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Iron-based superconducting materials have a high critical magnetic field and low anisotropy and exhibit important application potential in the high field region. High-performance iron-based superconducting wires are the foundation for the high field and larger current applications of iron-based superconducting materials. This article reviewed the development of iron-based superconducting wires over the past 10 years, especially the latest progress in improving wire properties and coil development in recent years. It also put forward prospects for the main key technologies that need to be innovated in iron-based superconducting wires, providing a reference for the industrial application of iron-based superconducting wires in future.

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铁基超导材料具有临界磁场高、各向异性小等优点,在强磁场领域具有重要的应用潜力,获得高性铁基超导线材是铁基超导材料高场强电应用的基础。文章回顾了铁基超导线材10多年来的发展历程,尤其是近年来在线材性能提高及线圈研制方面取得的最新进展,并对未来实用化铁基超导线材需要重点突破的主要关键技术提出展望,以期为后续铁基超导线材的产业化应用提供参考。

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张现平,研究员,博士研究生导师。主要从事实用化超导材料制备研究,如二硼化镁和铁基超导线材制备及应用等。承担了国家重点研发计划、国家自然科学基金、北京市自然科学基金等项目。入选北京市科技新星等。获北京市科技奖自然科学奖和教育部自然科学奖等。发表论文200余篇,申请发明专利20余件。电子信箱:

马衍伟,研究员,博士研究生导师。中国科学院电工研究所副所长,中国科学院大学工程科学学院副院长。国家杰出青年科学基金获得者,IEEE Fellow,美国应用超导国际大会程序委员会委员等。主要从事高温超导线带材制备研究。获2019年国际应用超导杰出贡献奖(亚洲首次获奖)、教育部自然科学奖等省部级一等奖3项、2019中国科学年度十大新闻人物、2024年日内瓦国际发明展金奖、2024年纽伦堡国际发明展金奖、中国科协第三届“科创中国”先导技术榜单等。电子信箱:

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张现平,研究员,博士研究生导师。主要从事实用化超导材料制备研究,如二硼化镁和铁基超导线材制备及应用等。承担了国家重点研发计划、国家自然科学基金、北京市自然科学基金等项目。入选北京市科技新星等。获北京市科技奖自然科学奖和教育部自然科学奖等。发表论文200余篇,申请发明专利20余件。电子信箱:

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张现平,研究员,博士研究生导师。主要从事实用化超导材料制备研究,如二硼化镁和铁基超导线材制备及应用等。承担了国家重点研发计划、国家自然科学基金、北京市自然科学基金等项目。入选北京市科技新星等。获北京市科技奖自然科学奖和教育部自然科学奖等。发表论文200余篇,申请发明专利20余件。电子信箱:

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马衍伟,研究员,博士研究生导师。中国科学院电工研究所副所长,中国科学院大学工程科学学院副院长。国家杰出青年科学基金获得者,IEEE Fellow,美国应用超导国际大会程序委员会委员等。主要从事高温超导线带材制备研究。获2019年国际应用超导杰出贡献奖(亚洲首次获奖)、教育部自然科学奖等省部级一等奖3项、2019中国科学年度十大新闻人物、2024年日内瓦国际发明展金奖、2024年纽伦堡国际发明展金奖、中国科协第三届“科创中国”先导技术榜单等。电子信箱:

"}, bioImg=JumXzGKVn5Pomnx3bK8fgw==, bioContent=

马衍伟,研究员,博士研究生导师。中国科学院电工研究所副所长,中国科学院大学工程科学学院副院长。国家杰出青年科学基金获得者,IEEE Fellow,美国应用超导国际大会程序委员会委员等。主要从事高温超导线带材制备研究。获2019年国际应用超导杰出贡献奖(亚洲首次获奖)、教育部自然科学奖等省部级一等奖3项、2019中国科学年度十大新闻人物、2024年日内瓦国际发明展金奖、2024年纽伦堡国际发明展金奖、中国科协第三届“科创中国”先导技术榜单等。电子信箱:

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新型铁基超导线材的发展及其关键技术
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张现平 1, 2 , 姚超 1, 2 , 董持衡 1, 2 , 黄河 1, 2 , 王栋樑 1, 2 , 马衍伟 1, 2,
前瞻科技 | 综述与述评 2025,4(1): 70-80
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前瞻科技 | 综述与述评 2025, 4(1): 70-80
新型铁基超导线材的发展及其关键技术
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张现平1, 2 , 姚超1, 2, 董持衡1, 2, 黄河1, 2, 王栋樑1, 2, 马衍伟1, 2,
作者信息
  • 1.中国科学院电工研究所,北京 100190
  • 2.中国科学院大学,北京 100049
  • 张现平,研究员,博士研究生导师。主要从事实用化超导材料制备研究,如二硼化镁和铁基超导线材制备及应用等。承担了国家重点研发计划、国家自然科学基金、北京市自然科学基金等项目。入选北京市科技新星等。获北京市科技奖自然科学奖和教育部自然科学奖等。发表论文200余篇,申请发明专利20余件。电子信箱:

