Article(id=1295068244289803230, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1295068070071005445, articleNumber=null, orderNo=null, doi=10.19666/j.rlfd.202507136, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1753372800000, receivedDateStr=2025-07-25, revisedDate=1756310400000, revisedDateStr=2025-08-28, acceptedDate=1756915200000, acceptedDateStr=2025-09-04, onlineDate=1786697930642, onlineDateStr=2026-08-14, pubDate=1779638400000, pubDateStr=2026-05-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1786697930642, onlineIssueDateStr=2026-08-14, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1786697930642, creator=13701087609, updateTime=1786697930642, updator=13701087609, issue=Issue{id=1295068070071005445, tenantId=1146029695717560320, journalId=1210938733613449225, year='2026', volume='55', issue='5', pageStart='1', pageEnd='186', issueExtLink='null', onlineDate='null', pubDate='1779638400000', pubDateStr='2026-05-25', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1786697889106, creator='13701087609', updateTime=1786698835709, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1295072040462078420, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1295068070071005445, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1295072040462078421, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1295068070071005445, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=33, endPage=41, ext={EN=ArticleExt(id=1295068244457575391, articleId=1295068244289803230, tenantId=1146029695717560320, journalId=1210938733613449225, language=EN, title=Experimental study on the properties of fly ash-steel slag composite phase change heat storage materials, columnId=1295068070763065606, journalTitle=Thermal Power Generation, columnName=Energy storage and renewable energy technology, runingTitle=null, highlight=null, articleAbstract=

In response to the escalating energy crisis and the mounting pressure associated with industrial solid waste disposal, the development of efficient and stable composite phase change heat storage materials is of paramount significance. This study uses solar salt as the phase change medium, with steel slag and fly ash employed as porous skeleton materials. A novel composite phase change heat storage material is synthesized via the cold pressing and hot sintering process. Through systematic optimization of material composition, the optimal mass ratio is determined as fly ash: steel slag: solar salt equal to 25:25:50. The characterization results demonstrate excellent chemical compatibility among the composite components, with no formation of new phases. The composite exhibits superior thermal energy storage performance, with a phase change latent heat of 57.96 J/g, a heat storage density of 291.968 J/g within the temperature range of 100~400 ℃ and a thermal conductivity of 0.952 W/(m·K). Mechanical property testing reveals a high compressive strength of 55.0 MPa. Crucially, the material maintains stable phase change behavior and structural integrity after 3 600 thermal cycles, with a mass loss rate below 0.05%. This research not only facilitates the high-value-added utilization of industrial solid wastes but also provides novel insights into the material design for medium and high-temperature thermal energy storage systems.

, authors=Yanan SU1, Yaxuan XIONG1, 2, Meng LI1, Meichao YIN1, Miao HE1, Yuting WU3, Cancan ZHANG3, Yulong DING4, authorsList=Yanan SU, Yaxuan XIONG, Meng LI, Meichao YIN, Miao HE, Yuting WU, Cancan ZHANG, Yulong DING, authorCompany=null, correspAuthors=Yaxuan XIONG, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1295068248203088888, articleId=1295068244289803230, tenantId=1146029695717560320, journalId=1210938733613449225, language=CN, title=粉煤灰-钢渣复合相变储热材料性能实验研究, columnId=1295068072533061896, journalTitle=热力发电, columnName=储能与可再生能源技术, runingTitle=null, highlight=null, articleAbstract=

面对日益严峻的能源危机和工业固废处置压力,开发高效稳定的复合相变储热材料具有重要意义。研究选取太阳盐作为相变材料,钢渣和粉煤灰作为多孔骨架,采用冷压热烧结法制备出新型复合相变储热材料。通过优化材料配比,确定粉煤灰、钢渣和太阳盐最佳质量配比为25:25:50。研究结果表明:复合材料各组分间具有良好的化学相容性,未产生新物相;该材料表现出优异的储热性能,相变潜热达到57.96 J/g,在100~400 ℃温度范围内储热密度达291.968 J/g,其最大热导率为0.952 W/(m·K);根据力学性能测试分析,复合材料表现出优异承压能力,抗压强度高达55.0 MPa;经过3 600次热循环后,材料仍保持稳定的相变性能和结构完整性,质量损失率低于0.05%。研究不仅实现了工业固废的高附加值利用,还为中高温储热系统的材料开发提供了新思路。

, authors=苏娅楠1, 熊亚选1, 2, 李萌1, 尹美超1, 何苗1, 吴玉庭3, 张灿灿3, 丁玉龙4, authorsList=苏娅楠, 熊亚选, 李萌, 尹美超, 何苗, 吴玉庭, 张灿灿, 丁玉龙, authorCompany=null, correspAuthors=熊亚选, authorNote=

