Article(id=1236611786091319756, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1236611783876727231, articleNumber=null, orderNo=null, doi=10.19666/j.rlfd.202412265, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1735228800000, receivedDateStr=2024-12-27, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1772760824940, onlineDateStr=2026-03-06, pubDate=1753372800000, pubDateStr=2025-07-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1772760824940, onlineIssueDateStr=2026-03-06, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1772760824940, creator=13701087609, updateTime=1772760824940, updator=13701087609, issue=Issue{id=1236611783876727231, tenantId=1146029695717560320, journalId=1210938733613449225, year='2025', volume='54', issue='7', pageStart='1', pageEnd='159', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=0, createTime=1772760824412, creator=13701087609, updateTime=1772761154835, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1236613169855123924, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1236611783876727231, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1236613169855123925, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1236611783876727231, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=127, endPage=134, ext={EN=ArticleExt(id=1236611786405892558, articleId=1236611786091319756, tenantId=1146029695717560320, journalId=1210938733613449225, language=EN, title=Performance enhancement for thermal conductivity and thermal energy storage of sludge-incinerated slag/KNO3 phase change composites, columnId=1211002409397129992, journalTitle=Thermal Power Generation, columnName=Power generation technology forum, runingTitle=null, highlight=null, articleAbstract=

The industrial production and urban residents’ lives have led to a large amount of wastewater and sludge, and the landfilling of sludge has caused severe ecological damage. To facilitate the large-scale disposal of municipal sludge, transform waste into valuable resources, and prepare low-carbon, low-cost thermal storage materials, an idea is innovatively proposed, in which the silicon carbide, boron nitride, and expanded graphite is added as thermal conductivity enhancers to enhance the thermal conductivity of sludge incineration ash/potassium nitrate composite phase change thermal storage materials (50% sludge incineration ash+50% potassium nitrate). The composite phase change thermal storage materials were prepared, and the effects of thermal conductivity enhancers on thermal performance of these materials were investigated. The results indicate that, the expanded graphite is not suitable as a thermal conductivity enhancer for sludge incineration ash/potassium nitrate composite phase change thermal storage materials. The addition of a thermal conductivity enhancer with a mass fraction of 2% is optimal for improving melting latent heat, with boron nitride performing better than silicon carbide. The samples with 2% boron nitride shows the most significant increase in thermal conductivity, rising by 65%, 93%, 117%, and 203% compared with samples SC3 (without thermal conductivity enhancers) at temperatures of 100 ℃ to 400 ℃, respectively. After undergoing 1 000 cycles of heating/cooling, the samples with 2% boron nitride have a latent heat of 35.29 J/g and a thermal storage density of 292.1 J/g, while the samples with 2% silicon carbide have a latent heat of 40.90 J/g and a thermal storage density of 334.9 J/g. The heat transfer rates for the samples with 2% silicon carbide and 2% boron nitride are 0.16 ℃/s and 0.17 ℃/s, respectively. This preliminary evidence demonstrates the feasibility of using silicon carbide and boron nitride as thermal conductivity enhancers for sludge incineration ash/potassium nitrate composite phase change thermal storage materials.

