAB建立的PCM储热罐数值模型使用REFPROP获取制冷剂的热物理特性
实验Yu Zhibin[59]回收离开冷凝器制冷剂中的显热除霜采用水箱搭建热泵实验台
数值模拟Huang Haotian等[68]太阳能供热系统源侧热管理基于MATLAB建立的PCM蓄热单元数值模型通过Type155实现数值模型和基于TRNSYS搭建的系统的联合仿真
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压缩式热泵耦合相变储热的研究进展
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杨耿 1 , 肖鑫 1, 2 , 王云峰 2
制冷学报 | 2025,46(1): 32-45
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制冷学报 | 2025, 46(1): 32-45
压缩式热泵耦合相变储热的研究进展
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杨耿1, 肖鑫1, 2 , 王云峰2
作者信息
  • 1东华大学环境科学与工程学院 空气环境与建筑节能研究所 上海 201620
  • 2云南省农村能源工程重点实验室 昆明 650500

通讯作者:

肖鑫,男,副教授,东华大学环境科学与工程学院,18964749723,E-mail:。研究方向:相变蓄能及柔性热管理。
Research Progress of Compression Heat Pump Coupled with Heat Storage of Phase Change Materials
Geng Yang1, Xin Xiao1, 2 , Yunfeng Wang2
Affiliations
  • 1.Institute of Air Environment and Building Energy Conservation, College of Environmental Science and Engineering, Donghua University, Shanghai, 201620, China
  • 2.Yunnan Provincial Rural Energy Engineering Key Laboratory, Kunming, 650550, China
出版时间: 2025-02-16 doi: 10.12465/j.issn.0253-4339.2025.01.032
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近年来,潜热储能热管理在热泵中的应用受到广泛关注。将相变蓄热技术与热泵结合可提升热泵性能及对可再生能源的利用率,但仍需进一步降本增效。综述了近年来压缩式热泵与相变材料耦合储热的研究进展,分类概述了不同应用场景下相变材料相关热物性的适用条件及其表征方法。概括了热泵储能系统性能的优化途径,包括相变材料选取原则与改良方法、储热器的优化设置思路和相关原理、系统的动态优化控制策略等。梯级相变蓄热型热泵在提升供给侧舒适性和提高可再生能源利用率等方面的突出表现,表明了梯级蓄热应用于热泵储能系统中的广阔前景,提出非共晶混合相变材料作为梯级蓄热备选材料的观点。指出需要总结和开发储能相变材料热物性可调控的新方法,使相变材料的选取和改良技术与梯级蓄热装置的热力学理论优化研究相适应,进一步提升相变蓄热型热泵的供热脱碳能力。

The application of latent thermal energy storage with heat pumps has been extensively studied in recent years. The combination of phase change heat storage and a heat pump can improve the performance of the heat pump and the utilization of renewable energy; however, further cost reduction and efficiency increase are required. Therefore, this study reviews the progress of heat pumps coupled with solid-liquid phase change materials and summarizes the applicable conditions and characterization methods for phase change materials applied to heat pumps. The optimization approaches for the performance of the heat pump system are summarized, including the selection and improvement of phase change materials, the optimal setting of the heat exchanger, and the dynamic optimization control strategy of the system. The outstanding performance of heat pumps with cascade heat storage in improving the supply-side comfort and utilization rate of renewable energy indicates the broad prospect of cascade heat storage being applied to heat pump energy storage systems. Herein, mixed, non-eutectic phase change materials are proposed as alternative materials for cascade heat storage. Notably, summarizing and developing new methods for adjusting the thermophysical properties of phase change materials for energy storage is necessary for adapting the selection and improvement of phase change materials to the optimization of the thermodynamic cycle of cascade heat storage devices and further improving the heating decarbonization ability of latent heat storage heat pumps.