苏娅楠(2001),女,硕士研究生,主要研究方向为固废复合相变储热,

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熊亚选(1977),男,教授,主要研究方向为固废储热和低碳建筑技术,
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Construction and Building Materials, 2022, 361: 129638., articleTitle=Waste semicoke ash utilized to fabricate shape-stable phase change composites for building heating and cooling, refAbstract=null), Reference(id=1295068259355742316, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1295068244289803230, doi=null, pmid=null, pmcid=null, year=2022, volume=238, issue=null, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=[14], rfOrder=21, authorNames=WU J, ZHANG C, XU X, journalName=Solar Energy Materials and Solar Cells, refType=null, unstructuredReference=WU J, ZHANG C, XU X, et al. Ceramic-molten salt composites (CPCMs) for high-temperature thermal energy storage: improving sinter ability and thermal stability by using solid wastes as skeletons[J]. 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Science of The Total Environment, 2024, 920: 170667., articleTitle=A review of solid wastes-based stabilizers for remediating heavy metals co-contaminated soil: applications and challenges, refAbstract=null), Reference(id=1295068259603206255, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1295068244289803230, doi=null, pmid=null, pmcid=null, year=2022, volume=32, issue=null, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=[17], rfOrder=24, authorNames=FRANCISCA F M, MOZEJKO C A, journalName=Geomechanics for Energy and the Environment, refType=null, unstructuredReference=FRANCISCA F M, MOZEJKO C A. Hydraulic and mechanical behavior of compacted silts modified by waste steel slag[J]. Geomechanics for Energy and the Environment, 2022, 32: 100323., articleTitle=Hydraulic and mechanical behavior of compacted silts modified by waste steel slag, refAbstract=null), Reference(id=1295068259666120816, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1295068244289803230, doi=null, pmid=null, pmcid=null, year=2021, volume=413, issue=null, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=[18], rfOrder=25, authorNames=ANAGNOSTOPOULOS A, NAVARRO M E, STEFANIDOU M, journalName=Journal of Hazardous Materials, refType=null, unstructuredReference=ANAGNOSTOPOULOS A, NAVARRO M E, STEFANIDOU M, et al. Red mud-molten salt composites for medium-high temperature thermal energy storage and waste heat recovery applications[J]. Journal of Hazardous Materials, 2021, 413: 125407., articleTitle=Red mud-molten salt composites for medium-high temperature thermal energy storage and waste heat recovery applications, refAbstract=null), Reference(id=1295068259737423985, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1295068244289803230, doi=null, pmid=null, pmcid=null, year=2012, volume=86, issue=10, pageStart=2897, pageEnd=2911, url=null, language=null, rfNumber=[19], rfOrder=26, authorNames=IVERSON B D, BROOME S T, KRUIZENGA A M, journalName=Solar Energy, refType=null, unstructuredReference=IVERSON B D, BROOME S T, KRUIZENGA A M, et al. Thermal and mechanical properties of nitrate thermal storage salts in the solid-phase[J]. Solar Energy, 2012, 86(10): 2897-2911., articleTitle=Thermal and mechanical properties of nitrate thermal storage salts in the solid-phase, refAbstract=null), Reference(id=1295068259829698674, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1295068244289803230, doi=null, pmid=null, pmcid=null, year=2010, volume=null, issue=null, pageStart=1, pageEnd=null, url=null, language=null, rfNumber=[20], rfOrder=27, authorNames=null, journalName=null, refType=null, unstructuredReference=混凝土结构设计规范:GB 50010—2010[S]. 北京:中国建筑工业出版社,2010:1., articleTitle=null, refAbstract=null), Reference(id=1295068259888418931, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1295068244289803230, doi=null, pmid=null, pmcid=null, year=2010, volume=null, issue=null, pageStart=1, pageEnd=null, url=null, language=null, rfNumber=[20], rfOrder=28, authorNames=null, journalName=null, refType=null, unstructuredReference=Code for design of concrete structures: GB 50010—2010[S]. 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elemental distribution maps of sample FS6 before and after cycling, figureFileSmall=8l/KfBZneoZXhkZY/HQowQ==, figureFileBig=e47/mbQ6u5l98MjiKCBUag==, tableContent=null), ArticleFig(id=1295068255312433230, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1295068244289803230, language=CN, label=图12, caption=循环前后样品FS6的EDS元素分布图谱, figureFileSmall=8l/KfBZneoZXhkZY/HQowQ==, figureFileBig=e47/mbQ6u5l98MjiKCBUag==, tableContent=null), ArticleFig(id=1295068255383736399, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1295068244289803230, language=EN, label=Tab.1, caption=

Mass fractions of the compositions of the skeleton materials

, figureFileSmall=null, figureFileBig=null, tableContent=
SiO2Al2O3Fe2O3CaOK2OSO3其他
钢渣25.747.1637.6211.091.844.1712.38
粉煤灰50.0035.924.724.241.130.973.02
), ArticleFig(id=1295068257082429520, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1295068244289803230, language=CN, label=表1, caption=