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工业生产及城市居民生活产生大量污水污泥,污泥的填埋严重破坏生态环境。为大规模消纳市政污泥,变废为宝,将其制备成低碳低成本储热材料,提出添加碳化硅、氮化硼和膨胀石墨为导热增强剂,以强化污泥焚烧灰渣/硝酸钾复合相变储热材料(50%污泥焚烧炉渣+50%硝酸钾)导热性能的思路。通过制备复合相变储热材料,研究导热增强剂对复合相变储热材料热性能的影响。结果表明:膨胀石墨不适合作为污泥焚烧灰渣/硝酸钾复合相变储热材料的导热增强剂;添加质量分数为2%的导热增强剂在熔化潜热改善方面是最优的,且添加氮化硼优于添加碳化硅;添加质量分数为2%氮化硼的样品的导热系数提升最为显著,在100~400 ℃时分别比样品SC3(不加导热增强剂)升高65%、93%、117%、203%;经历1 000次加热/冷却循环后,氮化硼质量分数为2%的样品潜热为35.29 J/g,储热密度为292.1 J/g,碳化硅质量分数为2%的样品潜热为40.90 J/g,储热密度为334.9 J/g;碳化硅质量分数为2%的样品、氮化硼质量分数为2%的样品传热速率分别为0.16、0.17 ℃/s。研究结果初步证明碳化硅和氮化硼作为污泥焚烧灰渣/硝酸钾复合相变储热材料的导热增强剂是可行的。

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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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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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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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journalId=1210938733613449225, articleId=1236611786091319756, language=CN, label=图10, caption=循环前样品放热过程中的温度变化, figureFileSmall=FubiYGHR8VNN8nXR82zXlQ==, figureFileBig=2nYioZsVgX8dO76n84Lg8A==, tableContent=null), ArticleFig(id=1236611796795183128, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236611786091319756, language=EN, label=Tab.1, caption=

Compositions of the composite phase change thermal storage material

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序号样品编号导热增强剂炉渣质量分数/%硝酸钾质量分数/%导热增强剂质量分数/%
1DA1SiC49501
2DA2SiC48502
3DA3SiC47503
4DA4SiC46504
5DA5SiC45505
6DB1BN49501
7DB2BN48502
8DB3BN47503
9DB4BN46504
10DB5BN45505
11DC1EG49501
12DC2EG48502
13DC3EG47503
14DC4EG46504
15DC5EG45505
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复合相变储热材料样品配比

, figureFileSmall=null, figureFileBig=null, tableContent=
序号样品编号导热增强剂炉渣质量分数/%硝酸钾质量分数/%导热增强剂质量分数/%
1DA1SiC49501
2DA2SiC48502
3DA3SiC47503
4DA4SiC46504
5DA5SiC45505
6DB1BN49501
7DB2BN48502
8DB3BN47503
9DB4BN46504
10DB5BN45505
11DC1EG49501
12DC2EG48502
13DC3EG47503
14DC4EG46504
15DC5EG45505
), ArticleFig(id=1236611797038452774, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236611786091319756, language=EN, label=Tab.2, caption=

Phase transition characteristics of the samples

, figureFileSmall=null, figureFileBig=null, tableContent=
DA1DA2DA3DB1DB2DB3
熔点/℃327.4327.8328.9327.3327.5327.7
潜热/(J·g–1)41.3344.1943.4439.6545.2242.06
), ArticleFig(id=1236611797134921774, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236611786091319756, language=CN, label=表2, caption=

样品的相变特性

, figureFileSmall=null, figureFileBig=null, tableContent=
DA1DA2DA3DB1DB2DB3
熔点/℃327.4327.8328.9327.3327.5327.7
潜热/(J·g–1)41.3344.1943.4439.6545.2242.06
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污泥焚烧灰渣/硝酸钾复合相变材料传热储热性能强化
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熊亚选 1 , 高梓靖 1 , 张艾桐露 1 , 钱向瑶 2 , 宋超宇 1 , 何苗 1 , 吴玉庭 3 , 丁玉龙 4
热力发电 | 发电技术论坛 2025,54(7): 127-134
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热力发电 | 发电技术论坛 2025, 54(7): 127-134
污泥焚烧灰渣/硝酸钾复合相变材料传热储热性能强化
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熊亚选1 , 高梓靖1, 张艾桐露1, 钱向瑶2, 宋超宇1, 何苗1, 吴玉庭3, 丁玉龙4
作者信息
  • 1.北京建筑大学未来新材料研究院,北京 100044
  • 2.北京京能热力发展有限公司通州分公司,北京 101100
  • 3.北京工业大学传热强化与过程节能教育部重点实验室,北京 100124
  • 4.英国伯明翰大学伯明翰储能中心,伯明翰 B15 2TT
  • 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,

Performance enhancement for thermal conductivity and thermal energy storage of sludge-incinerated slag/KNO3 phase change composites