    马衍伟,研究员,博士研究生导师。中国科学院电工研究所副所长,中国科学院大学工程科学学院副院长。国家杰出青年科学基金获得者,IEEE Fellow,美国应用超导国际大会程序委员会委员等。主要从事高温超导线带材制备研究。获2019年国际应用超导杰出贡献奖(亚洲首次获奖)、教育部自然科学奖等省部级一等奖3项、2019中国科学年度十大新闻人物、2024年日内瓦国际发明展金奖、2024年纽伦堡国际发明展金奖、中国科协第三届“科创中国”先导技术榜单等。电子信箱:

通信作者:

Development and Key Technologies of New Iron-based Superconducting Wires
Xianping ZHANG1, 2 , Chao YAO1, 2, Chiheng DONG1, 2, He HUANG1, 2, Dongliang WANG1, 2, Yanwei MA1, 2,
Affiliations
  • 1. Institute of Electrical Engineering, Chinese Academy of Sciences, Beijing 100190, China
  • 2. University of Chinese Academy of Sciences, Beijing 100049, China
出版时间: 2025-03-20 doi: 10.3981/j.issn.2097-0781.2025.01.007
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铁基超导材料具有临界磁场高、各向异性小等优点,在强磁场领域具有重要的应用潜力,获得高性铁基超导线材是铁基超导材料高场强电应用的基础。文章回顾了铁基超导线材10多年来的发展历程,尤其是近年来在线材性能提高及线圈研制方面取得的最新进展,并对未来实用化铁基超导线材需要重点突破的主要关键技术提出展望,以期为后续铁基超导线材的产业化应用提供参考。

超导材料  /  铁基超导线材  /  载流性能  /  关键技术

Iron-based superconducting materials have a high critical magnetic field and low anisotropy and exhibit important application potential in the high field region. High-performance iron-based superconducting wires are the foundation for the high field and larger current applications of iron-based superconducting materials. This article reviewed the development of iron-based superconducting wires over the past 10 years, especially the latest progress in improving wire properties and coil development in recent years. It also put forward prospects for the main key technologies that need to be innovated in iron-based superconducting wires, providing a reference for the industrial application of iron-based superconducting wires in future.

