Article(id=1271501738331807995, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1271501633826530070, articleNumber=PA20260121_3GQNfkvM, orderNo=null, doi=10.19666/j.rlfd.202503041, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1741968000000, receivedDateStr=2025-03-15, revisedDate=1743955200000, revisedDateStr=2025-04-07, acceptedDate=1744819200000, acceptedDateStr=2025-04-17, onlineDate=1781079237778, onlineDateStr=2026-06-10, pubDate=1769270400000, pubDateStr=2026-01-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1781079237777, onlineIssueDateStr=2026-06-10, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1781079237777, creator=admin, updateTime=1781079237777, updator=admin, issue=Issue{id=1271501633826530070, tenantId=1146029695717560320, journalId=1210938733613449225, year='2026', volume='55', issue='1', pageStart='1', pageEnd='186', issueExtLink='null', onlineDate='null', pubDate='1769270400000', pubDateStr='2026-01-25', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1781079212860, creator='ztmeta', updateTime=1786698917413, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1295072383149301815, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1271501633826530070, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1295072383149301816, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1271501633826530070, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=113, endPage=121, ext={EN=ArticleExt(id=1271501739812397310, articleId=1271501738331807995, tenantId=1146029695717560320, journalId=1210938733613449225, language=EN, title=Performance optimization of Mn-based thermochemical coating for high-temperature receivers to dampen solar irradiance fluctuations, columnId=1211002405299294959, journalTitle=Thermal Power Generation, columnName=Thermal energy science research, runingTitle=null, highlight=null, articleAbstract=

The Brayton cycle-based tower solar thermal power system features a flexible layout and operates at high receiver temperatures. However, fluctuations in solar irradiance can lead to thermal fatigue of receiver materials or excessive surface temperatures, necessitating effective strategies to mitigate temperature fluctuations. This study develops a manganese-based thermochemical thermal protection coating utilizing a reversible redox reaction. When solar radiation intensifies and the temperature exceeds 978 ℃, the coating undergoes a reduction endothermic reaction, reducing the heating rate. Conversely, when solar radiation decreases and the temperature drops below 878 ℃, an oxidation exothermic reaction occurs, slowing the cooling rate, thereby stabilizing receiver surface temperature fluctuations. Experimental results indicate that when the mass ratio of the coating material to the binder is 4:3, the adhesion strength reaches the highest national standard level, and the solar weighed average absorptivity achieves 94.93%. After undergoing 500 hours of thermal aging at 950 ℃, 100 cycles of thermal cycling, and 200 cycles of redox reaction tests, the coating’s weighed average absorptivity decreased by only 0.82, 0.98, and 2.61 percentage points, respectively, while maintaining the highest adhesion strength. Under a sudden change in concentrated solar radiation flux of ±9.7 kW/m², the heating and cooling rates in the first 100 seconds were reduced by 59.66% and 67.09%, respectively. Additionally, the time required for a 20 ℃ increase and decrease was extended by 182.50% and 438.60%, respectively. The manganese-based thermochemical coating demonstrates excellent aging resistance and effectively suppresses absorber temperature fluctuations, making it highly promising for applications in Brayton cycle-based tower solar thermal power systems.

, authors=Tian ZHANG1, Jing LIU2, Tianjin SUN3, Liping SHI3, Rui HU3, Wei SHUAI1, Yibin HE1, Peiwang ZHU1, 4, Gang XIAO1, 4, authorsList=Tian ZHANG, Jing LIU, Tianjin SUN, Liping SHI, Rui HU, Wei SHUAI, Yibin HE, Peiwang ZHU, Gang XIAO, authorCompany=null, correspAuthors=Gang XIAO, 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=1271501739741094141, articleId=1271501738331807995, tenantId=1146029695717560320, journalId=1210938733613449225, language=CN, title=平抑太阳能波动的高温吸热器锰基热化学涂层性能优化, columnId=1211002405437706993, journalTitle=热力发电, columnName=热能科学研究, runingTitle=null, highlight=null, articleAbstract=

