Article(id=1239230396894868477, tenantId=1146029695717560320, journalId=1238823019242635269, issueId=1239230393547804821, articleNumber=null, orderNo=null, doi=10.12465/j.issn.0253-4339.2025.03.032, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1730736000000, receivedDateStr=2024-11-05, revisedDate=1734624000000, revisedDateStr=2024-12-20, acceptedDate=1735833600000, acceptedDateStr=2025-01-03, onlineDate=1773385150406, onlineDateStr=2026-03-13, pubDate=1750003200000, pubDateStr=2025-06-16, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773385150406, onlineIssueDateStr=2026-03-13, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773385150406, creator=13701087609, updateTime=1773385150406, updator=13701087609, issue=Issue{id=1239230393547804821, tenantId=1146029695717560320, journalId=1238823019242635269, year='2025', volume='46', issue='3', pageStart='1', pageEnd='166', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773385149609, creator=13701087609, updateTime=1773385254705, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1239230834402717933, tenantId=1146029695717560320, journalId=1238823019242635269, issueId=1239230393547804821, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1239230834402717934, tenantId=1146029695717560320, journalId=1238823019242635269, issueId=1239230393547804821, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=32, endPage=38, ext={EN=ArticleExt(id=1239230397129748481, articleId=1239230396894868477, tenantId=1146029695717560320, journalId=1238823019242635269, language=EN, title=Analysis of the Characteristics of Solution Absorption Heat Storage Cycles, columnId=1239230395695288481, journalTitle=Journal of Refrigeration, columnName=Energy Storage Technology, runingTitle=null, highlight=null, articleAbstract=

Solution absorption energy storage is a new energy storage and release technology characterized by high energy storage density, low heat loss, good mobility, and long-term energy storage. Energy storage density and energy storage efficiency are the key indexes for measuring the energy storage capacity of absorption energy storage systems and the key parameters for evaluating the energy conversion efficiency of absorption energy storage systems, respectively. Based on thermodynamic principles, the energy storage