superconducting material  /  iron-based superconducting wire  /  current-carrying  /  key technology
张现平, 姚超, 董持衡, 黄河, 王栋樑, 马衍伟. 新型铁基超导线材的发展及其关键技术. 前瞻科技, 2025 , 4 (1) : 70 -80 . DOI: 10.3981/j.issn.2097-0781.2025.01.007
Xianping ZHANG, Chao YAO, Chiheng DONG, He HUANG, Dongliang WANG, Yanwei MA. Development and Key Technologies of New Iron-based Superconducting Wires[J]. Science and Technology Foresight, 2025 , 4 (1) : 70 -80 . DOI: 10.3981/j.issn.2097-0781.2025.01.007
超导材料具有零电阻、完全抗磁性和宏观量子效应等奇特的物理性质,在能源、交通、医疗、重大科学工程等方面具有重要的应用价值。随着科技的发展,磁共振成像系统、核磁共振谱仪等高端仪器装备,高能加速器、核聚变等大科学工程,以及超导电力装备、磁悬浮轨道交通等诸多领域,对超导材料及其应用技术的需求愈发迫切,发展高性能的超导材料及其应用技术对经济和社会的发展具有重要意义。
超导材料是超导技术得以广泛应用的基础,实用化超导材料主要分为低温超导材料和高温超导材料。以铌钛和铌三锡为主的低温超导材料,由于具有优良的机械加工性能及载流性能,目前在超导市场处于主导地位。以钇钡铜氧涂层导体为代表的高温超导带材,具有优异的高场载流性能,在可控核聚变等应用需求带动下,近年取得了较大的突破,性价比得到不断提高。
2008年发现的新型铁基超导材料,具有较高的临界转变温度、极高的上临界场及较小的各向异性,被认为是适合高场领域应用的实用化超导材料,特别是在高能加速器、高场磁共振成像、可控核聚变等领域具有独特的应用优势[1]。高性能超导线材是实现超导材料强电高场应用的基础。自铁基超导材料被发现以来,科学家在铁基超导线材制备关键技术方面不断取得突破,铁基超导线材的载流性能得到迅速提高,并初步应用于高场内插线圈、跑道型线圈、大电流换位超导电缆等的研制。
由于铁基超导材料硬度高且具有脆性,难以塑性变形加工,因此不能采用制备铌钛和铌三锡超导线时使用的金属塑性变形工艺。目前,粉末套管法(Powder-in Tube, PIT)是最常用的铁基超导线材制备方法,即通过将脆性粉末装入金属管,然后经过机械加工成为线材。该方法由于工艺简单、成本低廉,已成功应用于铋系铜氧化物超导线材和二硼化镁超导线材的商业化制备。铁基超导材料与铋系超导材料的晶粒均为片状,加工特性基本相似。另外,铁基超导体的超导电流在通过大角度晶界时受到的衰减相对较小,因此PIT工艺非常适合铁基超导线带材的制备研究。从未来实际应用来看,由于设备成本低且机械加工工艺简单,PIT在铁基超导线材的低成本、规模化制备方面具有显著优势。
为了推进铁基超导体的实用化进程,众多国内外知名研究机构陆续开展了铁基超导线带材的制备研究工作,不断提高超导线带材在强磁场下的载流性能,促进其实用化。美国、日本及欧洲等国家和地区均设立了铁基超导材料方面的重大项目,例如:日本科技振兴会设立的“世界领先的科技创新研发资助计划(FIRST)”,欧洲核子研究中心设立的面向下一代加速器的铁基超导材料研究项目等。目前国外从事铁基超导线带材研究的主要单位包括日本国立材料研究所、日本东京大学、日本产业技术综合研究所、美国佛罗里达高场实验室、美国橡树岭国家实验室、意大利热那亚大学、澳大利亚伍仑贡大学等。
美国佛罗里达州立大学是国际上较早开展铁基超导线材研究的单位之一。2008年,该校研究人员铁基超导多晶样品中发现全局电流的确实存在,但晶内与晶间电流具有明显不同的温度依赖性。他们采用磁光成像和剩余磁化率测量等方式对晶内和晶间电流进行了分析,认为晶界杂相是影响多晶样品载流性能的关键[2]。爱荷华州立大学开展了类似的工作,研究人员采用磁光成像方法分析了NdFeAsO0.9F0.1的静态和动态涡旋行为及其对多晶样品载流性能的影响[3]
威斯康星大学研究团队在Ba(Fe1-xCox)2As2孪晶上的研究发现,尽管Ba(Fe1-xCox)2As2的上临界场Hc2附近具有低各向异性、强涡旋钉扎和高不可逆场,但薄膜Ba(Fe1-xCox)2As2孪晶的[001]倾斜晶界(Grain Boundary, GB)上的临界电流密度Jc被强烈抑制,表明由于低载流子密度和非常规配对对称性,铁基超导材料具有类似于铜氧化物的晶界弱连接特性[4]