骨架材料成分的质量分数

, figureFileSmall=null, figureFileBig=null, tableContent=
SiO2Al2O3Fe2O3CaOK2OSO3其他
钢渣25.747.1637.6211.091.844.1712.38
粉煤灰50.0035.924.724.241.130.973.02
), ArticleFig(id=1295068257153732689, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1295068244289803230, language=EN, label=Tab.2, caption=

Samples with different mass ratios

, figureFileSmall=null, figureFileBig=null, tableContent=
样品FS1FS2FS3FS4FS5FS6FS7FS8FS9FS10FS11
粉煤灰50454035302520151050
钢渣05101520253035404550
太阳盐5050505050505050505050
), ArticleFig(id=1295068257229230162, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1295068244289803230, language=CN, label=表2, caption=

不同质量配比的样品

, figureFileSmall=null, figureFileBig=null, tableContent=
样品FS1FS2FS3FS4FS5FS6FS7FS8FS9FS10FS11
粉煤灰50454035302520151050
钢渣05101520253035404550
太阳盐5050505050505050505050
), ArticleFig(id=1295068257317310547, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1295068244289803230, language=EN, label=Tab.3, caption=

The mass and mass loss rate of sample FS6 before and after cycling

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样品循环前质量/g循环后质量/g质量损失率/%
FS6-11.006 41.006 10.03
FS6-20.999 90.999 60.03
FS6-31.003 21.003 10.01
), ArticleFig(id=1295068257430556756, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1295068244289803230, language=CN, label=表3, caption=

样品FS6循环前后的质量与质量损失率

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样品循环前质量/g循环后质量/g质量损失率/%
FS6-11.006 41.006 10.03
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粉煤灰-钢渣复合相变储热材料性能实验研究
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苏娅楠 1 , 熊亚选 1, 2 , 李萌 1 , 尹美超 1 , 何苗 1 , 吴玉庭 3 , 张灿灿 3 , 丁玉龙 4
热力发电 | 储能与可再生能源技术 2026,55(5): 33-41
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热力发电 |储能与可再生能源技术 2026 , 55 (5) : 33 -41
粉煤灰-钢渣复合相变储热材料性能实验研究
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苏娅楠1 , 熊亚选1, 2 , 李萌1, 尹美超1, 何苗1, 吴玉庭3, 张灿灿3, 丁玉龙4
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 102600
  • 2.北京建筑大学未来新材料研究院,北京 102600
  • 3.北京工业大学传热与能源利用北京市重点实验室,北京 100124
  • 4.英国伯明翰大学伯明翰储能中心,伯明翰 B15 2TT
通讯作者:
熊亚选(1977),男,教授,主要研究方向为固废储热和低碳建筑技术,
作者简介:

苏娅楠(2001),女,硕士研究生,主要研究方向为固废复合相变储热,

Experimental study on the properties of fly ash-steel slag composite phase change heat storage materials
Yanan SU1 , Yaxuan XIONG1, 2 , Meng LI1, Meichao YIN1, Miao HE1, Yuting WU3, Cancan ZHANG3, Yulong DING4
Affiliations
  • 1.Beijing Key Lab of Heating, Gas Supply, Ventilating and Air Conditioning Engineering, Beijing University of Civil Engineering and Architecture, Beijing 102600, China
  • 2.Institute of Advanced Materials, Beijing University of Civil Engineering and Architecture, Beijing 102600, China
  • 3.Beijing Key Laboratory of Heat Transfer and Energy Conversion, Beijing University of Technology, Beijing 100124, China
  • 4.Birmingham Center for Energy Storage, University of Birmingham, Birmingham B15 2TT, UK
出版时间: 2026-05-25 doi: 10.19666/j.rlfd.202507136
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面对日益严峻的能源危机和工业固废处置压力,开发高效稳定的复合相变储热材料具有重要意义。研究选取太阳盐作为相变材料,钢渣和粉煤灰作为多孔骨架,采用冷压热烧结法制备出新型复合相变储热材料。通过优化材料配比,确定粉煤灰、钢渣和太阳盐最佳质量配比为25:25:50。研究结果表明:复合材料各组分间具有良好的化学相容性,未产生新物相;该材料表现出优异的储热性能,相变潜热达到57.96 J/g,在100~400 ℃温度范围内储热密度达291.968 J/g,其最大热导率为0.952 W/(m·K);根据力学性能测试分析,复合材料表现出优异承压能力,抗压强度高达55.0 MPa;经过3 600次热循环后,材料仍保持稳定的相变性能和结构完整性,质量损失率低于0.05%。研究不仅实现了工业固废的高附加值利用,还为中高温储热系统的材料开发提供了新思路。