塔式光热布雷顿循环发电系统的布置灵活,其吸热器工作温度较高,太阳能波动容易造成吸热器材料热疲劳或表面超温,亟需探索平抑吸热器温度波动的有效途径。开发了一种基于可逆氧化还原反应的锰基热化学热防护涂层,当太阳辐射增强且温度超过978 ℃时,涂层材料发生还原吸热反应,降低升温速率;当太阳辐射减弱且温度低于878 ℃时,发生氧化放热反应,减缓降温速率,进而平抑吸热器表面温度波动。研究表明:涂层材料与黏结剂的质量比为4:3时附着力可达国家标准的最高级,太阳光加权平均吸收率达到94.93%;在950 ℃恒温老化500 h、冷热交变老化100次循环以及氧化还原反应试验200次循环后,涂层加权平均吸收率仅分别衰减0.82百分点、0.98百分点和2.61百分点,且附着力保持在最高级;在±9.7 kW/m2的聚光辐射能流突变条件下,前100 s升温和降温速率分别降低59.66%和67.09%,升温和降温20 ℃所需的时间分别延长182.50%和438.60%。锰基热化学涂层表现出优秀的抗老化性能,并能有效平抑吸热器的温度波动,在塔式光热布雷顿循环系统中具有广阔的应用前景。

, authors=张添1, 刘静2, 孙田津3, 石丽萍3, 胡锐3, 帅威1, 何艺彬1, 祝培旺1, 4, 肖刚1, 4, authorsList=张添, 刘静, 孙田津, 石丽萍, 胡锐, 帅威, 何艺彬, 祝培旺, 肖刚, authorCompany=null, correspAuthors=肖刚, authorNote=

张添(1998),男,硕士,主要研究方向为热化学防护涂层,

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ArticleFig(id=1295064690502165129, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1271501738331807995, language=CN, label=图8, caption=能流减弱时吸热管上壁面温度变化曲线, figureFileSmall=Aj2yf2mcaLs8RiQ5ZeKPqw==, figureFileBig=61LF0mwAfHdH24A/FyQf6w==, tableContent=null), ArticleFig(id=1295064690560885386, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1271501738331807995, language=EN, label=Tab.1, caption=

Thermal protection test results of the coatings under solar lamps

, figureFileSmall=null, figureFileBig=null, tableContent=
涂层类型能流密度增强能流密度减弱总和波动温差/℃
前100 s升温速率/(℃·s–1升温20 ℃所需时间/s最终升温温度/℃前100 s降温速率/(℃·s–1降温20 ℃所需时间/s最终降温温度/℃
Pyromark 2 500 涂层(20 μm)0.2338034.80.2345737.772.5
锰基热化学涂层(20 μm)0.16914131.00.16518933.764.7
锰基热化学涂层(100 μm)0.09422621.60.07730723.545.1
), ArticleFig(id=1295064690653160075, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1271501738331807995, language=CN, label=表1, caption=

太阳能模拟灯下涂层热防护性能测试结果

, figureFileSmall=null, figureFileBig=null, tableContent=
涂层类型能流密度增强能流密度减弱总和波动温差/℃
前100 s升温速率/(℃·s–1升温20 ℃所需时间/s最终升温温度/℃前100 s降温速率/(℃·s–1降温20 ℃所需时间/s最终降温温度/℃
Pyromark 2 500 涂层(20 μm)0.2338034.80.2345737.772.5
锰基热化学涂层(20 μm)0.16914131.00.16518933.764.7
锰基热化学涂层(100 μm)0.09422621.60.07730723.545.1
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平抑太阳能波动的高温吸热器锰基热化学涂层性能优化
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张添 1 , 刘静 2 , 孙田津 3 , 石丽萍 3 , 胡锐 3 , 帅威 1 , 何艺彬 1 , 祝培旺 1, 4 , 肖刚 1, 4
热力发电 | 热能科学研究 2026,55(1): 113-121
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热力发电 |热能科学研究 2026 , 55 (1) : 113 -121
平抑太阳能波动的高温吸热器锰基热化学涂层性能优化
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张添1 , 刘静2, 孙田津3, 石丽萍3, 胡锐3, 帅威1, 何艺彬1, 祝培旺1, 4, 肖刚1, 4
作者信息
  • 1.浙江大学能源高效清洁利用全国重点实验室,浙江 杭州 310027
  • 2.中国石油新疆油田分公司采油工艺研究院,新疆 克拉玛依 834000
  • 3.杭州华源前线能源设备有限公司,浙江 杭州 310030
  • 4.浙江大学青山湖能源研究基地,浙江 杭州 311300
通讯作者:
肖刚(1979),男,博士,教授,主要研究方向为太阳能热发电、热化学储热、布雷顿循环、多能互补技术,
作者简介:

张添(1998),男,硕士,主要研究方向为热化学防护涂层,

Performance optimization of Mn-based thermochemical coating for high-temperature receivers to dampen solar irradiance fluctuations
Tian ZHANG1 , Jing LIU2, Tianjin SUN3, Liping SHI3, Rui HU3, Wei SHUAI1, Yibin HE1, Peiwang ZHU1, 4, Gang XIAO1, 4
Affiliations
  • 1.State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China
  • 2.Oil Production Technology Research Institute, PetroChina Xinjiang Company, Kelamayi 834000, China
  • 3.Hangzhou Runpaq Energy Equipment Co., Ltd., Hangzhou 310030, China
  • 4.Qingshanhu Energy Research Center, Zhejiang Univeristy, Hangzhou 311300, China
出版时间: 2026-01-25 doi: 10.19666/j.rlfd.202503041
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塔式光热布雷顿循环发电系统的布置灵活,其吸热器工作温度较高,太阳能波动容易造成吸热器材料热疲劳或表面超温,亟需探索平抑吸热器温度波动的有效途径。开发了一种基于可逆氧化还原反应的锰基热化学热防护涂层,当太阳辐射增强且温度超过978 ℃时,涂层材料发生还原吸热反应,降低升温速率;当太阳辐射减弱且温度低于878 ℃时,发生氧化放热反应,减缓降温速率,进而平抑吸热器表面温度波动。研究表明:涂层材料与黏结剂的质量比为4:3时附着力可达国家标准的最高级,太阳光加权平均吸收率达到94.93%;在950 ℃恒温老化500 h、冷热交变老化100次循环以及氧化还原反应试验200次循环后,涂层加权平均吸收率仅分别衰减0.82百分点、0.98百分点和2.61百分点,且附着力保持在最高级;在±9.7 kW/m2的聚光辐射能流突变条件下,前100 s升温和降温速率分别降低59.66%和67.09%,升温和降温20 ℃所需的时间分别延长182.50%和438.60%。锰基热化学涂层表现出优秀的抗老化性能,并能有效平抑吸热器的温度波动,在塔式光热布雷顿循环系统中具有广阔的应用前景。

热化学材料  /  涂层  /  太阳能吸热器  /  热防护

The Brayton cycle-based tower solar thermal power system features a flexible layout and operates at high receiver temperatures. However, fluctuations in solar irradiance can lead to thermal fatigue of receiver materials or excessive surface temperatures, necessitating effective strategies to mitigate temperature fluctuations. This study develops a manganese-based thermochemical thermal protection coating utilizing a reversible redox reaction. When solar radiation intensifies and the temperature exceeds 978 ℃, the coating undergoes a reduction endothermic reaction, reducing the heating rate. Conversely, when solar radiation decreases and the temperature drops below 878 ℃, an oxidation exothermic reaction occurs, slowing the cooling rate, thereby stabilizing receiver surface temperature fluctuations. Experimental results indicate that when the mass ratio of the coating material to the binder is 4:3, the adhesion strength reaches the highest national standard level, and the solar weighed average absorptivity achieves 94.93%. After undergoing 500 hours of thermal aging at 950 ℃, 100 cycles of thermal cycling, and 200 cycles of redox reaction tests, the coating’s weighed average absorptivity decreased by only 0.82, 0.98, and 2.61 percentage points, respectively, while maintaining the highest adhesion strength. Under a sudden change in concentrated solar radiation flux of ±9.7 kW/m², the heating and cooling rates in the first 100 seconds were reduced by 59.66% and 67.09%, respectively. Additionally, the time required for a 20 ℃ increase and decrease was extended by 182.50% and 438.60%, respectively. The manganese-based thermochemical coating demonstrates excellent aging resistance and effectively suppresses absorber temperature fluctuations, making it highly promising for applications in Brayton cycle-based tower solar thermal power systems.