美国国家强磁场实验室研究团队在研究多晶样品中电流传输时发现,只有少数晶粒到晶粒的传输电流路径,而大部分晶界电流传输路径在施加磁场时无效。这些区域通常发生在电流穿过Fe-As的地方,而Fe-As是围绕Sm1111晶粒的金属润湿相。他们提出需要减少晶界润湿Fe-As相的量和晶粒内的裂纹密度,因为这些缺陷会形成电流阻断网络[5]。佛罗里达州立大学研究团队制备了未掺杂的多晶Ba0.6K0.4Fe2As2块体和具有高晶界密度的圆形线材。他们认为样品较好的超导性能主要归因于两方面:一是较高的相纯度带来的良好的晶粒连接性;二是这种低各向异性化合物具有的强磁通钉扎能力。他们在采用高能球磨工艺混合Ba0.6K0.4Fe2As2时观察到了机械激活的自我维持反应,并形成了平均粒径<1 μm的Ba122主相。虽然高温(1 120 ºC)和高压下热处理可得到高相纯度的致密样品,但磁光成像只能观察到颗粒电流。相比之下,在常压下进行短时低温(600 ºC)热处理时,即使样品密度较低且杂相更多,整个块体样品中也有整体电流流动,显示出多晶铁基超导材料制备过程中工艺的重要性[6]
美国西北大学研究团队针对K、Co掺杂的多晶BaFe2As2、SrFe2As2超导体临界电流密度较低的问题开展了研究,利用原子探针断层扫描分析了高临界电流密度的K、Co掺杂BaFe2As2多晶中的晶粒和GB组成。他们发现,样品所有晶界在几个相干长度范围内显示出显著的成分变化,以及氧杂质的强烈偏析。基于对晶界主要元素比例波动的现象,可以认为晶界电流阻断主要由外界因素所致,可通过制备工艺优化来改进[7]
圣路易斯大学研究团队在高达65 T的脉冲磁场中对Ba(Fe0.92Co0.08)2As2、Ba(Fe0.91Co0.09)2As2多晶块状超导体的上临界磁场和不可逆磁场进行了全面研究,获得了从1.5 K开始的全磁场温度(H-T)相图。他们还在高达18 T的磁场中进行了Ba(Fe0.91Co0.09)2As2样品的电阻率和交流磁化率测量,研究了其热辅助磁通流和磁通钉扎能[8]
洛斯阿拉莫斯国家实验室研究团队通过对不同平均晶粒尺寸的Ba0.6K0.4Fe2As2、Ba(Fe0.95Ni0.05)2As2、Ba(Fe0.94Ni0.06)2As2、Ba(Fe0.92Co0.08)2As2和Ba(Fe0.91Co0.09)2As2多晶块状超导体开展研究,获得了K掺杂样品在28 K下上临界场Hc2高达65 T的磁场温度(Hc2-T)相图,得出最小亚微米晶粒尺寸样品的临界电流密度测量值高达105 A/cm2。他们认为,高的上临界场Hc2、不可逆场Hirr和临界电流密度Jc表明这些材料适用于磁体设计,同时因其具有良好的机械强度和随机晶粒排列特性,有望应用于下一代磁体制造方面[9]
2024年,美国强磁场实验室Kametani等[10]采用高分辨透射电镜等手段研究了国际上两种工艺制备的具有类似高Jc的Ba122超导带材中的晶粒和晶界纳米结构,发现热压制备的银包覆带具有更大、更多的板状晶粒,具有更好的晶粒取向,但很多晶界存在FeAs和Ba-O杂相。相比之下,用Ag-Sn/不锈钢包套冷压制备的带材具有更少的板状颗粒和较弱的晶粒取向,但具有干净的、连接性好的晶界和更多的电流流通路径。该工作强调了实现高临界电流密度对良好晶粒排列和清洁晶界的强烈需求,也证实目前国际上制备的最高性能铁基超导带材仍存在巨大的性能提升空间。
在国家战略规划方面,2021年《美国高能加速器领域战略规划白皮书》(White paper for the accelerater frontier snowmass ′21)指出,铁基超导材料正在从实验室走向产业化。2024年,美国国家科学院《强磁场科学与技术现状与未来发展方向》(The current status and future direction of high-magnetic-field science and technology in the United States)战略报告特别介绍了基于铁基超导体运行于10 T背景场的跑道型线圈,认为铁基超导体是未来高场超导磁体的一个重要候选材料。
日本先后有多家单位开展了铁基超导线材研究,包括日本国立材料研究所、日本东京大学、日本产业技术综合研究所等。
日本国立材料研究所研究团队早期的工作主要集中在FeSe基超导线材制备方面。2009年,他们通过特殊的PIT制备了Fe(Se,Te)超导线。在这项工作中,外层纯铁管不仅起着包套的作用,而且是合成超导相的原料,最终在Fe(Se,Te)线材的电流-电压测量中成功得到了传输电流。他们还发现,采用先位PIT制备的FeTe0.5Se0.5超导线材,在没有任何热处理的情况下即可测到超导电流。与此同时,他们还使用淬火技术提高了FeSe线材的超导性能。例如,淬火线材在约10 K时实现了零电阻率,比多晶FeSe块体高约2 K;淬火线材的Jc比炉冷线材高3倍等[11]