characteristics and applicability of absorption energy storage systems were investigated using six types of absorption solutions under different conditions. The results show that both energy storage density and energy storage efficiency increase with an increase in heat source temperature and cooling water temperature and decrease with solution concentration. At a heat source temperature of 70-120 ℃ and condensing temperature of 24-36 ℃, NaOH-H2O has the largest energy storage density and efficiency, CaCl2-H2O has the smallest energy storage density and efficiency, and LiBr-H2O has the widest applicability of temperature range.

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Wang Gang, male, lecturer, School of Environment and Energy Engineering, Beijing University of Civil Engineering and Architecture, 86-15911066230, E-mail: . Research fields: absorption heat pumps and thermochemical energy storage technology.
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溶液吸收式蓄能是一种热能存储和释放的新型技术,具有蓄能密度高、热量损失小、流动性好、可实现热能长期储存等优点。蓄能密度和蓄能效率是衡量系统热能储存能力和评估系统能量转化效率的关键指标参数。基于热力学原理,对比研究了6种吸收工质溶液在不同工况条件下的系统蓄能特性和适用性。结果表明:蓄能密度和蓄能效率均随热源温度、冷却水温度的升高而增大,随溶液浓度的升高而减小。热源温度为70~120 ℃、冷凝温度为24~36 ℃时,NaOH-H2O的蓄能密度和蓄能效率最大,CaCl2-H2O的蓄能密度和蓄能效率最小,LiBr-H2O的温度范围适用性最广。

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王刚,男,讲师,北京建筑大学环境与能源工程学院,15911066230,E-mail:。研究方向:吸收式热泵及热化学蓄能技术。
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tableContent=null), ArticleFig(id=1239230412023722598, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239230396894868477, language=EN, label=Tab.1, caption=Physical property equations, figureFileSmall=null, figureFileBig=null, tableContent=
类型方程
温度t1=f1X1pe);t3=trt1t4=f2X4pe
焓值h1=f3t1X1);h3=f4t3X3);h4=f5t4X4);hL,1=f6t1pe);hv,3=f7t3pg);hL,4=f8t4pe
压力pg=f9t3);pc=f10t4
), ArticleFig(id=1239230413491729013, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239230396894868477, language=CN, label=表1, caption=物性方程, figureFileSmall=null, figureFileBig=null, tableContent=
类型方程
温度t1=f1X1pe);t3=trt1t4=f2X4pe
焓值h1=f3t1X1);h3=f4t3X3);h4=f5t4X4);hL,1=f6t1pe);hv,3=f7t3pg);hL,4=f8t4pe
压力pg=f9t3);pc=f10t4
), ArticleFig(id=1239230413604975228, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239230396894868477, language=EN, label=Tab.2, caption=Simulation parameters for system operation, figureFileSmall=null, figureFileBig=null, tableContent=