粉煤灰  /  钢渣  /  太阳盐  /  复合相变储热  /  储热性能

In response to the escalating energy crisis and the mounting pressure associated with industrial solid waste disposal, the development of efficient and stable composite phase change heat storage materials is of paramount significance. This study uses solar salt as the phase change medium, with steel slag and fly ash employed as porous skeleton materials. A novel composite phase change heat storage material is synthesized via the cold pressing and hot sintering process. Through systematic optimization of material composition, the optimal mass ratio is determined as fly ash: steel slag: solar salt equal to 25:25:50. The characterization results demonstrate excellent chemical compatibility among the composite components, with no formation of new phases. The composite exhibits superior thermal energy storage performance, with a phase change latent heat of 57.96 J/g, a heat storage density of 291.968 J/g within the temperature range of 100~400 ℃ and a thermal conductivity of 0.952 W/(m·K). Mechanical property testing reveals a high compressive strength of 55.0 MPa. Crucially, the material maintains stable phase change behavior and structural integrity after 3 600 thermal cycles, with a mass loss rate below 0.05%. This research not only facilitates the high-value-added utilization of industrial solid wastes but also provides novel insights into the material design for medium and high-temperature thermal energy storage systems.

fly ash  /  steel slag  /  solar salt  /  composite phase change heat storage  /  heat storage performance
苏娅楠, 熊亚选, 李萌, 尹美超, 何苗, 吴玉庭, 张灿灿, 丁玉龙. 粉煤灰-钢渣复合相变储热材料性能实验研究. 热力发电, 2026 , 55 (5) : 33 -41 . DOI: 10.19666/j.rlfd.202507136
Yanan SU, Yaxuan XIONG, Meng LI, Meichao YIN, Miao HE, Yuting WU, Cancan ZHANG, Yulong DING. Experimental study on the properties of fly ash-steel slag composite phase change heat storage materials[J]. Thermal Power Generation, 2026 , 55 (5) : 33 -41 . DOI: 10.19666/j.rlfd.202507136
随着全球能源体系结构变革以及“双碳”战略目标的实施,在工业化进程加速与城镇化扩张的双重驱动下,能源消费总量呈现持续攀升态势,传统化石能源所引发的环境污染问题日益显著,这驱动全球能源体系向清洁可持续方向加速转型[1]。太阳能、风能等可再生能源凭借自身储量丰富且清洁无污染的特性,已成为科研领域与实际应用中的关注焦点[2]。然而此类可再生能源自身存在间歇性与不稳定的缺陷,这阻碍了其大规模且高效地开发利用[3]。为突破这一技术障碍,发展先进的储能技术尤为重要。