随后研究团队通过熔融和变形的组合过程合成了多晶(Ba,K)Fe2As2超导块材。与通过传统烧结工艺制备的样品相比,该样品的杂相更少、密度更高。尽管块状样品的密度很高,但电流流通路径仍受到很大程度抑制,其中晶界处的弱连接是制约块材样品体电流的最主要原因[12]。2011年,他们采用先位PIT工艺制备了添加银的(Ba,K)Fe2As2超导线材,并在该线材中得到了较大Jc。线材制备过程中,首先采用熔融工艺制备前驱体块材,接着将块材研磨成粉末并放入银管,然后将复合棒材冷加工成线材,并在850 ºC下进行热处理。此外,通过重复轧制和热处理的组合过程也是提高Ag包套(Ba,K)Fe2As2(Ba-122)线材超导性能的方法。试验发现,这种方法制备的薄带(0.3 mm厚)具有致密的晶粒结构,裂纹和空隙也较少,这被认为是Jc大幅增强的原因[13]。在铁基超导带材变形的最后阶段施加单轴冷压也是提高其超导性能的可行方法。硬度测量和微观结构研究表明,冷扁轧和单轴压制的组合过程可带来超导芯的高致密度、更多的织构晶粒和微裂纹结构的变化[14]
庆应义塾大学研究团队尝试了使用先位PIT制备SmFeAsO1-xFx超导线材,合成超导芯的原材料包括Sm1111粉末和氟化钐、砷化钐和砷化铁。尽管Sm1111的F质量分数在线材热处理过程中有所降低,但SmF3的存在对F质量分数进行补偿,从而防止超导转变温度降低和超导体积分数减小。为了减少多晶SmFeAsO1-xFx带材中由于随机存在的非晶态FeAs化合物对超导电流的阻碍作用,他们尝试在超导芯中添加金属铟,结果发现将铟添加到多晶SmFeAsO1-xFx中可以去除这些非晶区域,并诱导超导晶粒的聚集,从而带来晶粒总接触面积的增大[15]
东京大学研究团队早期也开展了利用扩散法制备FeSe基超导线材方面的研究,但很快转到对Ba122超导线材制备的研究。2013年,研究人员通过粉末装管法结合热等静压技术制备了(Ba,K)Fe2As2超导线材,在线材超导芯中获得较大的晶间Jc。该方法还被用于制备(Sr,K)Fe2As2超导圆线,同样在超导芯中获得了较大的晶间[16]。他们还研究了在线材制备过程中(Ba,K)Fe2As2超导性能的演变,发现线材超导芯的性能在每次拉拔过程中均有所退化,而热处理时又会有所恢复。拉拔工艺会导致超导芯的退化、微裂纹的形成、晶粒之间的弱连接和晶粒的随机取向。他们还尝试了(Sr,Na)Fe2As2、(Ba,Na)Fe2As2和CaKFe4As4等超导线材的制备[17],并先后在2021、2023年分别采用单芯和7芯(Ba,A)Fe2As2(A: Na,K)线材制备了铁基超导线圈。结果发现,随着芯丝数量的增加,线材的临界电流密度有所降低,可能是由于在拉丝过程中超导芯的退化、同心织构的降低及“香肠效应”增强所致。采用单芯和7芯线材制备的超导线圈在4.2 K下分别产生了2.6 kOe和1.0 kOe的中心磁场[18]
日本产业技术综合研究所研究团队采用PIT制备了(Sr,Na)Fe2As2的超导带材,多晶Sr1-xNaxFe2As2x=0.55)被用作起始粉末,将银管孔型轧制成方形线材,并平轧成带状,然后进行单轴冷压。结果显示,即使没有向起始粉末中添加Ag,(Sr,Na)Fe2As2晶粒之间也存在一些富含Ag和As的材料。研究人员认为这种富含Ag和As的材料可以增强晶粒的连接性,并有助于改善传输Jc。随后他们在采用PIT制备Ba1-xKxFe2As2超导带材时优化了钾掺杂的浓度(x=0.3,0.4),发现与x=0.4相比,x=0.3带材的磁化温度依赖性显示出更陡峭的超导转变,低场下的传输临界电流也较高。而x=0.4带材在较高的磁场(>0.5 T)中显示出较大的Jc。他们认为通过优化加工和热处理工艺,特别是对于x=0.3带材,可以改善超导芯的晶粒连接性,从而进一步增强Jc[19]
意大利国家核物理研究所研究团队比较了SmFeAsO1-xFx和Fe1+yTe1-xSex两个铁基超导体的输运和超导性能,包括电阻率、磁阻、霍尔效应、塞贝克效应、热导率、上临界场等。在常见的铁基超导家族中,SmFeAsO1-xFx具有最大的Tc、各向异性;Fe1+yTe1-xSex具有最大的Hc2,以及最小的Tc、各向异性。在Fe1+y(Te1-x,Sex)中,发现由Se化学计量调节过量Fe有两方面作用:一方面,在系统中掺杂电子;另一方面,引入了局部磁矩,导致库珀对的断裂。因此,铁过量在影响超导特性(如临界温度Tc和上临界场Hc2)方面也起着至关重要的作用。Fe1+yTe1-xSex样品的巨大Hc2值由脏极限定律描述,与SmFeAsO1-xFx样品的干净极限行为相反[20]
意大利国家研究理事会下属的人工智能和创新实验室研究团队制备了SmFeAsO和SmFeAs(O0.93F0.07)相,发现烧结处理显著提高了晶粒的连通性,但同时会导致超导相与Sm2O3的热力学稳定性之间的竞争,从而影响样品的纯度。磁化和电阻率测量都表明F掺杂样品中存在两种不同的磁性来源:前者与Fe磁有序有关,后者则源于Sm离子在低温下反铁磁性有序。在140 K下,F掺杂样品中的抗磁特征消失,并在低温下出现超导转变[21]