杨耿, 肖鑫, 王云峰. 压缩式热泵耦合相变储热的研究进展. 制冷学报, 2025 , 46 (1) : 32 -45 . DOI: 10.12465/j.issn.0253-4339.2025.01.032
Geng Yang, Xin Xiao, Yunfeng Wang. Research Progress of Compression Heat Pump Coupled with Heat Storage of Phase Change Materials[J]. Journal of Refrigeration, 2025 , 46 (1) : 32 -45 . DOI: 10.12465/j.issn.0253-4339.2025.01.032
在供热领域,热泵可以有效节约产自化石燃料燃烧的电能,从而减少硫化物和氮氧化物的污染以及温室气体的排放,被认为是供热脱碳的关键技术。据国际能源署跟踪统计,热泵目前仍只能满足全球建筑物供暖需求的约10%[1]。2021年全球用于供热的能源占据总能源消耗的约50%,而其中46%的能源用于建筑供暖和热水供应,可再生供热消耗同比增长超过3.5%[2]。然而,热泵在利用低品位能源时存在时空不平衡问题。热能储存(thermal energy storage,TES)技术作为利用余热和可再生能源供热管理的重要解决方案,众多学者聚焦于热泵中集成TES技术的潜力。其本质是将蒸发器侧或冷凝侧的热能储存,按需为负荷侧供给热量。
集成TES装置的热泵系统储热形式目前主要分为显热储能和潜热储能。常用水等显热蓄热介质在较宽的温度范围进行蓄/放热。但储热介质温度升高不利于热泵运行的稳定性[3],且随着供热温度的升高或热源温度的降低间接导致压缩机的排气压力和功耗波动,热泵的性能均会出现不同程度的衰减[4]。而潜热蓄热原理是利用相变材料(phase change materials,PCM)在特定温度下的相态变化来储存能量。PCM主要分为有机、无机、共晶和非共晶材料,本文主要关注为建筑供暖和热水生产的中低温(<100 ℃)热泵,集成的材料以固液PCM为主。PCM的高蓄热密度不仅可以减少蓄热单元的空间占用,而且可在较窄的温度范围内进行热泵需求侧管理,使PCM在热泵中的应用前景广阔。近年来,提高TES装置传热性能的课题一直是该领域的研究热点,主要集中于TES装置设计,包括热力学性能最优理论[5]、加装肋片[6]、设计尺寸与运行参数的多目标参数优化[7]和传热流体的流态[8]等。此外,单级潜热储能装置的传热流体(heat transfer fluid,HTF)流向温度的急剧下降导致相变热驱动力降低,PCM的非一致性相变行为将会降低蓄热效率。而多个不同熔点的PCM模块呈梯级排布的梯级储热(cascade thermal storage,CTS)解决方案受到广泛关注。与单级TES装置相比,CTS装置的优点在于工作温度范围更宽且PCM与HTF温差更均匀,能提高PCM的传热驱动力、充分利用HTF中的热能[9]、更快的蓄/放热过程[10]和实现热能的多重利用[11]。目前大多数关于CTS性能优化的研究基于确定的材料,对CTS装置的设计尺寸和运行参数进行多目标参数优化,但极大地降低了实际应用时储热集成的适用性和灵活性。从设计装置到材料的研究方法对CTS的构建具有较强的适应性和灵活性,关键在于CTS对材料相变温度呈梯级排布的要求。为了获得具有合适相变温度的PCM,开发有效的方法来调节PCM的相变温度是必要的。常见的方法是将水合盐与其他无机物或有机物按一系列比例混合,从而形成水合盐基混合物。可将水合盐基混合物分为共晶和非共晶混合物。现阶段有较多研究报道了多元共晶和非共晶混合物对PCM熔化行为的改变,G. Baran等[12]为潜热储能系统制备了一种相变点为52.3 ℃的棕榈酸和硬脂酸的共晶混合物作为PCM。Ling Ziye等[13]为太阳能热水系统的潜热蓄热装置开发了共晶复合PCM,实验表明质量分数为35%~50%的Mg(NO32·6H2O可与MgCl2·6H2O形成共晶系,将MgCl2·6H2O的熔点从111 ℃调至58 ℃。