thermochemical material  /  coating  /  solar receiver  /  thermal protection
张添, 刘静, 孙田津, 石丽萍, 胡锐, 帅威, 何艺彬, 祝培旺, 肖刚. 平抑太阳能波动的高温吸热器锰基热化学涂层性能优化. 热力发电, 2026 , 55 (1) : 113 -121 . DOI: 10.19666/j.rlfd.202503041
Tian ZHANG, Jing LIU, Tianjin SUN, Liping SHI, Rui HU, Wei SHUAI, Yibin HE, Peiwang ZHU, Gang XIAO. Performance optimization of Mn-based thermochemical coating for high-temperature receivers to dampen solar irradiance fluctuations[J]. Thermal Power Generation, 2026 , 55 (1) : 113 -121 . DOI: 10.19666/j.rlfd.202503041
太阳能热发电通过吸热器吸收聚光太阳能产生高温热能,并将其转化为电能[1-3]。太阳能热发电可耦合储热系统,出力稳定,是一种稳定高效的可再生能源利用技术[4-6]。塔式太阳能布雷顿循环发电系统的布置灵活,非常适合热电联供,但其工作温度高,太阳能波动容易造成吸热器热疲劳或超温[7-8]。吸热器作为塔式光热系统的核心部件,直接影响发电效率和度电成本,因此亟需探索平抑温度波动的有效途径[9-10]
李军等[11]研究了基于图像分析的天空云层运动预测特性,并尝试在云遮挡发生前后调整镜场聚焦状态以维持吸热器表面温度的稳定。冯蕾等[12]研究了云遮挡时吸热器表面的温度下降速率。郭磊等[13]提出在云遮挡时采用吸热器保温隔热罩覆盖吸热器降低吸热器表面的降温速率。这些方法均需要人工干预,且运维复杂。基于储热材料的热化学防护涂层可通过自发热化学反应平抑吸热器表面温度波动。Portilla-nieto等人[14]采用氧化钴储热材料制成热障涂层可有效缓解热冲击,且经历15次反应循环后仍保持87%的反应活性。Yuan等人[15]利用钙钛矿储热材料开发热防护涂层,有效降低熔融盐吸热器在太阳辐射波动条件下的温度变化幅度。然而目前开发的涂层材料防护温度普遍在600 ℃左右,难以满足更高温度吸热器的热防护需求。
另一方面,涂层附着力和太阳光吸收率是决定热化学涂层性能的关键指标。周志伟[16]的仿真计算表明,吸热器热效率与涂层吸收率呈正相关关系。Boubault等人[17]研究发现,较高的涂层吸收率和较低的老化速率可有效降低光热发电成本。Torres等人[18]研究了在云遮条件下非线性温度交变老化对涂层吸收率的影响,指出快速降温后的保温过程是导致涂层开裂的主要因素。Noc等人[19]分析了长期在等温条件下的老化对涂层性能的影响,发现基材表面形成的氧化层是涂层性能衰减的主要原因。Sahar等人[20]通过长期高温老化实验探究了涂层在高温条件下的老化规律和老化机理。锰基金属氧化物(Mn2O3/Mn3O4)作为热化学储热材料,具有成本低廉、安全无毒、反应温区广等优点。研究表明,掺杂摩尔分数20%铁的锰基复合金属氧化物展现出良好的可逆性和循环稳定性,其还原反应温度可达900 ℃以上,是理想的高温热化学防护涂层原料[21]。针对塔式光热布雷顿循环系统的应用需求及太阳能波动特性,亟需开发适用于高温吸热器的低成本锰基热化学涂层材料,并对其性能进行优化研究。
锰基热化学涂层结构及工作原理如图1所示。当太阳辐射增强且温度超过978 ℃时,锰基复合氧化物发生还原吸热反应,降低吸热器表面升温速率;当太阳辐射减弱且温度低于878 ℃时,发生氧化放热反应,减缓降温速率,进而平抑吸热器的温度波动[21]。该氧化还原反应可表示为:
6(Mn0.8Fe0.2)2O34(Mn0.8Fe0.2)3O4+O2
式中:(Mn0.8Fe0.22O3为高价态锰基复合氧化物,(Mn0.8Fe0.23O4为低价态锰基复合氧化物的化学式表达。实际产物为MnFe2O4核与Mn2.7Fe0.3O4壳层的复杂结构[22]