Yaxuan XIONG1 , Zijing GAO1, Aitonglu ZHANG1, Xiangyao QIAN2, Chaoyu SONG1, Miao HE1, Yuting WU3, Yulong DING4
Affiliations
  • 1.Institute of Advanced Materials, Beijing University of Civil Engineering and Architecture, Beijing 100044, China
  • 2.Beijing Jingneng Thermal Power Development Co., Ltd., Tongzhou Branch, Beijing 101100, China
  • 3.Key Laboratory of Enhanced Heat Transfer and Energy Conservation, Beijing Municipality, Beijing University of Technology, Beijing 100124, China
  • 4.Birmingham Center for Energy Storage, University of Birmingham, Birmingham B15 2TT, UK
出版时间: 2025-07-25 doi: 10.19666/j.rlfd.202412265
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工业生产及城市居民生活产生大量污水污泥,污泥的填埋严重破坏生态环境。为大规模消纳市政污泥,变废为宝,将其制备成低碳低成本储热材料,提出添加碳化硅、氮化硼和膨胀石墨为导热增强剂,以强化污泥焚烧灰渣/硝酸钾复合相变储热材料(50%污泥焚烧炉渣+50%硝酸钾)导热性能的思路。通过制备复合相变储热材料,研究导热增强剂对复合相变储热材料热性能的影响。结果表明:膨胀石墨不适合作为污泥焚烧灰渣/硝酸钾复合相变储热材料的导热增强剂;添加质量分数为2%的导热增强剂在熔化潜热改善方面是最优的,且添加氮化硼优于添加碳化硅;添加质量分数为2%氮化硼的样品的导热系数提升最为显著,在100~400 ℃时分别比样品SC3(不加导热增强剂)升高65%、93%、117%、203%;经历1 000次加热/冷却循环后,氮化硼质量分数为2%的样品潜热为35.29 J/g,储热密度为292.1 J/g,碳化硅质量分数为2%的样品潜热为40.90 J/g,储热密度为334.9 J/g;碳化硅质量分数为2%的样品、氮化硼质量分数为2%的样品传热速率分别为0.16、0.17 ℃/s。研究结果初步证明碳化硅和氮化硼作为污泥焚烧灰渣/硝酸钾复合相变储热材料的导热增强剂是可行的。

污泥焚烧灰渣  /  硝酸钾  /  复合相变储热材料  /  导热增强剂  /  储热性能  /  热稳定性

The industrial production and urban residents’ lives have led to a large amount of wastewater and sludge, and the landfilling of sludge has caused severe ecological damage. To facilitate the large-scale disposal of municipal sludge, transform waste into valuable resources, and prepare low-carbon, low-cost thermal storage materials, an idea is innovatively proposed, in which the silicon carbide, boron nitride, and expanded graphite is added as thermal conductivity enhancers to enhance the thermal conductivity of sludge incineration ash/potassium nitrate composite phase change thermal storage materials (50% sludge incineration ash+50% potassium nitrate). The composite phase change thermal storage materials were prepared, and the effects of thermal conductivity enhancers on thermal performance of these materials were investigated. The results indicate that, the expanded graphite is not suitable as a thermal conductivity enhancer for sludge incineration ash/potassium nitrate composite phase change thermal storage materials. The addition of a thermal conductivity enhancer with a mass fraction of 2% is optimal for improving melting latent heat, with boron nitride performing better than silicon carbide. The samples with 2% boron nitride shows the most significant increase in thermal conductivity, rising by 65%, 93%, 117%, and 203% compared with samples SC3 (without thermal conductivity enhancers) at temperatures of 100 ℃ to 400 ℃, respectively. After undergoing 1 000 cycles of heating/cooling, the samples with 2% boron nitride have a latent heat of 35.29 J/g and a thermal storage density of 292.1 J/g, while the samples with 2% silicon carbide have a latent heat of 40.90 J/g and a thermal storage density of 334.9 J/g. The heat transfer rates for the samples with 2% silicon carbide and 2% boron nitride are 0.16 ℃/s and 0.17 ℃/s, respectively. This preliminary evidence demonstrates the feasibility of using silicon carbide and boron nitride as thermal conductivity enhancers for sludge incineration ash/potassium nitrate composite phase change thermal storage materials.