但共晶混合物的共晶点测定方法成本高,耗时长,可供选择的相变温度单一[14]。然而,非共晶复合PCM由于各组分占比的不同,凝固和熔化行为可在一定温度范围内发生改变,可供实际应用选择的相变温度范围更广,但如何保证其循环蓄/放热过程中性能的热可靠性是应用的重要环节。Fu Wanwan等[14]在三水合乙酸钠(sodium acetate trihydrate,SAT)中加入甘氨酸形成非共晶混合物,实现了48.34~58.38 ℃的系列相变温度调控,在100次循环蓄/放热实验后,相变范围无明显波动,相变焓仅下降了6.9%。Jin Xin等[15]为空气源热泵开发了以乙酰胺(acetamide,AC)作熔点改性剂的SAT非共晶PCM,在AC不同添加量的复合PCM中实现了42.8~53.0 ℃的系列相变温度调控,且通过增稠剂和成核剂的加入,有效解决了过冷和相分离问题,200次循环蓄/放热的潜热损失仅为7.4%。虽然已有较多研究报道了非共晶混合物对PCM熔化行为的改变,但少有研究将非共晶混合物作为CTS装置的备选材料。此外,如何有效描述PCM在固液相变过程中的自然对流传热效应[16],对于数值模拟研究PCM的储热特性十分重要,特别是对蓄热装置底部传热不良区域的结构改进[17]
目前关于CTS的PCM相关实验研究方向多数是从确定的材料出发,基于一定假设的梯级优化理论来优化设计CTS尺寸和排布。其中PCM选取缺乏对理论优化中关于材料物性假设的考虑,需要总结和开发新的方法,使PCM的选取和改良技术与CTS装置的热力学理论优化研究相适应。已有文献综述了PCM在热泵中的应用[18-19],而关于PCM应用于热泵中相关热物性的适用条件、表征方法、性能改良材料及配比和系统性能的优化途径鲜有全面综述。PCM在压缩式热泵中的应用如图1所示,包括梯级蓄热优化原理和PCM选取与改良[15,20]、空气源热泵内集成[21]、地源热泵外集成[22]及太阳能热泵外集成[23]。本文从材料、蓄热装置和系统应用3个环节综述了相变储能热泵技术近年来的研究进展,阐明了相变材料选取原则与改良方法、储热器的优化设置思路和制定系统的动态优化控制策略的途径。
热泵根据工作原理主要分为吸收式和压缩式,本文主要关注压缩式热泵。压缩式热泵通常由压缩机、冷凝器、膨胀阀和蒸发器构成,将PCM集成在不同换热器侧,其特定温度的相变行为和热物性参数对系统的性能影响起主导作用。热泵理论性能系数(coefficient of performance,COP)定义为[24]
式中:Tc为冷凝温度;Tv为蒸发温度;Tm为供热介质温度;ΔTc为冷凝温度与供热介质温差;Tamb为低品位热源温度;ΔTv为蒸发温度与低品位热源温差,上述所有温度单位均为℃。若ΔTv固定,理论COP会随着ΔTc的增加而减小。若PCM集成在冷凝器侧,吸收冷凝器放热从而发生相变达到储热的目的,其温度变化可忽略不计,这使换热介质与冷凝器之间的温差保持较小,从而提高系统COP。此外,若使用的PCM储存其他热源的热量集成于蒸发器侧,为热泵在低温热源运行工况下进行补能,或作为热泵逆循环除霜的辅助热源[25]。用于热泵系统的无机PCM具有潜热大、不可燃的特性,但由于存在过冷和相分离的现象,制约了其在需要循环使用的热泵系统中的应用。用于热泵系统的有机PCM有石蜡、乙二醇(聚合物)和脂肪酸等[26-27]。有机PCM物理化学稳定性好、无腐蚀等,但大部分缺点为储能密度低、导热系数低、易燃、成本较高等。其中石蜡具有化学惰性,在500 ℃以下稳定,熔融时体积变化小,因此国内外学者对不同熔点和形态石蜡[28-30]这类烷烃的混合物进行了大量研究。石蜡被用作PCM与太阳能集热器组合,用作生活热水加热[31]。Wu Jianghong等[32]使用膨胀石墨(expanded graphite,EG)改善石蜡的导热系数,将EG/石蜡复合PCM与换热器相结合应用于空气源热泵热水器。在热泵系统应用PCM实验研究的纯材料的热物性如表1所示,复合PCM的热物性如表2所示。