根据储热机理的差异,现阶段热能存储技术可分为基于温度变化的显热储能、利用相变过程的潜热储能及通过化学反应实现的热化学储能[4]三类体系。其中潜热储热技术(即相变储热)通过材料相变过程中的潜热吸收或释放进行能量储存,相较于显热储热系统,其具有更稳定的温度控制能力和更优的系统运行特性,并且储热密度可达显热储热的5~10倍[5],这些特性使其在建筑供暖系统优化、太阳能集热装置、电池热管理以及工业废热回收利用等多个领域展现出重要应用价值[6-7]
复合相变储热材料(PCC)是一种形状稳定、导热增强的复合相变材料,其通常由相变材料(PCM)和支撑骨架材料两部分组成,通过物理或化学方法复合而成。理想的支撑骨架材料应具备高孔隙率、良好导热性、与相变物质相容性好等特点[8]。近年来,工业固体废弃物因其多孔结构,且含有丰富矿物质,被视为潜在的优质骨架材料。粉煤灰作为燃煤电厂的副产物,含有大量SiO2、Al2O3等成分,经过适当处理可形成多孔结构[9],且具有优异的热力学性能和稳定的化学性质;钢渣是炼钢过程中的主要工业副产物,富含CaO、Fe2O3等成分,具有较高的导热潜力和机械强度[10]。将这2种固废协同利用作为复合骨架材料,有望发挥各自优势,进而开发出性能优异的复合相变材料。
现有研究表明,固废基复合相变储热材料不仅能有效封装相变物质,防止泄漏,还能改善导热性能,同时实现固废的高附加值利用。杨洋等[11]采用固碳处理的电石渣-钢渣复合骨架材料,通过优化配比,制备得到一系列PCC样品,其中热性能最优样品的储热密度可达444.2 J/g。王辉祥等[12]以电石渣作为骨架材料,成功制得Na2CO3/电石渣PCC,结果表明,当Na2CO3质量分数为47.5%时样品性能最佳,在100~900 ℃温度区间内储热密度为993 J/g。Xiong等人[13]以兰炭灰和硝酸钠分别作为骨架材料和相变材料,最佳样品的储热能力达到325.91 J/g,机械强度高达96.98 MPa。Wu等人[14]利用钛铁渣和废玻璃作为骨架材料支撑Na2SO4-NaCl熔盐,研究得出,废玻璃能促进PCC粘滞流动和烧结能力,从而提高PCC的抗压强度。Wang等人[15]以碳酸钾为PCM,以改性粉煤灰为骨架材料制备得到PCC,结果表明含质量分数40%改性粉煤灰的PCC具有最优性能,在150次热循环后热导率为0.44 W/(m·K),潜热为122.1 J/g,并且具有良好的循环稳定性。然而,关于粉煤灰和钢渣的配比优化、孔隙结构调控及其对太阳盐负载行为和储热性能的影响机制尚不明确,尤其对于复合材料在长期热循环过程中的稳定性表现,还有其腐蚀行为特征,亟待开展系统性的研究。
基于以上背景及团队研究基础,本文以粉煤灰和钢渣为复合骨架材料,太阳盐为相变材料,通过研究粉煤灰与钢渣的协同作用机制,对二者的配比及其制备工艺进行优化,进而开发高性能复合相变储热材料。
本研究中,选用太阳盐作为相变材料,组分为NaNO3(分析纯,国药集团化学试剂有限公司)和KNO3(分析纯,国药集团化学试剂有限公司),选用粉煤灰(采自山东魏桥某矿场)和钢渣(采自鞍钢集团有限公司)作为骨架材料。实验前粉煤灰和钢渣均在900 ℃高温下煅烧8 h进行预处理,煅烧后的粉煤灰和钢渣的组成成分见表1
首先分别将NaNO3、KNO3在高速粉碎机中粉碎20 s,将粉碎后的粉末状样品置于干燥箱中,恒温170 ℃干燥24 h;然后按6:4的质量比称取干燥后的NaNO3和KNO3充分混合均匀后放入刚玉坩埚中搅拌均匀,置于马弗炉中,在380 ℃下恒温4 h,使样品完全熔化、充分混合均匀,制备得到太阳盐熔盐;最后将其取出在室温下自然冷却凝固,将制得的太阳盐块体在高速粉碎机中粉碎20 s,粉碎后继续研磨至粒径为38 μm的粉末,放置于干燥箱中保存以备后续使用。太阳盐制备流程如图1所示。
实验前先将粉煤灰与钢渣在马弗炉中900 ℃煅烧8 h进行预处理,煅烧后研磨至粒径为38 μm的粉末放入干燥箱中等待后续使用。
实验采取冷压烧结法制备粉煤灰-钢渣/太阳盐复合相变储热材料,制备工艺流程见图2。具体实验步骤如下:将材料从干燥箱中取出,使用分析天平(ME104)按照预设质量比分别对粉煤灰、钢渣、太阳盐粉末进行精确称量;将称量后的混合粉末置于行星球磨机(KE-2L)中,设定转速为200 r/min进行球磨混合30 min;称取1.00 g混合均匀后的粉末装入内径13 mm的圆柱模具中,利用液压压力机(MSY-50)施加2 MPa压力并保压3 min,脱模得到圆柱形PCC样品生料;将压制好的样品置于空气气氛马弗炉(SX2-5-12A)中,程序设定为第一阶段以5 ℃/min的升温速率从30 ℃升温至120 ℃,保温1 h去除样品中残留的水分,第二阶段继续以5 ℃/min的升温速率从120 ℃升温至280 ℃保温2 h,完成烧结后关闭马弗炉,等待样品自然冷却至室温后转移至恒温干燥箱中保存,用于后续性能表征。为确保实验可重复性,每组配比均制备3个平行试样用于后续测试。