sludge-incinerated ash and slag  /  potassium nitrate  /  composite phase change thermal storage material  /  thermal conductivity enhancer  /  thermal energy storage performance  /  thermal stability
熊亚选, 高梓靖, 张艾桐露, 钱向瑶, 宋超宇, 何苗, 吴玉庭, 丁玉龙. 污泥焚烧灰渣/硝酸钾复合相变材料传热储热性能强化. 热力发电, 2025 , 54 (7) : 127 -134 . DOI: 10.19666/j.rlfd.202412265
Yaxuan XIONG, Zijing GAO, Aitonglu ZHANG, Xiangyao QIAN, Chaoyu SONG, Miao HE, Yuting WU, Yulong DING. Performance enhancement for thermal conductivity and thermal energy storage of sludge-incinerated slag/KNO3 phase change composites[J]. Thermal Power Generation, 2025 , 54 (7) : 127 -134 . DOI: 10.19666/j.rlfd.202412265
2020年我国提出的“双碳”目标使非化石能源利用和化石能源高效利用成为能源技术发展的关键方向。然而,可再生能源具有强波动性、周期性,工业余热和电网低谷电具有可持续性,使得能源供应与需求在时间和空间上极度不匹配,需要通过大规模能源存储技术和能源输配管网实现能源的大规模跨时间和空间的调配,达到非化石能源和化石能源的高效利用。其中,储热技术成本低,能够实现能源的大规模长时存储,是当前实现低成本储能、高效用能的主要储能技术[1]
储热技术主要分为显热储热、相变储热、热化学储热和复合相变储热技术[2]。其中,显热储热材料通常储热密度低,占地面积大,给工业过程带来了诸多不便。相变储热技术因其储热密度大,能高效存储能量等优势,在工业领域展现出巨大的应用潜力。然而,材料相变过程中存在易泄漏、相分离、腐蚀容器以及导热系数低等固有缺陷。热化学储热技术则仍处于实验室阶段[3]。对此问题,大量学者提出利用骨架材料封装相变储热材料达到填补缝隙防止材料泄漏的效果。根据目前的研究,可以作为骨架材料的有氧化镁、膨胀石墨、碳化硅、赤藓糖醇、高炉矿渣、膨胀蛭石等。复合相变储热技术在实施过程中,先是将相变材料与多孔骨架显热储热材料进行巧妙耦合。经过一系列工艺处理,成功制成定型复合相变储热材料。凭借这种独特的材料构造,不但避免了相变材料与容器直接接触,使得容器腐蚀问题得以解决,而且在很大程度上缓解了相变材料的相过冷和相分离现象,进而为高效储热技术的发展开辟了新方向。药晨华等[4]以兰炭灰为骨架材料,硝酸钠为相变材料制备复合相变储热材料,结果表明,在100~380 ℃范围内,兰炭灰与硝酸钠的最佳质量比为5:5,储热密度达到338.24 J/g。Liu等人[5]通过熔融浸渍法制备了Na2SO4/多孔莫来石复合相变储热材料,储热密度高于350 J/g。敖慈[6]以膨胀石墨(EG)为支撑填料,用相同方法制备了硬脂酸(SA)/EG复合相变材料。在EG质量分数为12%时,导热系数高达6.54 W/(m·K)。储热系统中,储热材料的导热性能决定着储/放热过程中热量存储和释放的速度。Xiong等人[7]创新性地选择了碳化物渣-钢渣的1:1混合物作为CO2封存的固碳材料,以碳封存的碳化物渣钢渣材料为骨架材料,制成碳封存碳化物渣-钢渣/NaNO3相变复合材料。表征了材料的固碳和储热性能。结果表明,样品的储热密度达到444.2 J/g,热导率为1.057 W/(m·K)。较低的导热系数会产生较高的热阻、较低的热能储存和释放效率,同样会制约储热材料的工程应用[8]