该氧化还原反应在发生过程中伴随一定的热量吸收或释放,而热化学成分自身温度始终保持不变,有助于有效缓冲吸热器的温度波动,从而减缓吸热器材料的热疲劳,提升其热安全性,并延长使用寿命[23]
锰基热化学涂层的制备过程主要可以分为基材预处理、锰基粉末材料制备和涂层制备3个部分。
涂层基材采用Inconel 625镍基合金,其中板材尺寸为30 mm×30 mm×2 mm,管材为外径27 mm、壁厚1.5 mm、长度150 mm。基材首先通过四氯乙烯进行化学清洗,然后置入80 ℃烘箱内干燥,再用粒径为18 μm的砂纸打磨基材表面,以获得均匀的轻度粗糙表面,将打磨好的基材浸入无水乙醇中超声波清洗10 min,最后再次置入80 ℃烘箱内至完全干燥。
锰铁复合金属氧化物采用溶胶-凝胶法制备[22],所得金属氧化物经球磨机研磨后得到复合金属氧化物粉末。
涂层黏结剂采用枞阳县三金颜料有限公司生产的环氧改性有机硅树脂SJ-804,并按照一定质量比将复合金属氧化物粉末与黏结剂混合,经球磨机湿磨20 min充分分散,得到均匀的涂料浊液。将涂料浊液经孔径为75 μm的纱布过滤后倒入喷枪内,在275 kPa的压力下,保持喷枪喷口与基材垂直距离10~15 cm,以均匀横扫方式进行喷涂。喷涂完成后,样品在通风橱中自然干燥24 h,之后置于马弗炉中进行三段式热处理以去除涂层样品中的有机成分(250 ℃加热30 min,400 ℃加热40 min,700 ℃加热20 min),最后缓慢冷却至室温后完成涂层制备。
利用扫描电子显微镜(SEM)观测涂层的微观形貌。涂层附着力测试依据《色漆和清漆划格试验》(GB/T 9286—2021),采用六刃刀具对涂层进行划格切割评估[24]。涂层光谱吸收率根据ASTM E903-12进行测试,采用由高性能准直连续光源和积分球系统组成的RF-5000高精度光谱仪(图2a)),光谱间隔为0.2 nm,光源入射角度为8°,测量涂层样品300~2 500 nm范围内的光谱反射率[25],涂层的加权平均吸收率可由式(2)计算。
αws=λ1λ2αs(λ)Gs,λ(λ)dλλ1λ2Gs,λ(λ)dλ
式中:αws为加权平均吸收率,%;αsλ)为光谱吸收率,%;Gs,λλ)为参考太阳光谱辐射强度,W/(m2·nm);λ1λ2分别为计算的起始和结束波长,nm。
根据ASTM G173-03的参考太阳光辐射强度数据,380~1 600 nm波段的太阳辐射总辐照度约为920 W/m2,占300~2 500 nm波段约962.6 W/m2总辐照度的95.6%[26]。锰基涂层在380~1 600 nm波段与300~2 500 nm波段的加权平均吸收率数据相对误差不超过0.5%,为简化计算,本文只计算380~1 600 nm波段的加权平均吸收率。
为模拟吸热器涂层在高温运行、日常启停以及太阳辐射波动工况下的性能,对涂层样品分别进行恒定高温老化、冷热交变老化及氧化还原反应循环实验。涂层老化实验采用可编程的马弗炉设备(图2b))。恒定高温老化温度设置为950 ℃,冷热交变老化温度设置为30~900 ℃,升降温速率设置为20 ℃/min,且在30、900 ℃各保温30 min。氧化还原反应循环使用热天平系统(图2c)),空气流量设置为2 m3/h,升降温速率设置为10 ℃/min,在750~1 050 ℃循环升降温,并在每个目标温度下保温30 min确保完全反应。通过天平重量变化计算涂层的反应转化率,如果涂层样品第1次还原和氧化的反应转化率为100%,则i次反应后的转化率为:
αi=m0mim0m1
式中:αi为第i次反应的转化率,%;m0为反应开始前样品质量,mg;m1为第1次反应结束时的样品质量,mg;mi为第i次反应结束时的样品质量,mg。