参数
初始溶液质量M1/kg给定
稀溶液浓度X1/%26~50
浓溶液浓度X2/%36~60
稀/浓溶液浓度差ΔX/%初始为5
热源温度tr/℃70~120
蓄能温差Δt1/℃初始为5
蓄能温度t3/℃t3=trt1
冷凝温度t4/℃27~36
初始状态溶液焓值h1/(kJ/kg)溶液t=t1X=X1时的焓值
浓溶液焓值h3/(kJ/kg)溶液t=t3X=X3时的焓值
水蒸气焓值hv,1-3/(kJ/kg)p=p3t=t3时饱和水蒸气的焓值
发生压力pg/kPapg=25.014 kPa
冷凝压力pc/kPape=1.226 kPa
), ArticleFig(id=1239230413684667009, tenantId=1146029695717560320, journalId=1238823019242635269, articleId=1239230396894868477, language=CN, label=表2, caption=系统运行模拟参数, figureFileSmall=null, figureFileBig=null, tableContent=
参数
初始溶液质量M1/kg给定
稀溶液浓度X1/%26~50
浓溶液浓度X2/%36~60
稀/浓溶液浓度差ΔX/%初始为5
热源温度tr/℃70~120
蓄能温差Δt1/℃初始为5
蓄能温度t3/℃t3=trt1
冷凝温度t4/℃27~36
初始状态溶液焓值h1/(kJ/kg)溶液t=t1X=X1时的焓值
浓溶液焓值h3/(kJ/kg)溶液t=t3X=X3时的焓值
水蒸气焓值hv,1-3/(kJ/kg)p=p3t=t3时饱和水蒸气的焓值
发生压力pg/kPapg=25.014 kPa
冷凝压力pc/kPape=1.226 kPa
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溶液吸收式蓄能循环特性分析
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陈泽华 1 , 王刚 1, 2 , 赵泳涵 1 , 张群力 1
制冷学报 | 面向零碳能源消纳的储冷储热技术 2025,46(3): 32-38
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制冷学报 | 面向零碳能源消纳的储冷储热技术 2025, 46(3): 32-38
溶液吸收式蓄能循环特性分析
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陈泽华1, 王刚1, 2 , 赵泳涵1, 张群力1
作者信息
  • 1北京建筑大学 供热、供燃气、通风及空调工程北京市重点实验室 北京 100044
  • 2江苏白雪电器股份有限公司 苏州 215500

通讯作者:

王刚,男,讲师,北京建筑大学环境与能源工程学院,15911066230,E-mail:。研究方向:吸收式热泵及热化学蓄能技术。
Analysis of the Characteristics of Solution Absorption Heat Storage Cycles
Zehua Chen1, Gang Wang1, 2 , Yonghan Zhao1, Qunli Zhang1
Affiliations
  • 1.Beijing Key Laboratory of Heating, Gas Supply, Ventilation and Air Conditioning Engineering, Beijing University of Civil Engineering and Architecture, Beijing, 100044, China
  • 2.Jiangsu Baixue Electric Appliance Co., Ltd., Suzhou, 215500, China
出版时间: 2025-06-16 doi: 10.12465/j.issn.0253-4339.2025.03.032
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溶液吸收式蓄能是一种热能存储和释放的新型技术,具有蓄能密度高、热量损失小、流动性好、可实现热能长期储存等优点。蓄能密度和蓄能效率是衡量系统热能储存能力和评估系统能量转化效率的关键指标参数。基于热力学原理,对比研究了6种吸收工质溶液在不同工况条件下的系统蓄能特性和适用性。结果表明:蓄能密度和蓄能效率均随热源温度、冷却水温度的升高而增大,随溶液浓度的升高而减小。热源温度为70~120 ℃、冷凝温度为24~36 ℃时,NaOH-H2O的蓄能密度和蓄能效率最大,CaCl2-H2O的蓄能密度和蓄能效率最小,LiBr-H2O的温度范围适用性最广。

吸收式  /  蓄能  /  蓄能密度  /  蓄能效率