PCM在热泵系统中的应用离不开对材料的热物性表征,其传热和储热能力决定着TES装置对热泵系统的热管理效果。为了提高PCM的储热效能、集成于热泵运行的灵活性和稳定性,传统的方法是将具有高导热性的材料与纯PCM复合形成复合PCM,如EG[32]、石墨烯[43-44]、泡沫金属[45-46]等。复合PCM的制备原理有:将微小或纳米级的高导热粒子分散至PCM中、将PCM渗透至高孔隙率和高导热系数的多孔结构中等。为增强PCM导热性,可将EG压缩成石墨泡沫,也可直接与液体PCM混合并浸渍以形成复合PCM[44]。此外,在多孔泡沫金属中浸渍PCM也是制备导热性能优异的复合PCM的有效方式[45]。常用的低温共熔法、物理吸附法是比较简易的制备方法,特点是操作简单,成本较低,但缺点是制成的材料通常孔隙率较大,由于接触热阻的存在,试样的表面粗糙度会极大地影响后续热物性测量精度[46]。而真空浸渍法在制备石蜡-碳泡沫复合PCM中被证明十分有效[47],浸渍率接近100%。多孔结构浸渍不充分导致微孔内气泡的残留,这将会降低复合PCM的传热性能。因此,对复合PCM的微观形貌分析是必要的。可使用扫描电子显微镜,在微观层面上直观显示复合PCM的结合情况。
表1可知,单一PCM的导热系数较低,如石蜡RT-44HC[34]导热系数仅为0.20W/(m·K)。在蓄热热泵的蓄能装置中,复合PCM的导热系数直接影响PCM熔化和凝固所需的温度梯度以及响应时间,低导热系数必然导致蓄/放热的周期过长。针对壳管式潜热储能装置,忽略相变过程的导热系数变化,在蓄热阶段管壁沿外径方向的传热过程可看作半无限大物体非稳态导热,其热渗透层与热扩散率和特征时间乘积的几何均值呈线性相关。在保证最外层PCM蓄热有效性的前提下,相变材料的导热系数对其厚度进行了一定的限制,即存在最大值。其他形式的蓄热装置在设计时仍应当考虑PCM物性参数,进行参数优化设计。为了量化分析复合PCM导热性能优劣,导热系数是必要的测量物理量之一。常用的表征方法有:瞬态平面源法[48]、热线法[49]、闪光法[50]等。此外,添加各种高导热性的材料无疑会减少单位体积下PCM的占比,以损失部分相变潜热量为代价来提升PCM导热系数,进而减小其储热密度和储热量。因此,导热系数的改良有一定限度,需要保证复合后的PCM具有可观的相变潜热,保留PCM在缩减储热容积的优势。
探明PCM相变点的目的是让PCM相变点与系统HTF的工作温度相匹配。研究表明,为了使PCM在系统循环中发生全相变,蓄热热泵HTF在加热过程中的工作温度应高于PCM的熔化温度。表征PCM的相变点和相变潜热常用差示扫描量热法。如表1表2列出的PCM物性参数,大多数的无机盐类PCM的相变潜热较有机类PCM要高。但无机盐类PCM比有机类PCM存在较大的过冷现象,即凝固点小于熔点的现象。这将导致传热过程温度变化滞后,使系统无法在预设的温度下正常放热。消除或减少过冷最常用方法是向PCM中添加成核剂以降低过冷度。石墨烯和硼砂是常用的成核剂。这类材料具有用量小、效率高的特点。表3总结了部分PCM应用时的过冷度和熔点调控方法的相关研究。
在应对PCM过冷度这一特性上,C. Kutlu等[52]认为合理利用PCM的过冷度可减少储能热损失,通过在过冷SAT储存单元设置电触发器,实现可控的结晶和熔化。对比之前添加成核剂改性PCM的研究,这种电触发机制提升了带有过冷度的PCM在蓄热热泵中的适用性,且特别适用于长期储热的情况。除了电触发的方法以外,控制PCM结晶来实现灵活蓄/放热的方法还包括冲击振动[54]、局部冷却[55]、注入气泡[56]等,但电触发具有低成本、简单、易实现自动化的优势,有望在未来实现长期储热的灵活控制。另一种相变点调控方法是混合不同相变点的PCM来形成(准)共晶系PCM[57]。(准)共晶系PCM优势在于:诸如烷酸类等有机物以共晶点比例混合后相变介质性能稳定,具有稳定的相变点和相变潜热,应用于蓄热热泵中可以有效防止封装后的填料在循环相变中出现相分离和分布不均的现象。