2012年,意大利热那亚大学研究团队提出了一种基于熔融过程和退火处理制备块状Fe(Se0.5Te0.5)样品的新方法,它可以生产出更均匀、更致密的样品,其特征是晶粒大且相互连接良好。所得样品表现出最佳的临界温度值、陡峭的电阻和磁转变、大的磁滞回线和高的上临界场。研究人员尝试了不同的金属和合金作为包套材料(Cu、Ag、Nb、Ta、Ni、Fe、白铜、黄铜)制备Fe(Se,Te)线材,发现唯一不会对Fe(Se,Te)相产生实质性影响的包套材料是Fe,但Fe包套会在Fe(Se,Te)相中引入过量铁,进而影响线材的超导性能。在研究了热处理和粉末成分对超导性能的影响后,他们认为通过粉末装管法制造Fe(Se,Te)线具有相当大的挑战性,应该开发其他方法[22]
意大利国家研究理事会下属的超导和新型材料与器件研究所研究团队在2019年研究了在轧制织构基带上沉积Fe(Se,Te)薄膜的可行性。他们在市售的Ni-W(原子分数5%)金属基带上通过脉冲激光辅助沉积了CeO2层,为超导薄膜沉积提供织构并充当防止Ni扩散的屏障。2020年,研究人员研究了不同缓冲层的织构和厚度在制备Fe(Se,Te)涂层导体中的作用,发现缓冲层必须足够厚以阻止Ni从金属带到Fe(Se,Te)覆盖层的相互扩散,并且具有足够的织构以确保超导膜良好的面内织构,从而确保较高的Jc。使用高度织构的350 nm厚CeO2缓冲层获得了最佳的TcJc。该结果表明,Fe(Se,Te)涂层导体的超导性能取决于基材织构化水平,以及镍与超导膜之间的相互扩散程度[23]
德国慕尼黑大学的研究团队分析了不同热处理和加工工艺对(K, Ba)Fe2As2带材微观结构的影响,解决了超导芯中相纯度、内部孔隙和裂纹等问题,得到了晶界干净且连接良好但密度较差的超导芯。为了避免使用高活性的K,他们还使用BaFe2(P1-xAsx)2制备了超导带材。BaFe2(P1-xAsx)2非常稳定,而且在单晶和薄膜中表现出优异的Jc。但在带材中发现晶界处存在化学成分的不均匀性,制约了多晶带材的传输电流[24]
中国科学家在铁基高温超导体基础研究和实用化方面均走在了国际前列,先后有中国科学院电工研究所(简称电工所)、西南交通大学、西北有色金属研究院、天津大学、东南大学、上海交通大学等单位开展了铁基超导线材方面的研究。
电工所是国际上最早开展铁基超导线材研究的单位,线材制备技术和性能持续处于世界领先水平。在铁基超导体超导电性被发现后,该所研究人员迅速制备了国际第一根铁基超导线材。针对采用原位PIT制备的LaOFeAs线材超导芯中存在大量杂相、致密度较低,以及超导芯与包套反应等问题,他们先后开发了银包套、先位法、金属掺杂等铁基超导线材制备技术,显著提高了铁基超导线材的载流性能。2011年,针对铁基超导材料具有的晶界弱连接特性,提出了大变形平辊轧制的制备方法,提高了超导芯的织构化程度。针对超导芯致密度不高的问题,2013年提出采用冷压、热压等制备工艺,并于2014年在国际上首次将铁基超导线材的临界电流密度提高到1.0×105 A/cm2(4.2 K、10 T)以上[25],证实了铁基超导线材的实用化潜力。2024年,通过新型大变形工艺制备的122型铁基超导线材的临界电流密度已提高至2.6×105 A/cm2(4.2 K、10 T),即使在高达30 T的磁场中,铁基超导线材的临界电流密度仍然超过1.0×105 A/cm2,展示出铁基超导线材在高场领域的良好应用前景[26]
与此同时,电工所在铁基超导线材的实用化方面也开展了大量的工作。2013年,通过二次复合套管多芯成材工艺,先后成功制备出7芯、19芯、114芯等不同芯丝数量的多芯铁基超导线材[27]。与单芯铁基超导线材相比,多芯线材的临界电流随磁场增大衰减的速度更为缓慢,体现了更好的高场特性。研究人员还选用强度较高、导热导电性能良好的莫奈尔合金作为外层包套,与银包套Sr122单芯线进行复合,制备了高强度Fe/Ag/Sr122复合包套铁基超导带材。采用不锈钢作为包套材料,制备出的高强度不锈钢/Ag/Ba122复合包套铁基超导带材的机械强度达到300 MPa以上,能够有效保护超导芯不易受损,提高铁基超导带材的稳定性[28]
2016年,电工所研究团队通过对铁基超导长线的结构设计和加工技术的试验优化,成功解决了铁基超导线规模化制备中的均匀性和重复性等技术难点,制备出了长度达到115 m的铁基超导长线(图1[26]),经测试其载流性能表现出良好的均匀性和较弱的磁场衰减特性[29]。这一重大突破性成果表明中国已率先掌握了具有自主知识产权的铁基超导长线制备技术,为其在强电领域的实用化和产业化奠定了坚实基础。近年来,在国际首根百米级铁基超导长线的基础上,电工所又继续在元素掺杂、线带材成材、热处理工艺、微观结构等方面,对超导长线的前驱粉制备、线材结构设计和线材加工技术进行进一步试验优化,将百米级铁基超导长线的传输临界电流密度提高至6.6×104 A/cm2(4.2 K,10 T)[26]。目前,国际上有关铁基超导长线方面的报道,仅为日本东京大学研制出17 m级的铁基超导线材[18]