Solution absorption energy storage is a new energy storage and release technology characterized by high energy storage density, low heat loss, good mobility, and long-term energy storage. Energy storage density and energy storage efficiency are the key indexes for measuring the energy storage capacity of absorption energy storage systems and the key parameters for evaluating the energy conversion efficiency of absorption energy storage systems, respectively. Based on thermodynamic principles, the energy storage characteristics and applicability of absorption energy storage systems were investigated using six types of absorption solutions under different conditions. The results show that both energy storage density and energy storage efficiency increase with an increase in heat source temperature and cooling water temperature and decrease with solution concentration. At a heat source temperature of 70-120 ℃ and condensing temperature of 24-36 ℃, NaOH-H2O has the largest energy storage density and efficiency, CaCl2-H2O has the smallest energy storage density and efficiency, and LiBr-H2O has the widest applicability of temperature range.

absorption  /  energy storage  /  energy storage density  /  energy storage efficiency
陈泽华, 王刚, 赵泳涵, 张群力. 溶液吸收式蓄能循环特性分析. 制冷学报, 2025 , 46 (3) : 32 -38 . DOI: 10.12465/j.issn.0253-4339.2025.03.032
Zehua Chen, Gang Wang, Yonghan Zhao, Qunli Zhang. Analysis of the Characteristics of Solution Absorption Heat Storage Cycles[J]. Journal of Refrigeration, 2025 , 46 (3) : 32 -38 . DOI: 10.12465/j.issn.0253-4339.2025.03.032
面对全球能源需求的激增,实现能源的高效利用是能源行业关注的焦点问题[1]。太阳能和工业余热是实现能源高效利用的重要可再生能源。但太阳能受气候条件影响且波动性大,工业余热资源受行业分布影响且相对分散。因此,可再生能源在能源供给侧与需求侧间存在时间、空间和能量强度不一致的问题[2]。热能储能技术是解决上述问题的关键技术,溶液吸收式蓄能是利用吸收工质溶液对水蒸气的吸收和解吸过程来实现热能储存的技术,如LiBr-H2O、NH3-H2O等,对提高能源利用效率与环境保护具有重要的现实意义[3-4]
溶液吸收式蓄能与传统的显热和潜热蓄能相比,具有储能密度高、热量损失小、流动性好、可实现能量长期储存等特点[5]。国内外学者已经开展了吸收式蓄能的实验和应用研究[6-7],R. Weber等[8]研究了一种基于NaOH-H2O溶液的吸收式溶液储能实验装置,该装置利用闭式吸收式系统,通过在低气压条件下的热储/释能过程,实现了高效的季节性热能储存,结果表明,与传统水蓄能相比,该装置在低温空间供暖方面的热容量提高6倍,在65~70 ℃的家用热水供应方面提高3倍。常明慧等[9]研究了一种基于盐溶液的热泵循环系统,该系统结合了压缩热泵和盐溶液储能2个子系统,形成了1个复合循环,并采用多层储液概念设计盐溶液储罐的结构,实现储能密度与热能品位的提升。N. I. Ibrahim等[10]研究了一种集成式太阳能驱动的且结合吸收式溶液储能的LiBr-H2O溶液吸收式制冷系统,结果表明,该集成系统能够在太阳光照射期间同时提供冷却和储存能量,冷却效果随太阳辐射变化,最大冷却能力达20 kW。制冷性能系数(coefficient of performance,COP)为0.69,吸收式能量储存的储能密度为119.6 kW·h/m3。Xu Zhenyuan等[11]提出一种新的单级吸收式蓄热循环系统,对循环系统进行理论计算,并与传统循环进行对比,蓄能密度提高138%,COP降低21%。H. Liu等[12]对太阳能长周期吸收式蓄能供热系统进行研究,对不同工质对的蓄能容量和效率进行对比分析,研究表明,蓄能容量会随蒸发温度和吸收前溶液温度的升高而增加,随着吸收温度的升高而减小。K. E. N'tsoukpoe等[13]模拟研究了基于LiBr-H2O溶液的吸收式蓄能系统,结果表明,热交换器的尺寸、溶液流量、吸收率对储能系统的蓄能密度和热效率均有较大影响,其中溶液流量是影响储能整个过程中的关键参数。Zhang Xiaoling等[14]实验研究了基于LiBr-H2O为工质对的溶液储能系统,通过实验验证了LiBr-H2O工质对的蓄/释能能力,分析了其在不同应用中的蓄能效率和密度。S. L. Grassie等[15]分析了太阳能驱动的吸收式溶液蓄能系统,并提出了氨水蓄能系统作为有效供热方式。