涂层热防护性能实验采用模拟灯系统进行测试(图2d)),系统包括14盏太阳能模拟灯,涂层样品,温度测量系统和数据记录器。对比样品包括20 μm厚的Pyromark 2 500涂层、20 μm厚的锰基涂层以及100 μm厚的锰基涂层。实验中,14盏模拟灯依次编号,选取1号模拟灯设定输出功率,其光斑中心处的能流密度经测量为9.7 kW/m2,在后续实验过程中保持1号模拟灯功率恒定。实验开始前,将K型热电偶焊接至吸热管上表面中心处,并连接至数据记录器。将涂层样品放置在1号模拟灯光斑中心处,开启2号—14号模拟灯并调整功率,使吸热管温度稳定在970 ℃,随后打开1号模拟灯,使能流密度突增,记录样品的升温曲线。升温曲线记录完成后,降低2号—14号模拟灯功率,使样品温度重新稳定在890 ℃,然后关闭1号模拟灯,使能流突降,记录样品降温曲线。
涂层配方中锰基复合金属氧化物和黏结剂的混合比例直接影响涂层中热化学成分的含量,从而决定涂层的热防护性能。本文按照锰基氧化物与黏结剂的质量比4:1、2:1、4:3和1:1 4种比例分别制备了厚度为100 μm的涂层样品,并进行了性能对比分析。在4:1比例下,由于黏结剂含量较低,混合浊液黏度过高,导致喷涂过程中雾化效果不佳,涂层表面出现明显的结块现象。相比之下,按照质量比2:1、4:3和1:1制备出来的涂层外观较为平整,但随着黏结剂的比例增高,涂层的黑度逐渐降低,热处理后加权平均吸收率依次为95.37%、94.93%和93.26%。
在后续的老化实验中,锰基氧化物与黏结剂质量比2:1的涂层出现了早期脱落现象,推测是由于黏结剂含量不足,导致老化后附着力迅速下降。综合对比,4:3比例的涂层配方能同时实现较高的加权平均吸收率和附着力,因此后续实验均基于锰基氧化物与黏结剂质量比4:3涂层样品进行。涂层样品热处理前的涂层表面光滑,呈黑色镜面反射状;热处理后,涂层变为哑光黑色,表面略微粗糙,热处理后加权平均吸收率较热处理前平均提升约5.81百分点。
经过500 h恒定高温老化、100次冷热交变老化和300次氧化还原反应循环后的100 μm涂层外观如图3所示。涂层整体完整无脱落,但黑度均有一定程度的降低,表明实验后涂层的加权平均吸收率均有一定程度的降低。划格实验结果显示,所有实验后的涂层均无粉化或剥落现象,附着力等级均达到最高级0级。
热处理前后的涂层表面SEM形貌如图4a)、图4b)所示。热处理前黏结剂均匀包裹锰铁颗粒,表面略微粗糙,热处理后黏结剂的有机成分在高温下热解,内部颗粒裸露,形成涂层表面的孔隙光陷阱结构,此时锰铁颗粒的粒径主要分布在0.1~0.4 μm。经过实验后的涂层SEM形貌如图4c)—图4e),锰铁颗粒粒径均有所增长,冷热交变老化后粒径增长至0.6 μm左右,恒定高温老化后粒径进一步增长至0.8 μm,氧化还原反应后粒径增长尤为明显,部分颗粒达到1.0 μm。此外,涂层的孔隙大小随颗粒增长而扩大,颗粒间界限更为清晰。利用ImageJ软件进行图像处理分析,计算得出涂层的表面孔隙率约为30%(图4f))。
涂层老化实验结果如图5所示。经过500 h的高温老化后,涂层的加权平均吸收率下降了0.82百分点,且加权平均吸收率随高温老化的时间增加而呈现近似线性下降的趋势。从光谱吸收率分析可见,在300~750 nm波段内涂层光谱吸收率衰减不明显,750~2 500 nm内光谱吸收率均存在一定程度的衰减,其中750~1 100 nm和1 800~2 500 nm的波段内的衰减尤为显著。
冷热交变老化的吸收率结果见图5c)、图5d)。涂层在前20个循环内加权平均吸收率快速下降,然后随着循环次数的增加下降速率显著减缓;100个循环后,加权平均吸收率共下降0.98百分点。从光谱吸收率来看,衰减主要集中在300~1 300 nm和1 750~2 500 nm两段波段内,其中300~1 000 nm的衰减更为显著,1 300~1 750 nm波段的光谱吸收率衰减不明显。
涂层的反应转化率和加权平均吸收率随氧化还原反应次数的衰减结果如图6所示。涂层在前20次循环内反应转化率迅速下降,还原反应转化率和氧化反应转化率分别降低至89.35%和89.17%;之后反应转化率衰减速率显著减缓,100次循环后反应转化率趋于稳定,还原反应和氧化反应转化率分别维持在86.88%和84.42%左右。涂层加权平均吸收率的衰减则主要体现在前5次循环内,加权平均吸收率快速下降1.54百分点,可能是由于锰铁复合金属氧化物颗粒在反应过程中发生体积变化,改变了涂层的均匀分布和多孔结构,导致加权平均吸收率有所衰减;5次循环后涂层加权平均吸收率衰减速率逐渐降低,40次循环后呈现线性缓慢衰减趋势,200次循环后涂层仍保有92.32%的加权平均吸收率。