基于表2设计的不同质量配比方案,采用前述制备工艺,成功制得了11组PCC样品,并依次编号为FS1到FS11。
本研究通过多种表征方法对材料性能进行系统分析。使用X射线荧光光谱分析仪(XRF,AxioMax,PANalyticalB.V.)测定骨架材料的化学成分及质量分数。利用同步热分析仪(TG-DSC,STA449F3,NETSCH),在氮气气氛下采用铝坩埚测定样品的比热容、相变温度、熔化潜热。使用激光闪射仪(LFA467,NETSCH),在氮气保护环境下采用铝坩埚测定样品的热扩散系数。研究采用X射线衍射仪(XRD,SmartLab,Rigaku)以Cu靶辐射进行物相分析,扫描范围设定为5°~90°,评估相变材料与骨架材料间的化学稳定性。将被测样品制成直径13 mm、厚度13 mm的圆柱体,烧结后采用电子万能材料试验机(CMT4304,MTS)以恒速增压法对其进行力学性能测试。微观形貌观察采用扫描电子显微镜(SEM,SU8010,Hitachi),加速电压15 kV,配合能谱分析仪(EDS,X-MaxN50,HORIBA)进行元素分布分析。热循环测试使用实验室自制自动控制系统的热循环装置,样品在程序控制下随载样台周期性进出恒温280 ℃的电炉腔体,在炉腔内保温10 min。载样台设定的移动时间间隔为272 s,循环温度为室温至280 ℃。
通过冷压烧结法制备的粉煤灰-钢渣/太阳盐PCC的宏观形貌特征如图3所示。
从颜色上来看,不同质量比的样品在烧结处理后,因为钢渣呈黑色,粉煤灰呈黄褐色,所以随着钢渣含量的增加,样品从黄褐色逐渐变为黑褐色;样品均未出现明显的变形与裂纹,这主要是因为粉煤灰和钢渣具有良好的孔隙结构[16],经过高温煅烧处理后,吸附性孔道增加,比表面积增大,增大了内部孔洞。
值得注意的是,FS1—FS6底部没有出现明显泄漏,从FS7开始,随着骨架材料中钢渣含量的增加,样品出现泄漏(图4)。可以看出,FS6底部未出现太阳盐泄漏的情况,而FS7底部出现浅白色熔盐泄漏并重新凝固的痕迹,随着钢渣与粉煤灰质量比例的增加,FS8—FS11底部泄漏也随之增加。在烧结完成后样品黏附在样品盘中,这主要是由于粉煤灰的内部孔隙结构比钢渣表现良好,同时太阳盐在烧结过程中从固态转变为液态,当粉煤灰比例降低时,颗粒内部孔隙结构难以吸附并容纳熔融的相变材料,致使PCC内部应力分布不均匀。此外,气-固界面存在的毛细力和表面张力难以有效约束相变材料,导致烧结后的样品结构发生形变以及相变材料泄漏现象。
当粉煤灰、钢渣和太阳盐的质量比达到最优(样品FS6)时,骨架材料的孔隙刚好吸附熔融态太阳盐,避免了介质泄漏和结构变形。初步宏观形貌观察与泄漏测试表明,当钢渣的比例大于粉煤灰时,样品在相变熔化后发生液相渗漏,表明其已超出骨架的物理封装极限,不具备实际应用价值,故予以淘汰,同时鉴于钢渣的添加有助于提升PCC的力学性能[17],综合确定粉煤灰、钢渣和太阳盐的最佳质量比为25:25:50,以下研究内容将FS6作为主要研究对象。
热循环测试的主要目的是评估材料或器件在反复温度变化条件下的可靠性和耐久性,为了验证材料在温度循环过程中是否发生损坏、泄漏或其他热致退化现象,本研究在自制的热循环装置中对3组FS6样品(FS6-1、FS6-2、FS6-3)进行了加热冷却循环实验。以500次为检测周期,对其外观形貌及质量进行观测和称量。通过式(1)计算样品的质量损失率:
R=m1m2m1
式中:R为样品的质量损失率,%;m1为样品循环前的初始质量,g;m2为样品循环后的质量,g。
在整个热循环测试过程中,所有试样宏观形貌保持完整,没有出现相变材料泄漏、样品开裂等情况;经3 600次热循环测试后,试样表面观察到细微裂纹出现,据此可确定该材料可稳定承受3 600次加热冷却循环过程。质量变化及质量损失率见图5表3。经计算,3组样品的质量损失率均低于0.05%,质量几乎不变,说明该材料具有良好的耐久性与热稳定性,在中高温储热应用方面具有极好的应用前景。
复合相变储热材料在实际应用中需长期承受高温下的反复加热/冷却循环,因此骨架材料与相变材料之间的化学相容性成为影响材料稳定性的关键因素。图6展示了骨架材料、相变材料和样品FS6的X射线衍射图谱对比结果。
图6a)可以看出,太阳盐的晶体结构主要由NaNO3和KNO3组成,而骨架材料中粉煤灰的晶相以莫来石为主,钢渣的主要成分是Fe2O3,其他晶相因含量较低,衍射信号较弱。在FS6样品及其热循环后的样品中,主要晶相仍为莫来石、Fe2O3、NaNO3和KNO3,图谱中未新增衍射峰。这说明在本实验中,骨架材料与相变材料之间没有发生显著化学反应,化学相容性良好,具备实际应用的潜力。