综上所述,采用不同工质吸收剂时蓄能特性的差异性较大,筛选出适合溶液蓄能的吸收工质对尤为重要。现有文献对溶液吸收式蓄能的不同吸收工质对在不同工况下的蓄能特性研究相对较少。本文综合考虑吸收工质对的环保性、热力学特性、蓄能密度和经济实用性,基于文献[16-19],选择了LiCl-H2O、Li-Br-H2O、NaOH-H2O、CaCl2-H2O、KOH-H2O、SrBr2-H2O共6种不同的吸收工质溶液,再基于热力学原理,对比研究6种不同的吸收工质对在变工况下的溶液吸收式蓄能系统的蓄能特性。
溶液吸收式蓄能是一种热化学蓄能方式,通过蓄能介质之间的结合能发生可逆变化来储存和释放能量。由吸收剂和吸收质之间的热化学反应实现,其中吸收质在不同阶段相态不同,解析过程是蓄能过程,吸收过程是释能过程[18],该可逆吸收过程的充能/释能阶段可表示为[19]
AB是由A(吸收剂)、B(吸收质)2种物质混合而成的稀溶液,被称为工质对。吸收式蓄/释能过程原理如图1所示。蓄能过程,稀溶液AB(稀)在外部热量ΔQ的作用下被加热,浓缩成为浓溶液AB(浓),并释放出气态吸收质B。气态吸收质B通过水蒸气循环管在冷凝罐内冷凝成冷剂液并储存,如图1(a)所示。释能过程,储存的液态吸收质B吸收外部低温热源在低压环境下蒸发成冷剂水蒸气,经蒸气循环管进入吸收/发生器,浓溶液AB(浓)吸收水蒸气变成稀溶液AB(稀),释放溶解热,如图1(b)所示。在能量转换和储存的过程中,物质的状态和浓度(本文浓度均为质量分数)会发生变化,能量则转化为化学能,可长期或季节性储存,热损失小[20]
吸收工质对浓度随蓄能过程不断变化导致物性不断变化,该过程是动态平衡的。为便于建模,对溶液吸收蓄能过程进行简化,假设如下:1)溶液工质对的物性参数是恒定的;2)系统运行是稳态的;3)系统内处于真空状态,气液相平衡;4)系统与环境的热量损失被忽略;5)系统与换热器间的热量损失被忽略;6)溶质无相变,溶剂发生相变。
典型吸收式蓄能循环p-T图如图2所示。蓄能过程主要分为2大阶段:加热阶段1-2、浓缩阶段2-3,即加热主导蓄能阶段和浓缩主导蓄能阶段,稀溶液在加热作用下浓缩成浓溶液[21]
稀溶液浓缩时产生的水蒸气质量:
根据质量守恒,确定溶液工质对由状态点1变化至状态点3的浓度和溶液质量的关系:
根据能量平衡,确定溶液工质对由状态点1变化至状态点3的耗热量:
水蒸气进入冷凝器冷凝成冷剂水,能量守恒方程如下:
稀溶液变成浓溶液后,溶液内能的变化量为:
蓄能密度(energy storage density,ESD)和蓄能效率(energy storage efficiency,ESE)的定义式如下:
上述能量、质量方程中,溶液温度由溶液的浓度和压力关系式得到:
当溶液达到一定浓度时,溶液的焓值由溶液的温度和浓度关系式得到:
冷剂水在特定温度下蒸发,系统中水溶液蒸发压力由水溶液的温度决定:
为确保该方程组封闭,引入11个物性方程,如表1所示。
上述物性方程中,工质溶液对LiBr-H2O、NaOH-H2O的物性方程分别来自文献[22-24]、文献[25]。工质溶液对LiCl-H2O、CaCl2-H2O、KOH-H2O、SrBr2-H2O的物性方程来自于软件AspenPlusV11。
设定特定的温差和浓度差界限,通过调用溶液物性计算程序,利用MATLAB软件进行数值求解,所需参数如表2所示,模型求解流程如图3所示。
为验证模拟准确性,基于文献[27]设计的实验工况,以本文模拟计算值与文献[27]实验数据进行对比如图4所示。由图4可知,模拟数据与实验数据的最大相对误差为5.2%,最小相对误差为1.5%。本模型具有良好的准确性。
pg=pc=25.01 kPa,pa=pe=1.23 kPa,冷凝温度t4=35 ℃,6种不同吸收工质溶液(LiCl-H2O、LiBr-H2O、NaOH-H2O、CaCl2-H2O、KOH-H2O、SrBr2-H2O)在浓度为35%~55%时,蓄能密度和蓄能效率随热源温度的变化如图5图6所示。溶液工质对的蓄能密度和蓄能效率均随热源温度的升高而增大,与文献[21]中LiCl-H2O、LiBr-H2O、NaOH-H2O溶液在吸收式蓄能系统蓄能过程中热源温度对蓄能密度和蓄能效率影响的结论一致。随着热源温度的升高,发生器内消耗的热量Qg增加,溶液工质对的质量M1和冷凝热Qc保持不变,蓄能密度和蓄能效率均会增大。热源温度的升高,液体分子的平均动能增加,分子间的作用力相对减弱,分子更容易由液态逃逸到气态,溶液的蒸发潜热降低[28-29]