中高温热能储存(TES)系统的广泛应用可以实现建筑采暖和空调的高效运行,有助于提高建筑物的能源效率,减少对传统能源的依赖,促进建筑物碳中和目标的实现[9]。为了提升中高温储热系统的性能,高性能储热材料的研究和开发至关重要,这将直接影响系统的储热效率和能源利用率,因此,开发具有优异储热能力的材料已成为储热技术和清洁能源在建筑物中应用的重要研究方向。本文在团队前期研究污泥焚烧灰渣/硝酸钾复合相变储热材料工作[10]的基础上,针对优选的最优污泥焚烧灰渣/硝酸钾复配比,通过添加不同的导热增强剂(碳化硅、氮化硼、膨胀石墨),采用冷压烧结法[11]制备不同的污泥焚烧灰渣基复合相变储热材料,探索导热增强剂对该固废复合相变储热材料导热和储热性能的影响。
基于团队前期研究结果[10]实验所用碳化硅(SiC)、氮化硼(BN)和膨胀石墨(EG),检测纯度均不低于99%,上述材料细度均为75 μm(团队前期研究所用材料细度均为此规格),测试用的骨架材料和相变材料与文献[10]相同。本课题组前期工作已经获得污泥焚烧炉渣/硝酸钾复合相变储热材料的最佳配比50%污泥焚烧灰渣+50%硝酸钾(样品SC3)[10]。为研究导热增强剂对复合相变储热材料导热性能的强化效果,分别添加不同质量分数的碳化硅、氮化硼和膨胀石墨为导热增强剂,以改善污泥焚烧炉渣/硝酸钾复合相变储热材料的导热性能。实验制备的15种不同配比的复合相变储热材料的配比见表1
实验通过冷压烧结法制备污泥焚烧炉渣/硝酸钾复合相变储热材料,工艺流程如图1所示。具体操作步骤为:将一定量的污泥焚烧灰渣、硝酸钾、导热增强剂在干燥箱(202-3AB,天津市泰斯特仪器有限公司)中保持180 ℃干燥24 h以上;根据预设质量比,利用分析天平(ME104,梅特勒-托利多公司)分别对污泥焚烧炉渣、硝酸钾和导热增强剂粉末进行精确称量;利用行星球磨机(KE-2L,启东市宏宏仪器设备厂)将污泥焚烧炉渣、硝酸钾和导热增强剂粉末以200 r/min的转速球磨30 min,得到混合粉末;精确称取1.0 g复合粉末放入内径为13 mm的圆柱形模具中,在压力机(MSY-50,青岛孚润汽车保修设备有限公司)上对粉末施加54 MPa压力并保持该压力3 min,得到圆片形复合相变储热材料;利用空气气氛马弗炉(SX2-5-12A,苏州九联科技有限公司)以2 ℃/min的升温速率从室温加热至120 ℃,保持该温度1 h从而除去样品中残留的水分,然后设置马弗炉以2 ℃/min的升温速率从120 ℃加热至370 ℃,达到该温度后保温2 h,完成上述操作后关闭马弗炉,待复合圆柱体自然冷却至室温,最后保存在恒温180 ℃的干燥箱中以备后续实验使用。实验中每一种配比的复合相变储热材料制备3个样片,用于重复性验证测试。
图2为掺杂不同比例导热增强剂制备的污泥焚烧炉渣/硝酸钾复合相变储热材料的宏观形貌。由图2可以看出,样品DA1—DA5外形结构稳固,表面无明显裂纹。其中,样品DA1、DA2和DA3未出现相变材料明显泄漏情况,而样品DA4和DA5底部存在白色结晶物,是块体中相变材料在煅烧时泄漏所致。样品DB1—DB5同样表面结构稳定,均未观察到相变材料的明显泄漏。其中样品DB1、DB2和DB3形貌完好,而样品DB4和DB5呈现表皮鼓包现象。样品DC1—DC5整体结构均稳定,未出现裂纹及形变,但所有样品均出现不同程度的相变材料泄漏,其中样品DC4和DC5表面相变材料泄漏非常严重,这是因为膨胀石墨传热快,形成液相,而且与硝酸钾的相容性不好[12]。因此,膨胀石墨不适合作为污泥焚烧炉渣/硝酸钾复合相变储热材料的导热增强剂。
下文仅对样品DA1—DA3和样品DB1—DB3的储热、导热和热稳定性进行深入分析研究。
材料的储热性能由比热容和熔化潜热进行表征,即一定升/降温温差下单位质量材料的储热量。图3为使用同步热分析仪(STA 449F3,NETSCH)实验测得的样品DA1、DA2、DA3、DB1、DB2和DB3的热流曲线。