图6b)展示了样品经历热循环前后的XRD光谱分析结果。通过对比衍射图谱特征可以发现,经过3 600次加热冷却循环后,复合相变储热材料的特征衍射峰位置和相对强度均未发生明显变化,也没有出现新的衍射峰或原有衍射峰消失的现象。经XRD分析计算,太阳盐中NaNO3结晶度为39.6%,KNO3结晶度为16.5%,FS6中NaNO3与KNO3结晶度分别下降为22.5%和8.0%,而循环后FS6中二者的结晶度相比FS6各下降了0.1百分点。这表明,莫来石/Fe2O3多孔骨架与太阳盐之间产生了显著的界面作用,这源于物理空间约束和界面吸附,骨架材料限制了太阳盐分子的自由移动,部分抑制了其完美结晶。虽然这种作用力牺牲了部分储热能力,但极大地增强了界面结合力和空间约束效应,极大地抑制了液相泄漏。同时也抑制了多元盐在反复熔化-凝固过程中发生相分离。循环后结晶度的轻微下降也对应了其相变焓的降低。这些特征说明材料在反复热循环过程中晶体结构保持稳定。以上结果充分证明该样品的化学稳定性良好,能够在3 600次热循环过程中保持稳定的晶体结构和化学组成,没有发生相分离、氧化或其他化学反应,这为其长期稳定应用于储能系统奠定了基础。
本研究在温度100~400 ℃测量了太阳盐和循环前后样品FS6的潜热ΔHm、比热容cp和熔点Tm,具体如图7所示。太阳盐、循环前FS6和循环后FS6的熔点分别为224.4、220.4、220.4 ℃,在测试的温度范围内,太阳盐的熔点高于复合相变储热材料,骨架材料的加入显著影响了太阳盐的结晶行为,随着骨架比例的增加,相变材料结晶度逐渐降低,这直接导致其熔化温度相应降低,这符合Anagnostopoulos等人[18]的研究结果。在升温过程中,太阳盐和循环前后样品FS6均出现2个熔融峰,第1个熔融峰位于200~215 ℃,对应材料的固-固相变过程,第2个显著的熔融峰出现在215~230 ℃,表明此时发生固-液相变。
太阳盐、循环前FS6和循环后FS6的潜热分别为107.80、57.96、51.29 J/g。相变潜热随相变材料含量的降低而降低,这是因为骨架材料含量的增加降低了PCM的质量分数,导致相变潜热降低。
根据升温过程的不同阶段,相变储热可分为低温加热过程的显热储热、熔化过程的潜热储热和高温加热过程的显热储热3部分。PCC的储热密度可由式(2)计算。
Q=T1Tocp1dT+ΔHm+TtThcp2dT
式中:Q为材料的储热能力,J/g;ThTl分别为对应材料工作温度的上、下限,K;ToTt分别为相变过程的起始和终止温度,K;cp1cp2分别为相变前后的比热容,J/(g·K);ΔHm为材料的熔化潜热,J/g。
按式(2)计算得到太阳盐、FS6及循环后FS6的储热密度见图8
图8所示,各样品的储热密度随温度升高均呈现近似线性增长趋势,且太阳盐表现出最优的储热性能,其储热密度达341.325 J/g。在3 600次加热/冷却循环前,样品FS6的储热密度为291.968 J/g,经循环后其储热密度衰减6.86%。经分析,该性能下降主要由于循环过程中FS6潜热值的降低。尽管如此,实验结果表明,在测试温度区间内,FS6仍展现出良好的热循环稳定性。
热导率决定了材料的热传递能力,而热扩散率决定了材料内的热分散能力。以材料在温度100、200、300 ℃时的热扩散率为测试点,利用激光闪光分析(LFA 467)测试了样品FS6和3 600次热循环后的样品FS6在100~300 ℃ 3个温度点的热扩散率,根据下式计算对应的导热系数。
λ=α(T)ρ(T)cp(T)
式中:λ为材料的导热系数,W/(m∙K);αT)为材料的热扩散系数,mm2/s;ρT)为材料的密度,g/cm3cpT)为储热材料的比热容,J/(g∙K)。
图9显示了2组样品的实测热扩散率和热导率数据。
图9的分析表明,在100℃~300 ℃温度区间内,循环前后的样品FS6的热导率和热扩散率呈现相同的变化趋势,二者均随温度的升高而下降,这是绝大多数晶体材料和非金属固体的典型特征。循环前样品FS6的最大热导率达到0.952 W/(m·K),循环后样品FS6最大热导率为0.954 W/(m·K),均高于纯太阳盐的热导率0.79 W/(m·K)[19],并且2种样品的热扩散率与导热系数呈现相似的变化规律。该结果证实骨架材料的加入能有效提升复合相变储热材料的导热能力。经3 600次循环后,样品FS6的热扩散率和热导率未出现显著改变。这说明随着固-液相变次数的增加,太阳盐通过毛细作用持续填充骨架材料颗粒内部的孔隙,形成致密化结构,有效抑制了熔盐的泄漏。
复合相变材料的力学性能可通过抗压强度表征,该参数决定其在实际工程应用中的可靠性。实验采用万能材料试验机以3.0 mm/min的恒定速率压制圆柱形样品,记录试样被压至破裂时的峰值数据作为复合相变材料的最大抗压强度。图10为样品FS6循环前和循环后的机械性能。
