非晶合金作为能源存储和转化材料的研究

基金项目

广东省自然科学基金项目(2024B1515020010); 广东省科协青年科技人才培育计划项目(SKXRC2025192)资助

中图分类号:

TG139+.8 TB34

文献标识码:

A

作者简介

周丹(1988—),女,安徽马鞍山人,硕士,研究方向:金属能源材料领域专利检索和导航,E-mail:zhoudan_2@cnipa.gov.cn

通信作者

林怀俊,教授,E-mail:hjlin@jnu.edu.cn

卢彦杉,副教授,E-mail:yanshan.lu@gdut.edu.cn

流转信息

收稿日期 : 2025-03-13

修订日期 : 2025-04-24

引文格式

周丹,黄亮君,卢彦杉,林怀俊. 非晶合金作为能源存储和转化材料的研究[J]. 铜业工程,2026(2):86-98.

Amorphous Alloys as Energy Storage and Conversion Materials

Citations

ZHOU Dan,HUANG Liangjun,LU Yanshan,LIN Huaijun. Amorphous alloys as energy storage and conversion materials[J]. Copper Engineering,2026(2):86-98.

铜业工程    第2期    86-98
doi10.3969/j.issn.1009-3842.2026.02.009
材料制备与加工工程(Material Preparation and Process Engineering)

非晶合金作为能源存储和转化材料的研究

  • 周丹 1
  • 黄亮君 2
  • 卢彦杉 2
  • 林怀俊 3
1.国家知识产权局专利局专利审查协作广东中心材料部广东 广州 510535
2.广东工业大学先进材料与技术研究院广东 广州 510006
3.暨南大学先进耐磨蚀及功能材料研究院广东 广州 510632

作者简介

周丹(1988—),女,安徽马鞍山人,硕士,研究方向:金属能源材料领域专利检索和导航,E-mail:zhoudan_2@cnipa.gov.cn

通信作者

林怀俊,教授,E-mail:hjlin@jnu.edu.cn

卢彦杉,副教授,E-mail:yanshan.lu@gdut.edu.cn

基金项目

广东省自然科学基金项目(2024B1515020010); 广东省科协青年科技人才培育计划项目(SKXRC2025192)资助

中图分类号:

TG139+.8 TB34

文献标识码:

A

流转信息

收稿日期 : 2025-03-13     修订日期 : 2025-04-24     

引文格式

周丹,黄亮君,卢彦杉,林怀俊. 非晶合金作为能源存储和转化材料的研究[J]. 铜业工程,2026(2):86-98.

摘要

非晶合金也称为金属玻璃,其长程无序的原子排列结构,使其比传统晶态合金拥有更丰富的活性位点以及更优异的化学与催化活性,因此在氢能、太阳能、二次电池等能源储存和转换应用领域有广阔的前景。本文系统综述了非晶合金作为电催化水分解催化剂、储氢材料、锂离子电池和锂金属电池材料、水系锌离子电池材料、太阳能电池关键材料、超级电容器等的最新研究进展,重点总结了非晶合金在能源存储和转化材料应用中的优异表现,分析了非晶态原子结构对能源存储和转化特性的影响规律及机理,并对非晶合金结构与性能的调控策略进行了概述。最后,总结并展望了本领域研究的挑战和未来发展趋势。

关键词

非晶合金;能源存储材料;能源转化材料;催化剂;

Amorphous Alloys as Energy Storage and Conversion Materials

  • ZHOU Dan 1
  • HUANG Liangjun 2
  • LU Yanshan 2
  • LIN Huaijun 3
1.Materials DepartmentPatent Examination Cooperation Guangdong Center of the Patent OfficeGuangzhou 510535China
2.Institute of Advanced Materials and TechnologyGuangdong University of TechnologyGuangzhou 510006China
3.Institute of Advanced Wear & Corrosion Resistant and Functional MaterialsJinan UniversityGuangzhou 510632China

Citations

ZHOU Dan,HUANG Liangjun,LU Yanshan,LIN Huaijun. Amorphous alloys as energy storage and conversion materials[J]. Copper Engineering,2026(2):86-98.

Abstract

Amorphous alloys, also known as metallic glasses, have more active sites and better chemical and catalytic activity than traditional crystalline counterparts due to their long-range disordered atomic arrangement structure. Therefore, they have broad prospects in energy storage and conversion applications such as hydrogen energy, solar energy, and secondary batteries. This paper systematically reviewed the latest research progress of amorphous alloys utilized as electrocatalysis catalysts of water, hydrogen storage materials, lithium-ion battery and lithium battery materials, aqueous zinc-ion battery materials, key materials for solar cells, and supercapacitors, etc. Emphasizing the excellent performance of amorphous alloys, it focused on the influence of amorphous atomic structure on energy storage and conversion characteristics, and summarized tuning strategies of amorphous alloy structure and performance. Finally, it provided an outlook on the challenges and development trends in this field.