2019年,电工所和中国科学院高能物理研究所(简称高能物理所)合作,依据铁基超导线材的弯曲半径、最大拉伸应力等线圈绕制的控制参数,研制了世界首个基于铁基超导材料的高场内插线圈。在高达24 T的背景磁场下,线圈的临界电流仍然达到26 A,并展现了较弱的磁场依赖性,首次验证了铁基超导体在高场领域应用的可行性[30]
2021年,高能物理所研究团队采用电工所制备的高性能铁基超导百米长线,通过先绕制后热处理的方法研制出国际首个大尺寸跑道型铁基超导线圈。在10 T磁场下进行临界电流性能测试发现,铁基超导跑道线圈的临界电流达到了短样临界电流的86.7%,同时这一性能超过了线圈在零场下性能的80%,验证了铁基超导线材用于制备未来高场加速器磁体的可行性,证明了铁基超导材料用于发展下一代高场磁体的巨大潜力[31]
2023年,电工所与中国科学院强磁场科学中心合作,利用自研的铁基超导长线,开展了铁基超导高场内插线圈方面的研究。通过对内插线圈的优化设计,探索并完善了线圈的研制工艺,研制出外径120 mm、内径35 mm铁基超导线圈(图2[23])。在中国科学院强磁场科学中心稳态强磁场实验装置的大口径水冷磁体20 T的背景磁场下的测试结果表明,铁基超导高场内插线圈成功产生了1.03 T的中心磁场强度,是世界上首台1 T级的铁基超导高场内插线圈。东京大学Tamegai[33]专门发表评述,认为“已经进入实用型高场磁体家族”(Iron-based superconductors have joined the practical high-field magnet family)。
西南交通大学研究团队针对1111体系所含元素多、成相困难易生成杂相等问题,研究了杂相的存在对SmFeAsO0.8F0.2线材超导性能的影响,发现虽然超导芯磁化测量中显示出了较高的晶内电流,但晶间临界电流密度几乎为零[34]。2010年2月,电工所通过降低烧结温度,采用原位法成功制备了临界电流密度约为1 300 A/cm2(4.2 K、0 T)的Sm1111线材,这也是世界上首次在1111体系的带材中获得传输电流。2015年,电工所采用低温合成法制备了1111铁基超导带材,其临界电流密度进一步提高到3.95×104 A/cm2(4.2 K、0 T),是目前世界上在1111体系的带材样品中得到的最高临界电流密度[35]
东南大学研究团队在2016年采用原位PIT制备了FeSe0.5Te0.5线材,目前已制备出临界温度为15.7 K、临界电流密度高达104 A/cm2 (5 K、0 T)的带材。2018年,他们采用高能球磨辅助烧结(12 h、750 ºC)制备了Ba0.6K0.4Fe2As2前驱体粉末,并采用双轴冷压技术对线材进行致密化,所制备圆线的传输临界电流密度达到1.14×105 A/cm2(4.2 K、2 T)[36]
西北有色金属研究院研究团队采用PIT结合高能球磨辅助烧结工艺制备了具有高临界电流密度的铁包套FeSe超导线材。高能球磨工艺的引入不仅保证了前驱体粉末的原子均匀性,而且大大缩短了Fe与Se原子之间的扩散距离,有效地避免了非超导六方δFeSe相的形成,显著提高了FeSe线材的电流输运性能,4.2 K、0 T下Jc达到340 A/cm2[37]。他们还研究了Fe和Ag添加量对FeSe体系的相组成、微观结构、临界温度及晶粒连接性的影响,发现随着Fe和Ag添加量的增加,非超导六方FeSe相的含量降低,并在Fe1.10Se和Fe1.15Se体系中添加质量分数为10%的Ag均获得了最佳的超导性能[38]
中国科学院物理研究所研究团队报道了一种直接微波合成制备高质量Fe(Se,Te)多晶超导体的方法。微波合成的样品显示出几乎纯净的四方PbO型晶体,晶粒尺寸约为100 μm并具有高致密度。与固态反应合成的样品相比,这些微波辅助合成的超导块体可能不含间隙铁,有望用于大电流Fe(Se,Te)铁基超导线材的制备[39]
上海交通大学研究团队则开展了FeSe基涂层导体方面的工作。他们通过将CeO2缓冲层沉积金属基带上,采用脉冲激光沉积技术成功制备了1 m长的Fe(Se,Te)涂层导体。在4.2 K、0 T、1 m长的Fe(Se,Te)涂层导体的端到端临界电流高达108 A/cm[40]
针对铁基超导特层导体的应用需求,中国科学院等离子体研究所研究团队制备了具有4种稳定层和3种焊料的FeSe0.5Te0.5涂层导体,发现由铜层和Bi50Pb25Sn12.5Cd12.5封装的FeSe0.5Te0.5带材在自场下的临界电流约为400 A,在10 T下的临界电压约为25 A。2023年,研究人员采用FeSe0.5Te0.5涂层导体率先制备了线圈,并在0~10 T的背景磁场下测量了FeSe0.5Te0.5线圈的临界电流,展示出FeSe0.5Te0.5涂层导体在高磁场中具有的良好性能[41]
2023年,电工所研究团队首次通过脉冲激光沉积在LaMnO3缓冲层金属基带上沉积了厚度达2 μm的高性能FeSe0.5Te0.5涂层导体。通过交替生长10 nm厚的非超导层和400 nm厚的FeSe0.5Te0.5超导层,在超导膜中获得了良好的双轴织构。研究表明,FeSe0.5Te0.5薄膜的厚度效应可能与电荷载流子的波动对磁通钉扎的减弱有关[42]