如表3所示,G. Baran等[12]用不同比例的棕榈酸和硬脂酸制备了一系列二元体系,结果显示棕榈酸和硬脂酸的二元体系以质量比64.2∶35.8混合形成共晶。杜文清等[53]研发的二元共晶PCM在500次结晶循环中相变点的最大偏差为1.46%,显示出共晶PCM具有可靠的循环储热潜力。J. P. Da Cunha等[42]实验制备了质量分数为41%的六水硝酸镁和六水氯化镁共晶混合物,其能量密度是同体积水的近3倍。PCM作为蓄热材料应用于热泵系统中,连续的熔化和凝固需要PCM的化学成分保持稳定,其稳定性优劣是决定能否应用于实际热泵系统的关键,这也是关于非共晶PCM需要表征的重要环节。对于PCM稳定性的评价内容主要包括热稳定性、化学稳定性、化学相容性和循环稳定性。材料的热稳定性采用热重分析法测量,通过分析热重曲线,得出材料不同温度下的质量变化。G. A. Lane[58]指出石蜡暴露在空气中会缓慢氧化,因此需要封装容器。它们通常与所有的金属容器兼容,但会令一些塑料容器变软。对PCM的热稳定性表征对封装容器的选择和设计具有指导意义。PCM化学相容性主要采用傅里叶变换红外光谱技术来表征,循环稳定性分析主要是将PCM重复进行加热冷却,相变点与相变潜热变化情况仍然可采用差示扫描量热仪分析。
在热泵储能系统中,除了选择热物性合适的PCM备受关注以外,PCM的TES装置的结构组成以及与热泵系统匹配协调也是国内外学者研究的热点。对热泵的不同应用场合,TES装置的集成形式和部位各异。热泵生活热水供应系统负荷主要集中于早和晚,TES装置蓄热的时间约为8 h。此外,为实现蓄热热泵“谷时”电能的利用,需将TES装置集成在冷凝器侧,同时热量需求对装置的容积和包覆PCM的厚度进行了限定。对于传统的空气源热泵供暖场景,热泵系统需要考虑周期性的切换循环模式来进行除霜,将TES置于蒸发器侧,可在逆循环除霜时充当辅助热源。有研究将TES装置集成于冷凝器出口,用于回收离开冷凝器的制冷剂中所含的显热,通过内置的三通阀改进逆循环进行除霜[59]。两种除霜方式对PCM熔点的要求范围不同,这根据不同制冷剂和室内设定温度范围与地区的差异进行具体分析。针对集成低品位热源的热泵系统,如太阳能热泵干燥技术,则是侧重对分散性太阳能辐射热的收集,通常将TES装置集成在蒸发器侧,在日落后作为热泵的辅助热源。该场景下PCM的相变点要求与集热器的出口水温进行匹配。TES装置与热泵集成分内集成和外集成两种形式,对一体式热泵机组,内置的蒸发器和冷凝器与外部水循环系统进行热量交换。TES装置的外集成形成PCM—水换热器,这与集成在机组内部形成PCM—制冷剂换热器的要求不同,压缩管道多为铜管,TES装置的集成应考虑对集成部位制冷剂压降的影响[38]、对管道的压力和腐蚀情况、是否用分隔构件等。TES装置按照耦合部位的不同主要分3种形式:带PCM的组合型换热器、填充PCM的蓄热罐和热泵源侧的PCM集成。
M. B. Dominick等[28]设计了一种以石蜡RT4为PCM的蒸发器TES模块,研究了该模块的PCM、制冷剂和HTF通道的不同排列对热交换器性能的影响,TES1和TES2组成如图2所示,TES3与TES2区别是将制冷剂管路直接叠置于传热流体管路上方。实验表明,通道的不同排列会影响TES模块和热交换器模块的性能,其中,TES2各项性能指标较为适中。
Wu Jianghong等[32]设计了如图3所示的EG/石蜡热交换器,对空气源热泵热水器中冷水从冷凝器吸收热量的过程进行了模拟。实验中入口温度与有效生活热水量(温度高于45.0 ℃)呈正相关,而流速对其影响相反。此外,出口侧的热量利用不足是相变换热器的最大性能弱点。