蓄能密度由高至低依次为:NaOH-H2O>LiCl-H2O>KOH-H2O>LiBr-H2O>SrBr2-H2O>CaCl2-H2O;蓄能效率由高至低依次为:NaOH-H2O>KOH-H2O>LiCl-H2O>LiBr-H2O>SrBr2-H2O>CaCl2-H2O。相同温度和压力下,NaOH-H2O溶液的蓄能密度和蓄能效率最大,分别为257.16kJ/kg和57.68%;CaCl2-H2O溶液的蓄能密度和蓄能效率最小,分别为44.26kJ/kg和16.36%。
为防止溶液工质对出现结晶现象,热源最高温度需严格控制。如SrBr2-H2O溶液的温度控制区间为70~80 ℃;LiCl-H2O溶液的温度控制区间为70~95 ℃,LiBr-H2O溶液温度控制区间最大为70~120 ℃。
pg=pc=25.01 kPa,pa=pe=1.23 kPa,热源温度tr=80 ℃,冷凝温度t4=35 ℃,6种工质LiBr-H2O、LiCl-H2O、NaOH-H2O、CaCl2-H2O、KOH-H2O、SrBr2-H2O的浓度变化区间分别为50%~60%、26%~36%、40%~50%、40%~50%、40%~50%、30%~40%。6种吸收工质溶液的浓度变化对其在溶液吸收式蓄能装置中的蓄能密度和蓄能效率的影响如图7图8所示。随着溶液浓度的增大,蓄能密度和蓄能效率均降低,与文献[26]中基于NH3-H2O溶液储能远距离输送供能能量系统的蓄能密度和蓄能效率随溶液浓度的增加而降低的结论一致。当热源温度恒定,溶液浓度的增加直接影响了溶液工质对的热力学参数,如溶液的焓值,高浓度溶液导致稀溶液和浓溶液之间的焓差减小[26],焓差越小,溶液工质对在蓄能过程中能够存储的热量越小,蓄能密度和蓄能效率越低。相反,焓差越大,蓄能密度和蓄能效率越高。
相同温度和压力下,不同工质溶液浓度增大时,蓄能密度和蓄能效率的降幅有所不同。其中,蓄能密度、蓄能效率降幅最大的分别为LiCl-H2O溶液、KOH-H2O溶液,下降比率为38.2%、25.13%;蓄能密度、蓄能效率降幅最小的均为CaCl2-H2O溶液,下降比率分别为16.9%和13%。
LiCl-H2O溶液的蓄能密度最大,最大值为212.12kJ/kg,NaOH-H2O溶液的蓄能效率最大,最大值为51.2%;CaCl2-H2O溶液的蓄能密度和蓄能效率最小,最小值分别为77.06kJ/kg和25.36%。
pg=pc=25.01 kPa、pa=pe=1.23 kPa,热源温度tr=80 ℃,6种吸收工质溶液在浓度为35%~55%时,蓄能密度和蓄能效率随冷凝温度的变化如图9图10所示。随着冷凝温度增加,冷凝的制冷剂水温度上升,水蒸气与制冷剂水之间的焓差减小,冷凝器内的冷凝热Qc减小,溶液质量M1和耗热量Qg不变,溶液工质对的蓄能密度和蓄能效率均增大。
蓄能密度由高至低依次为:NaOH-H2O>LiCl-H2O>KOH-H2O>LiBr-H2O>SrBr2-H2O>CaCl2-H2O;蓄能效率由高至低依次为:CaCl2-H2O>NaOH-H2O>KOH-H2O>LiCl-H2O>LiBr-H2O>SrBr2-H2O。同一冷凝温度下,不同工质溶液的蓄能密度和蓄能效率存在显著差异,蓄能密度最大和最小的工质溶液对分别为NaOH-H2O溶液和CaCl2-H2O溶液,蓄能密度为278.72、73.96kJ/kg。蓄能效率最大和最小的工质溶液对分别为CaCl2-H2O溶液和SrBr2-H2O溶液,蓄能效率为43.32%、29.12%。随着冷凝温度的变化,各工质溶液蓄能密度和蓄能效率的相对大小保持稳定。
基于热力学基本原理,模拟研究了LiCl-H2O、LiBr-H2O、NaOH-H2O、CaCl2-H2O、KOH-H2O、SrBr2-H2O共6种不同的吸收工质对在变工况下的溶液吸收式蓄能装置的蓄能特性,得到如下结论:
1)蓄能密度和蓄能效率均随热源温度、冷却水温度的升高而增大,随溶液浓度的升高而减小。
2)热源温度、溶液浓度是影响溶液吸收式蓄能特性的关键参数。
3)NaOH-H2O的蓄能密度和蓄能效率最优,LiBr-H2O的热源温度区间最大。CaCl2-H2O不被推荐作为溶液吸收蓄能工质。
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2025年第46卷第3期
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doi: 10.12465/j.issn.0253-4339.2025.03.032
  • 接收时间:2024-11-05
  • 首发时间:2026-03-13
  • 出版时间:2025-06-16
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  • 收稿日期:2024-11-05
  • 修回日期:2024-12-20
  • 录用日期:2025-01-03
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    1北京建筑大学 供热、供燃气、通风及空调工程北京市重点实验室 北京 100044
    2江苏白雪电器股份有限公司 苏州 215500

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王刚,男,讲师,北京建筑大学环境与能源工程学院,15911066230,E-mail:。研究方向:吸收式热泵及热化学蓄能技术。
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