图3可以看出,所有样品的热流曲线均有2个峰,且各样品之间热流曲线存在明显的差异,热流曲线的左峰为相变材料(硝酸钾)固-固相变阶段,右峰为相变材料固-液相变阶段,这是硝酸钾的固有特性。导热增强剂的添加对污泥焚烧灰渣/硝酸钾复合相变储热材料的吸热过程产生了一定影响,且导热增强剂类型和添加量的不同对上述复合相变储热材料的显热阶段和相变阶段的吸热过程的影响是不同的。
使用差示扫描量热仪(DSC)测量每个样品的DSC曲线,找到样品吸热峰的起始点、峰值和终点温度来确定熔点,使用自带分析软件将峰面积转化为相变潜热。表2为样品DA1—DA3和样品DB1—DB3的熔点和潜热。由表2可以看出:添加不同类型和比例的导热增强剂后,样品的熔点波动较小,在1.5 ℃以内,但熔化潜热存在较大差异;添加质量分数2%的导热增强剂在熔化潜热改善方面表现最优,且添加BN优于添加SiC。适量的导热增强剂可以改善复合相变材料的微观结构,导热增强剂可能会填充在污泥焚烧灰渣的孔隙中,或者与硝酸钾形成更有序的界面,为硝酸钾的相转变提供更有利的条件;当导热增强剂添加量过高时,导热增强剂可能会干扰硝酸钾的结晶过程,使硝酸钾晶体的生长变得无序,从而影响其相转变的完整性和可逆性,导致潜热降低[13]
图4为样品DA1—DA3,样品DB1—DB3在100~400 ℃之间4个温度点时的比热容。由图4可以看出,添加导热增强剂的样品在每个温度点的比热容都得到提升,大多数样品(如DA1、DA2、DA3、DB2和DB3)的比热容值随着温度的升高逐渐增加,这与其材料内部结构的热激活或分子振动增强有关[14]。样品DB2(BN质量分数为2%)在各个温度点比热容的提升最为显著,在100~400 ℃时,样品DB2比热容分别比样品SC3提升55%、81%、103%、177%。可以看出,添加质量分数2%的导热增强剂在比热容改善方面表现最优,样品的比热容随导热增强剂质量分数的增加呈现先升高后降低的趋势。
导热系数决定着储热材料的传热性能,即储热材料储热放热过程中传热速率的快慢。实验采用激光闪射仪(LFA 427,德国耐驰仪器公司)测量样品的热扩散系数,测试了样品在100~400 ℃ 4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:为储热材料的导热系数,W/(m∙K);cp(T)为储热材料的比热容,(J/(g∙K)); α(T)为储热材料的热扩散率,mm2/s;ρ(T)为储热材料的密度,g/cm3
根据式(1)计算得到样品的导热系数。样品的热扩散率和导热系数如图5所示。
图5a)可以看出,在100 ~400 ℃范围内,随着温度的升高,所有样品的热扩散系数均呈现下降趋势。DB系列样品(添加BN)的热扩散率均大于样品SC3(未添加导热增强剂),DA系列样品(添加SiC)的热扩散率均小于样品SC3,且添加导热增强剂的2种样品随着导热增强剂质量分数的提高而呈现热扩散系数下降的趋势。样品温度为100 ℃时,添加SiC导热增强剂的样品中DA1(SiC质量分数为1%)的热扩散率最高,为0.701 mm2/s;添加BN导热增强剂的样品中DB1(BN质量分数为1%)的热扩散率最高,为0.923 mm2/s。样品温度为400 ℃时,添加SiC导热增强剂时样品DA1的热扩散率同样最高,为0.544 mm2/s;添加BN导热增强剂的样品DB1也同样最高,为0.699 mm2/s。
样品的导热系数与其密度、比热容及热扩散率密切相关。从图5b)可以看出,所有样品的导热系数在4个温度点均得到了提升,且DB2(BN质量分数为2%)在各个温度点比热容的提升最为显著。在100~400 ℃时样品SC3导热系数分别为1.22、1.02、0.90、0.64 W/(m∙K),样品DB2导热系数分别为2.01、1.97、1.95 、1.94 W/(m∙K),分别比样品SC3提高65%、93%、117%和203%。