传统的蓄热罐以蓄热水箱的形式被安置于热泵的冷凝器侧,在热泵供热系统中起着缓冲水温、平衡供需的作用。目前完全用PCM替代水箱的做法在经济性等方面还存在挑战,其较低的蓄热速率无法完全取代水箱对循环工质(通常为水)缓冲作用。因此,PCM常被集成到集热水箱中或与水箱分体连接使用。Zou Deqiu等[34]提出了一种使用水-石蜡RT-44HC储热罐,为了增加有效传热面积将冷凝器盘管缠绕在PCM层中使其充分接触,使PCM蓄热罐储热量增加了14%,运行时间缩短了13%,提升了供热水温的均匀性和系统COP。以太阳能为代表的可再生能源常被作为热泵源侧对象,利用PCM将白天辐射较强时的太阳能贮存起来,作为夜晚或阴天热泵的低品位补充热源,可解决热泵供热效率过低的问题。吴薇等[60]设计了一种蓄热型太阳能热泵热水器系统,以正葵酸作为真空集热管填充材料,对该系统进行能耗分析,分别与常见的生活热水供应方式的折合电价进行了对比。该系统比电热水器节能84.37%,比空气源热泵热水器节能22.81%,而初投资仅比空气源热泵热水器高30.43%。此外,耦合PCM的太阳能热泵系统蓄热技术分为光伏和光热技术,通常集热器的流体出口温度随太阳辐射的增强而升高,基于此波动热源的特性,如何对其集成后的热量进行调度管理是提高热泵性能的关键。朱传辉等[61]将带PCM蓄能芯的真空管与热泵集成,设计了一种用于太阳能热泵干燥的集热器装置,如图4所示。在干燥温度设置为50.0 ℃和60.0 ℃、风速为2~3 m/s条件下,对干燥室运行工况的温度分布及风速分布进行模拟分析,太阳能供热量占比约为66%,COP可达3.5。
与太阳能集热效率随进口温度升高而下降类似,光伏发电效率随工作温度升高而线性下降是太阳能利用效率不足的主要问题。Liu Wenjie等[62]将光伏和光热技术结合,对提出的一种直接膨胀式光伏和光热热泵系统进行了实验研究,通过工作流体流经冷却组件(吹胀板)带走光伏组件产生的余热来提高发电效率,同时集热器作为热泵机组的蒸发器用于回收余热。结果表明,集热模块面积与压缩机排量比值越大,COP越高,但集热效果下降,比单一的光伏或光热系统对太阳能的综合利用率提升17%。该项研究为PCM在光伏和光热热泵技术的集成提供了新的思路,PCM模块组合光电模块协同作用,提高太阳能的综合利用率。
在HTF与PCM温差较大的情形,沿流动方向上HTF温度的急剧下降导致相变热驱动力降低,这将降低TES蓄/放热效率,不利于热泵性能的提升。为了解决单级TES装置的传热驱动力降低的问题,M. M. Farid等[63]最早提出CTS的概念,被用于增加系统储存容量和储存不同温度范围的热能。国内外学者对CTS装置的性能分析和数值预测已开展了多项研究。Xu H. J.等[64]基于热力学原理建立了梯级蓄热系统模型,并对CTS系统的PCM温度、级数、HTF温度等参数进行了优化,结果显示,系统级数布置小于临界级数可提高热效率,对于固定热量的入口优化,级数应大于临界级数,但这将增加系统复杂性和运行成本。R. V. Seeniraj等[65]基于焓法对具有翅片管和CTS的管壳式换热器的热性能进行了数值模拟,得出单级和多级PCM换热器的出口HTF无因次温度随无因次时间的变化特性,如图5所示。
与单一PCM蓄热模块相比,沿流动方向提供了较高的HTF和PCM的传热温差,使换热出口温度均匀性得到提升,显著提高了储热性能。Guo Weimin等[66]数值研究了不同PCM胶囊体积比下梯级蓄热系统的平均传热速率,发现3种不同PCM存在最优体积比。本文对CTS装置的优化设置及其系统优化研究总结了如下原则:
1)根据不同的优化思路采用不同的优化模型,一般以(最大)优化或熵(最小)的条件来对各自目标优化函数进行数值求解,从而确定设计参数的有效范围,结合用户侧需求和填充的PCM的相变点和导热系数等物性参数指导CTS装置的设计。
2)由于理论计算大多数是假定PCM的物性参数进行计算,通过确定的CTS装置可求得PCM的梯级最优排布,而PCM的热物性一般非假设般处于理论最优状态,这也是目前CTS装置材料选取和改性的关键。在确定的设计尺寸和流动条件下,理论计算得到相变点梯级排布的相变温度,用于指导材料选取和改性。对于现存的热泵系统,该方法具有较强的适应性和灵活性。