实验数据表明,未循环的样品FS6的抗压强度峰值达到55.0 MPa。经3 600次加热/冷却循环后,样品的抗压强度提升至68.9 MPa,这一数值不仅高于循环前样品,也显著高于GB/T 50010—2010[20]中C60等级混凝土所要求的抗压强度标准值(60 MPa),这意味着该材料力学性能安全可靠,满足诸多工程环境下的抗压要求。这种性能提升主要归因于骨架材料与相变材料间界面结合通过热应力作用得到强化,促使两界面产生“热锻效应”;同时多孔结构有效约束相变材料的熔融/凝固过程,在反复加热冷却循环过程中,其内部孔隙实现了对相变材料的完整包覆,骨架材料颗粒与相变材料间界面结合强度达到最优状态,整体致密度显著提高,达到最好的抗压性能。综合评估表明,本实验制备出的样品FS6展现出卓越的力学性能与耐久性能。
为了观察样品FS6的微观结构变化,使用扫描电子显微镜分析了3 600次加热/冷却循环前后FS6的内部微观结构。将FS6破碎成碎块,并分别在5 000、8 000、12 000的放大倍率下观察横截面的显微组织。图11展示了在加热/冷却循环前后样品FS6的微观结构。
图11a)—图11c)所示,烧结后的样品FS6中的大量颗粒和孔隙对太阳盐进行了包封和固定。在整个3 600次加热/冷却循环中,太阳盐在高温下熔化成流体,在表面张力和毛细管力的影响下,太阳盐在孔隙间缓慢流动。冷却时,太阳盐与骨架材料融合良好,形成致密结构。随着循环次数的增加,相变材料产生微流动现象。从图11d)—图11f)可以看出,样品FS6的内部结构变得更加致密,骨架材料将相变材料包覆得更加完好。
图12显示了样品FS6在循环测试前后的元素分布特征。其中,Na和K元素作为太阳盐的代表元素,Fe、Ca、Al和Si元素则代表骨架材料的主要成分。从图12a)可见,烧结后的样品FS6的元素呈均匀分布状态,表明骨架材料对相变材料形成了有效的封装与空间约束。图12b)为样品在3 600次循环后的元素分布状况,可以看到部分骨架材料元素出现局部聚集现象,这归因于反复的相变过程中,熔融态太阳盐逐渐渗入骨架材料的孔隙结构,导致骨架材料元素在表征过程中更为凸显。但是这种微观尺度的元素分布变化并未显著影响材料整体元素的均匀性。上述结果充分证明样品FS6具有出色的热循环稳定性。
本研究采用工业固废钢渣和粉煤灰作为骨架材料,以太阳盐为相变材料,制备出一种新型复合相变储热材料,通过系统的实验研究和多维度表征分析,得出以下结论。
1)通过实验,确定了粉煤灰、钢渣、太阳盐的最佳质量配比为25:25:50。在此配比下,材料实现了储热性能与机械强度的最优平衡,为工业应用提供了可靠的配方依据。未来将系统研究其他不同相变材料负载量与骨架材料调控对复合材料综合热物性能的影响。
2)高温烧结后,复合材料各组分间具有良好的化学兼容性,在制备和使用过程中未发生化学反应,材料结构稳定。
3)复合材料在最优配比下,其相变潜热为57.96 J/g,在100~400℃温度范围内储热密度达291.968 J/g,最大热导率为0.952 W/(m·K),其具有高效的热量存储与传递能力,满足中高温储热应用需求。
4)材料展现出超高的抗压强度(55.0 MPa),经热循环后,材料的抗压强度得到显著提升(68.9 MPa),为材料在承重场合的应用提供了可能,突破了传统相变材料机械强度不足的限制。
5)经过3 600次热循环测试后,材料仍保持良好的储热性能和结构完整性,质量损失率低于0.05%,循环后材料微观宏观结构保持完整,无明显裂纹或孔隙产生,展现出优异的长期使用稳定性。
  • 北京市教委科技一般项目(KM202210005016)
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doi: 10.19666/j.rlfd.202507136
  • 接收时间:2025-07-25
  • 首发时间:2026-08-14
  • 出版时间:2026-05-25
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  • 收稿日期:2025-07-25
  • 修回日期:2025-08-28
  • 录用日期:2025-09-04
基金
Science and Technology General Project of Beijing Municipal Education Commission(KM202210005016)
北京市教委科技一般项目(KM202210005016)
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 102600
    2.北京建筑大学未来新材料研究院,北京 102600
    3.北京工业大学传热与能源利用北京市重点实验室,北京 100124
    4.英国伯明翰大学伯明翰储能中心,伯明翰 B15 2TT

通讯作者:

熊亚选(1977),男,教授,主要研究方向为固废储热和低碳建筑技术,
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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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