当温度为300 ℃时,添加导热增强剂的样品,其导热系数相比于SC3均得到大幅提高。样品SC3的导热系数为0.90 W/(m∙K),样品DA1、DA2、DA3、DB1、DB2和DB3的导热系数分别为1.42、1.38、1.11、1.23、1.95和1.52 W/(m∙K),分别提高了58%、53%、23%、37%、117%和69%。其主要原因是,当下相变材料正处于接近液态的临界状态。此时,由于分子热运动加剧,相变材料分子间的距离被拉大,分子间的相互作用势能降低,分子的振动能与转动能在总能量占比中增大,宏观上表现为分子间振动与旋转更为剧烈[15]。导热增强剂的存在促使液态相变材料分子之间的碰撞频率显著增加,同时加快了分子的运动速度,使得单位时间内分子传递的能量增多,最终有效提升了材料的导热系数。
导热和储热强化显示,样品DA2和样品DB2的平均比热容和导热性能强化效果最佳。因此,仅分析样品DA2和DB2的热稳定性。
利用自制的热循环试验台对样品DA2和DB2同时进行1 000次加热/冷却循环实验后,对样品的导热系数、比热容进行不同热环境下的稳定性分析。1 000次加热/冷却循环后的样品DA2和DB2分别编号为DA2-1000和DB2-1000。
图6为样品DA2和DB2加热/冷却循环前、后的热流曲线。由图6可以看出,经历1 000次加热/冷却循环后,样品DA2、DB2的熔点和潜热均降低。样品DA2-1000和DB2-1000的熔点分别为327.6、328.3 ℃。样品DA2的潜热由44.19 J/g下降至35.29 J/g,变化率为–20.1%。样品DB2的潜热由42.06 J/g下降至40.90 J/g,变化率为–2.7%。这是因为多次循环后,少量PCM蒸发导致样品的潜热降低。其中,样品DA2的潜热明显下降20.1%,样品DB2的潜热轻微下降2.7%,因此,从潜热角度来看,样品DB2具有更好的热稳定性。
样品SC3、DA2和DB2循环后的比热容如图7所示。由图7可以看出:所有样品的比热容较循环前都有提升且循环后的DB2-1000样品的比热容在各个温度点同样为最高;1 000次冷热循环前、后,样品DA2、DB2的比热容发生微小的变化。因此,从比热容角度来看,添加导热增强剂的样品具有更好的热稳定性。
图8为样品SC3、DA2和DB2经历1 000次加热/冷却循环后的导热系数。由图8可以看出,每个样品1 000次循环之后的导热系数相比于未循环均有所增加且随温度的上升呈下降趋势。样品DB2(BN质量分数为2%)在各个温度点的导热系数均最大,且DB2和DB2-1000曲线每个温度点的导热系数差值都不超过0.1 W/(m∙K),DB2样品表现出了良好的热稳定性。样品温度处于400 ℃时,样品SC3-1000的导热系数为1.06 W/(m∙K),样品DA2-1000和DB2-1000的导热系数分别高达1.66、1.93 W/(m∙K),分别提高了57%和82%,高于未添加导热增强剂的样品SC3-1000。综合图8图9,导热增强剂的添加有效提高了污泥焚烧灰渣/硝酸钾复合相变储热材料的高温热稳定性,其中样品DB2的热稳定性良好。
添加导热增强剂的样品在各个温度点的比热容均高于样品SC3,因此,下文仅分析1 000次冷热循环前、后样品DA2、DB2的储热密度。根据下式可以计算出1 000次冷热循环前、后样品在100~380 ℃范围内的储热密度。
q= TlTocp,1dT+ΔHm+TtThcp,2dT
式中:q为储热材料的单位质量储热密度,J/g;cp,1cp,2分别为储热材料相变前、后的比热容,J/(g⋅K);T1Th分别为储热材料的计算下限和上限温度,K;ToTt分别为相变过程的起始温度和终止温度,K;ΔHm为储热材料的相变潜热,J/g。
图9为根据式(2)计算出的100~380 ℃范围内,冷热循环前样品DA2、DB2储热密度。由图9可知,冷热循环前样品DA2、DB2储热密度分别为287.4、330.2 J/g,冷热循环后样品DA2-1000,DB2-1000储热密度分别为292.1、334.9 J/g,所以DB2样品具有更好的储热性能。