3)另一种思路是依据确定种类的PCM,对CTS装置的级数、级面积和容积等设计参数与系统运行参数进行多目标参数的优化匹配研究。
热泵储能系统的设计、运行和维护需要依靠系统模拟。一方面通过动态的数据实时交互可以缩短开发周期与降低成本,另一方面模型与实物系统可以相互验证,特别是热泵储能在不同地区和不同用途的设计中显得尤为重要。用户侧冷热源取用(如热水、空调等)的需求及其舒适性的保证关键在冷热库出水温度动态变化的优化控制。在耦合PCM的热泵动态运行中,优化控制难点在于蓄热装置进、出水温度与压缩机工况以及循环工质流速有关。如何合理地控制和匹配这些时变参量是热泵系统COP优化的研究方向。表4总结了部分梯级热泵储能系统的模拟和实验方法。
Jin Xin等[15]为提升空气源热泵系统COP,研制了测试包含不同配比的SAT/AC复合PCM,将其封装在潜热储罐中与储热水箱串联使用,如图6所示。实验结果表明,当流量为10~38 g/s时,热泵的COP从2.27增至3.12;系统的整体效率也呈上升趋势,COP从2.13提升至2.71。
为达到供暖系统在用电高峰期实现负载转移的目的,R. Hirmiz等[22]构建了蓄热热泵供暖系统的验证数值模型,如图7所示。该潜热储能罐的储热量是纯水储罐的3倍以上,6 h的用电负荷转移需要2.5 m3的水量,从系统优化层面上揭示了储罐容量与实际应用需求的联系。
C. Kutlu等[52]对太阳能辅助热泵与PCM储热单元的耦合进行了模拟研究,如图8所示。采用12 L/min的循环流量下,热水输送温度保持高于43 ℃,且对于给定的供热截面,PCM水箱和建筑物之间的水循环对输送温度无显著影响,使该系统有适应天气波动的潜力。
Yu Zhibin等[59]基于Evans-Perkins热泵循环,设计了一种集成蓄热器到蒸气压缩式循环中的柔性热泵系统,如图9所示,集成的蓄热器用来回收离开冷凝器的制冷剂中所含的显热。这种灵活的热泵循环可为PCM等蓄热材料提供结合位点,允许低品位热源和外部余热回收的进一步集成,为热泵供热和除霜提供辅助热源,提升系统整体COP。
曲明璐等[67]研究了复叠式空气源热泵在相变蓄能除霜循环中,消耗的相变蓄热器、系统管路和压缩机所提供热量的占比。在温湿度分别为-9 ℃和85%,结霜量为1.5 kg的室外工况下,相变蓄热器可提供45.2%的除霜能耗。为提高供热系统对太阳能的利用效率,Huang Haotian等[68]研究了PCM蓄热罐与水箱在不同系统配置下对太阳能供热系统效率的影响,系统配置如图10所示。结果表明,串联系统的太阳能利用率比单水箱系统提高约30%,比并联系统提高5%~12%。其中PCM蓄热罐与水箱的串联连接可以降低集热器进口温度,是提高太阳能集热效率的主要因素,同时强化了系统对供热温度的平衡性。
Zhu Chuanhui等[23]在太阳供热热泵系统源侧集成了相变储热罐,如图11所示,并对该系统进行了实验和TRNSYS动态仿真研究。结果表明,该系统的供热用电量约为无储热罐热泵供热系统的72.8%,日运行成本降至无储热罐热泵供热系统的41.2%,系统太阳能供热占比可达27.2%。
为优化蓄热热泵能源储存效率,Liu Fang等[69]将蓄能过程控制参数恒定,保持压缩频率和热水流量恒定,并基于实验制定膨胀阀开度和冷水流量与COP的经验相关性的动态控制策略。杨鹤等[70]建立了热泵储能系统的数值模型并进行热力学分析,采用多目标优化遗传算法对系统的状态点参数进行数值优化,得到往返效率与储能密度和功率密度的关系,表明储能密度和功率密度最优值的选择存在折中。此外,在大规模应用PCM模块的同时应考虑成本控制,以提高经济适用性。结合本文对材料、蓄热装置和系统集成形式的综述,可考虑从材料到系统运行策略制定环节的互相适应并形成闭环的全局优化。
本文综述了压缩式热泵与PCM耦合储热的研究进展,分类概述了不同应用场景下相变材料相关热物性的适用条件及其表征方法,总结了热泵储能系统性能的优化途径,得到如下结论:
1)各项研究表明将蓄热技术与热泵结合可提升热泵的性能,PCM储热密度高,温度波动范围小,在热泵供热管理具有较大优势,利用复合PCM对改善热泵系统性能有广阔的前景。
2)不同场合对PCM换热器的蓄/放热周期、集成部位的应用要求为PCM选取和蓄热集成方式指明了方向。对PCM相变点和过冷特性的理论优化要求可为PCM的制备和改良提供理论依据,需要对PCM各项物性参数进行表征。
3)蓄热型热泵系统的优化途径包括寻找和改良高性价比的PCM、蓄热器结构的优化设置、系统的布置及其动态优化控制策略。目前PCM选取缺乏对理论优化中关于材料物性假设的考虑,需要总结和开发新的方法,使PCM的选取和改良技术与CTS装置的热力学理论优化研究相适应。
目前,在实现梯级蓄热技术在热泵系统的集成中,非共晶混合PCM的相关研究显示出其作为备选材料的潜力,有必要对其进行数值和实验研究。未来值得研究的方向主要包括:
1)在提高PCM导热性和稳定性的同时,探明兼顾其合适的相变点、可观的储热量、较低的过冷度、稳定的热循环性能的方法,以满足多样化需求。而非共晶混合PCM展现的较共晶混合PCM大的相变温度范围的特点,可对其进一步研究。此外,对于严寒地带热泵系统长期储热的场景区别于短期储热,长期存放对PCM储热稳定性的要求需要重新处理并利用PCM的过冷度,需要开发除了低温触发之外的新的放热触发方式。
2)CTS装置作为比单级TES装置工作温度范围更宽、HTF温差更均匀、蓄/放热效率更高的潜热储能集成方式,是热泵储能系统未来很有前景的研究方向。可基于已有的CTS装置的热力学优化原理计算适配参数范围,沿该思路与现有的PCM改性方法结合,可探明合适的储能基材和性能改良材料以及合适的配比,为制备性能稳定高效的PCM提供指导。
3)热泵系统耦合TES装置的优化匹配还缺乏定量研究。可基于有限元分析软件的流固耦合传热接口,对TES装置运行工况进行数值仿真,得到其温度响应特性。该特性作为耦合热泵运行动态仿真的重要环节,是制定优化控制策略的重要途径。未来在系统的动态仿真和实验方面还有待进一步研究。
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2025年第46卷第1期
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doi: 10.12465/j.issn.0253-4339.2025.01.032
  • 接收时间:2023-12-06
  • 首发时间:2026-03-13
  • 出版时间:2025-02-16
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  • 收稿日期:2023-12-06
  • 修回日期:2024-01-05
  • 录用日期:2024-01-16
基金
Shanghai Pujiang Program(20PJ1400200)
上海市科委浦江人才计划(20PJ1400200)
Yunnan Provincial Rural Energy Engineering Key Laboratory(2022KF001)
云南省农村能源工程重点实验室开放基金项目(2022KF001)
Fundamental Research Funds for the Central Universities of China(2232021D-11)
中央高校基本科研业务费专项基金(2232021D-11)
作者信息
    1东华大学环境科学与工程学院 空气环境与建筑节能研究所 上海 201620
    2云南省农村能源工程重点实验室 昆明 650500

通讯作者:

肖鑫,男,副教授,东华大学环境科学与工程学院,18964749723,E-mail:。研究方向:相变蓄能及柔性热管理。
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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