根据老化实验和氧化还原反应循环实验的数据可以拟合得到涂层在不同实验条件下的加权平均吸收率衰减曲线。式(4)—式(6)分别为恒定高温老化实验、冷热交变老化实验和氧化还原反应循环实验下拟合的加权平均吸收率衰减曲线,3条拟合衰减曲线的标准差RSME依次为0.034 47、0.028 85和0.055 77。
αcon=1.591×103h+94.91
αcyc=0.678×exp(0.1845Ccyc)+94.24×exp(3.423×105Ccyc)
αrea=2.242×exp(0.2407Crea)+92.69×exp(2.114×105Crea)
式中:h为恒定高温老化下高温的累计持续时间,h;Ccyc为冷热交变老化下涂层累计经历的交变循环次数;Crea为氧化还原反应试验下累计经历的完全反应循环次数。
综合分析可知,氧化还原反应次数对涂层加权平均吸收率的衰减影响最大,尤其是在前20次循环中,加权平均吸收率迅速下降2.35百分点;此后的循环反应对加权平均吸收率的影响接近线性,并略高于950 ℃下恒定高温老化的衰减速率,因此可以认为20次循环后的加权平均吸收率衰减主要由高温老化引起。恒定高温老化和冷热交变老化对涂层性能也存在影响,恒定高温老化体现在800~1 600 nm波段,且加权平均吸收率随老化时间线性衰减,冷热交变老化则体现在380~1 000 nm波段,加权平均吸收率随循环次数先快速衰减再趋于平缓。结合以上衰减情况,并以高温空气吸热器每天仅进行1次完全升降温操作,工作温度维持8 h为例,且涂层已经历20次储/放热反应循环后,可预测涂层的加权平均吸收率随吸热器工作天数的衰减规律:
αpre=0.678×exp(0.1845D)+94.24×exp(3.423×105D)1.989×104D2.338
式中:αpre为预测加权平均吸收率,%;D为吸热器工作天数。
以青海省海西蒙古族藏族自治州德令哈地区为例,根据国家可再生能源实验室(NREL)的气象数据,2020年全年太阳辐射强度DNI高于700 W/m2的时段共1 795 h,约等于电站正常工作224天[27]。根据式(7)的计算,锰基热防护涂层的加权平均吸收率下降到90%需要561天,即电站正常工作2.5年,加权平均吸收率下降至85%则需要2 084天,约9.3年。
当能流密度突然增强了9.7 kW/m2时,吸热管上壁面的温度变化如图7所示。从整体上看,吸热管上壁面的温度变化呈现初始快速升高,后逐渐减慢并趋于稳定的规律。涂覆Pyromark 2 500涂层的吸热管温度在前100 s从970.2 ℃上升到993.5 ℃,平均升温速率0.233 ℃/s;100~280 s内温度缓慢升高至1 004.4 ℃;280 s后吸热管温度基本稳定在1 005.0 ℃左右。涂覆20 μm锰基热防护涂层的吸热管前100 s温度从970.8 ℃上升至987.7 ℃,平均升温速率0.169 ℃/s;后续缓慢升温并在280 s后稳定在1 001.2 ℃左右。由于锰基涂层发生还原反应,升温速率有所降低,但由于涂层较薄,储热容量较低,锰基金属氧化物发生还原反应的持续时间较短,因此热防护效果不明显。将涂层厚度增加到100 μm后,涂层储热容量大幅提高,在相同的温度下同时有更多的锰基复合氧化物分子参与还原反应,单位时间内吸收的热量更多,传导到吸热管上的热量则越少,热防护效果越显著。涂覆100 μm锰基热防护涂层的吸热管前100 s的平均升温速率减小至0.094 ℃/s,由于锰基复合金属氧化物持续发生还原反应,吸热管温度在70~120 s内出现1个小的平台,稳定在980.1 ℃左右;120 s后锰基金属氧化物几乎反应完全,吸热管温度继续缓慢上升并最终稳定在992.1 ℃。