为研究样品的蓄热性能,使用红外摄像机(Ti32,美国FLUKE)观察其温度随时间的变化,具体如图10所示。所有样品初始温度低于320 ℃,随着冷却过程的进行,在20 s时,样品DA1—DA3和样品DB1—DB3的温度分别为309.4、310.0、312.7、302.1、312.9、312.6 ℃;在1 700 s时,样品的温度分别为30.2、30.4、30.6、30.4、29.1、30.4 ℃。比较分析表明,DB2表现出最高的传热速率,为0.17 ℃/s,这表明其能够快速释放储存的能量,具有更好的导热性。
本文以污泥焚烧炉渣为骨架材料,硝酸钾为相变材料,通过分别添加导热增强剂SiC、BN和EG,冷压烧结法制备15种不同比例的复合相变储热材料,研究导热增强剂对污泥焚烧灰渣/硝酸钾复合相变储热材料宏观形貌、储热性能、导热性能和热稳定性的影响,主要结论如下。
1)EG不适合作为污泥焚烧炉渣/硝酸钾复合相变储热材料。
2)添加BN优于添加SiC。添加质量分数2%的导热增强剂在熔化潜热改善方面是最优的,SiC质量分数为2%的样品潜热为44.19 J/g,BN质量分数为2%的样品潜热为45.22 J/g。
3)添加BN的样品的导热系数提升最为显著。添加质量分数2%的样品在100~400 ℃时分别比样品SC3升高65%、93%、117%、203%。
4)BN质量分数为2%的样品具有更好的热稳定性。经历1 000次加热/冷却循环后,SiC质量分数为2%样品的潜热由44.19 J/g下降至35.29 J/g,变化率为-20.1%。BN质量分数为2%样品的潜热由42.06 J/g下降至40.90 J/g,变化率为-2.7%, 1 000次热循环后SiC质量分数为2%样品的储热密度为292.1 J/g,1 000次热循环后BN质量分数为2%样品的储热密度为334.9 J/g。
5)BN质量分数为2%的样品具有更好的蓄热性能。SiC质量分数为2%的样品、BN质量分数为2%的样品传热速率分别为0.16、0.17 ℃/s。
  • 北京市教育委员会科研计划项目(KM201910016011)
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2025年第54卷第7期
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doi: 10.19666/j.rlfd.202412265
  • 接收时间:2024-12-27
  • 首发时间:2026-03-06
  • 出版时间:2025-07-25
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  • 收稿日期:2024-12-27
基金
Research and Development Program of Beijing Municipal Education Commission(KM201910016011)
北京市教育委员会科研计划项目(KM201910016011)
作者信息
    1.北京建筑大学未来新材料研究院,北京 100044
    2.北京京能热力发展有限公司通州分公司,北京 101100
    3.北京工业大学传热强化与过程节能教育部重点实验室,北京 100124
    4.英国伯明翰大学伯明翰储能中心,伯明翰 B15 2TT
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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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