超导线材是超导强电装备的基础,线材特性直接决定电气装备的极限电磁参数。中国在高性能铁基超导线材的研制方面一直走在世界前列,目前在线材性能和长线制备方面处于世界领先地位,并率先开展了铁基超导线圈等实用化方面的研究。但是高性能铁基超导线材的进一步发展仍存在许多理论和技术上的问题亟待解决。
1)前驱粉是影响超导线材超导性能最关键的因素,因此获得规模化高质量前驱粉是制备高性能铁基超导长线的关键。目前载流性能最高的铁基超导线材体系是Ba122材料。该体系中含有易挥发元素K和As,这为高质量前驱粉合成过程中的成分控制带来了困难。易挥发元素偏离导致的杂相(如FeAs等)存在于晶界处,对超导电流的传输起到了阻碍作用。厘清杂相的形成机制、有效控制易挥发元素是宏量制备高质量前驱粉的关键。
2)铁基超导材料具有晶界弱连接特性,相对于铜氧化物超导材料,虽然铁基超导材料的晶界临界角较大,但获得具有良好织构的超导芯仍然是提高铁基超导线材载流性能的重要途径。目前制备的铁基超导线材的超导芯只有部分晶粒具有c轴织构,进一步增强超导芯的c轴织构,甚至引入类似于涂层导体的双轴织构,是显著提升线材载流性能的可行方法。
3)高强度铁基超导长线的制备也是推动铁基超导材料强电应用的重要工作。在长线加工过程中,高强度金属包套的使用会带来机械加工方面的困难。解决高强度金属包套与陶瓷性粉末的协同变形问题是目前实用化铁基超导线材制备的难点。在有限元模拟等指导下进行优化试验,可以快速推进长线机械加工方面的工作。
4)获得高性能铁基超导长线为铁基超导材料的应用提供了基础,但在大规模应用之前,还需要开展接头、电缆、线圈等方面的探索。例如,在使用高强度复合线材时,必须优化铁基超导线圈的设计和制造。针对特定应用场合和应用需求,对铁基超导线材的导体结构设计及综合性能进行研究,加强和完善材料与应用之间的相互促进和合作研究机制。因此建议超导产业界从宏观层面进行统筹,建立铁基超导材料、器件、装备与服役应用的顶层设计与规划,促进中国铁基超导材料产业的创新发展。
此外,铁基超导材料尚无统一的国际、国家或行业技术标准,需要加强对产品标准、测试标准等的研究与制定,从而规范和指导产业化发展。在上述工作完成后,相信高性能、低成本的铁基超导线材将广泛应用于如聚变反应堆、高能粒子加速器及高场核磁共振系统等强磁场领域。
超导材料及其应用是中国战略性新兴产业的重点突破方向,被列入国家多个发展战略规划。在“国际热核聚变实验堆计划”项目带动下,中国低温超导材料得到迅速发展,已进入国际先进行列。目前,美国商务部工业与安全局全面出口禁运除NbTi以外的超导线带材,发展具有自主知识产权的高温超导线材制备技术,是促进中国高温超导产业发展的关键。铁基超导材料是一种新型高温超导材料,我国在铁基超导材料的基础和实用化方面处于世界领先地位。开展新型实用化铁基超导材料的系统、原创性研究,对于发展具有自主知识产权的超导线材制备技术,突破制约高场超导磁体变革性技术发展的瓶颈,增强我国在超导领域的国际影响力和竞争力具有重要意义。
  • 国家自然科学基金(52172275)
  • 国家自然科学基金(52377032)
  • 国家自然科学基金(52377033)
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2025年第4卷第1期
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doi: 10.3981/j.issn.2097-0781.2025.01.007
  • 接收时间:2024-12-23
  • 出版时间:2025-03-20
  • 发布时间:2025-03-27
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  • 收稿日期:2024-12-23
  • 修回日期:2025-01-21
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国家自然科学基金(52172275)
国家自然科学基金(52377032)
国家自然科学基金(52377033)
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    1.中国科学院电工研究所,北京 100190
    2.中国科学院大学,北京 100049

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表12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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