能流密度突然减弱了9.7 kW/m2时,吸热管上壁面温度变化如图8所示。整体变化仍符合先快速变化后趋于稳定的趋势。由于能流密度突然减弱后吸热管仅靠空气自然对流散热,换热速度较慢,吸热管冷却至温度稳定所需的时间均长于能流密度突增的情况。涂覆Pyromark 2 500涂层的吸热管在前100 s降温23.4 ℃,平均降温速率0.234 ℃/s,最终稳定温度约为852.0 ℃。与能流密度突增情况相似,20 μm锰基热化学涂层的热防护效果不明显,吸热管前100 s平均降温速率降低至0.165 ℃/s,440 s后稳定在856.3 ℃左右。涂覆100 μm锰基热化学涂层的吸热管前100 s降温速率仅为0.077 ℃/s,温度下降至879.1 ℃左右出现温度平台,锰基复合金属氧化物发生氧化反应,持续约120 s,反应速率低于能流密度突增情况,最终温度为866.5 ℃。
表1列出了涂层热防护性能测试的结果。对比可知,厚度为100 μm的锰基涂层热防护效果显著,相比于Pyromark 2 500涂层,可将吸热管前100 s升/降温速率分别减少59.66%和67.09%,升/降温20 ℃所需的时间分别延长182.50%和438.60%,并将总和波动温差由72.5 ℃减小至45.1 ℃,波动范围减小37.79%。
本文开展了锰基复合金属氧化物热化学储热材料制备高温吸热器涂层的工艺方法研究,探讨了涂层配方性能和优化方法,主要结论如下。
1)锰基复合金属氧化物涂层配方中,涂层材料与黏结剂的质量比为4:3时,涂层展现出优异的加权平均吸收率和附着力。100 μm厚的涂层在老化前加权平均吸收率可达94.93%,经过500 h恒定高温老化、100次冷热交变老化和200次氧化还原反应循环后,加权平均吸收率分别仅下降0.82百分点、0.98百分点和2.61百分点,同时附着力仍保持在最高等级。
2)锰基热防护涂层的性能衰退主要受高温老化、冷热交变老化和氧化还原反应循环的影响,其中氧化还原反应对涂层性能的影响最为显著,高温老化导致涂层在750~2 500 nm波段内的光谱吸收率衰退,冷热交变老化则集中在300~1 300 nm和1 750~2 500 nm波段。
3)厚度为100 μm的锰基涂层展现出显著的热防护效果。与Pyromark 2 500涂层相比,在±9.7 kW/m²的辐射能流变化下,锰基涂层在前100 s的升温和降温速率分别减少59.66%和67.09%,升温和降温20 ℃所需的时间分别延长182.50%和438.60%。
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2026年第55卷第1期
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doi: 10.19666/j.rlfd.202503041
  • 接收时间:2025-03-15
  • 首发时间:2026-06-10
  • 出版时间:2026-01-25
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  • 收稿日期:2025-03-15
  • 修回日期:2025-04-07
  • 录用日期:2025-04-17
基金
Inner Mongolia Autonomous Region “Unveiling the List and Appointing Leaders” Project(2024JBGS0026)
内蒙古自治区“揭榜挂帅”项目(2024JBGS0026)
National Science Fund for Distinguished Young Scholars(52325605)
国家杰出青年基金项目(52325605)
作者信息
    1.浙江大学能源高效清洁利用全国重点实验室,浙江 杭州 310027
    2.中国石油新疆油田分公司采油工艺研究院,新疆 克拉玛依 834000
    3.杭州华源前线能源设备有限公司,浙江 杭州 310030
    4.浙江大学青山湖能源研究基地,浙江 杭州 311300

通讯作者:

肖刚(1979),男,博士,教授,主要研究方向为太阳能热发电、热化学储热、布雷顿循环、多能互补技术,
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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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