Keywords

amorphous alloy;energy storage material;energy conversion material;catalysts;



非晶合金也被称为金属玻璃,是一种具有长程无序原子结构的合金材料  汪卫华. 非晶合金材料发展趋势及启示[J]. 中国科学院院刊,2022,37(3):352-359.
 汪卫华. 金属玻璃的过去、现在和未来[J]. 自然杂志,2022,44(3):173-181.
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1-3
。1960年,Duwez等以避免结晶为目的,通过快速冷却的方法制备出了Au-Si非晶合金  KLEMENT W,WILLENS R H,DUWEZ P. Non-crystalline structure in solidified gold–silicon alloys[J]. Nature,1960,187:869-870.
4
。随后,美国加州理工学院W. Johnson、日本东北大学A. Inoue  INOUE A,TAKEUCHI A. Recent development and application products of bulk glassy alloys[J]. Acta Materialia,2011,59(6):2243-2267.
5
、中国科学院物理研究所汪卫华院士等国内外团队进一步研究并开发了具有独特性能的非晶合金  赵睿,于吉皓,程琪,等. 华人在金属玻璃领域的重要贡献[J]. 自然杂志,2022,44(5):398-410.
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7-8
。经过半个多世纪的发展,非晶态合金已经在许多领域中发挥着重要作用,如光伏太阳能  TARIGAN H J,KAHLER N,RAMOS N S,et al. Low reflectance of nano-patterned Pt-Cu-Ni-P bulk metallic glass[J]. Applied Physics Letters,2015,107(2):021903.
9
、生物医药  SINGER J P,GOPINADHAN M,SHAO Z,et al. Nanoimprinting sub-100 nm features in a photovoltaic nanocomposite using durable bulk metallic glass molds[J]. ACS Applied Materials & Interfaces,2015,7(6):3456-3461.
 KINSER E R,PADMANABHAN J,YU R,et al. Nanopatterned bulk metallic glass biosensors[J]. ACS Sensors,2017,2(12):1779-1787.
 郑航兵,闫梦阳,安蓉,等. 纳米非晶及其在生物医学中的应用[J]. 稀有金属,2023,47(6):854-872.
10-12
、软磁材料  姚可夫,施凌翔,陈双琴,等. 铁基软磁非晶/纳米晶合金研究进展及应用前景[J]. 物理学报,2018,67(1):8-15.
13
、有机合成  KANEKO T,TANAKA S,ASAO N,et al. Reusable and sustainable nanostructured skeleton catalyst:heck reaction with nanoporous metallic glass Pd (PdNPore) as a support,stabilizer and ligand-free catalyst[J]. Advanced Synthesis & Catalysis,2011,353(16):2927-2932.
14
、锂离子电池  TANAKA S,KANEKO T,ASAO N,et al. A nanostructured skeleton catalyst:Suzuki-coupling with a reusable and sustainable nanoporous metallic glass Pd-catalyst[J]. Chemical Communications,2011,47(21):5985-5987.
15
、储氢材料  林怀俊,黄亮君,黄建灵. Mg基非晶态储氢合金的研究进展[J]. 中国材料进展,2023,42(1):1-9.
16
、电催化剂材料  JIA Z,NOMOTO K,WANG Q,et al. A self-supported high-entropy metallic glass with a nanosponge architecture for efficient hydrogen evolution under alkaline and acidic conditions[J]. Advanced Functional Materials,2021,31(38):2101586.
 JIA Z,ZHANG W C,WANG W M,et al. Amorphous Fe78Si9B13 alloy:an efficient and reusable photo-enhanced Fenton-like catalyst in degradation of cibacron brilliant red 3B-A dye under UV–vis light[J]. Applied Catalysis B:Environmental,2016,192:46-56.
 吴用,余鹏. 非晶态合金在催化领域的应用[J]. 中国科学:物理学 力学 天文学,2025,55(8):123-139.
17-19
等。

长程无序的原子排列结构使得非晶合金拥有比传统晶态合金更丰富的活性位点,以及更优异的化学与催化活性  简希颖,李海文,林怀俊. 非晶合金的调控策略及其在能源材料中的应用[J]. 中国科学:物理学 力学 天文学,2025,55(8):152-166.
 田霖,李春燕,翟建树,等.非晶合金的功能性研究进展[J]. 稀有金属,2021,45(8):998-1009.
20-21
。近年来,非晶合金在氢能、太阳能、二次电池等能源存储和转化领域展现了非常广阔的应用前景。基于此,本文系统综述了非晶合金作为电催化水分解催化剂、储氢材料、锂离子和锂金属电池材料、水系锌离子电池材料、太阳能电池关键材料、超级电容器等的最新研究进展。 除分析非晶合金在以上应用的优异表现之外,本文还特别关注非晶态原子结构对能源存储和转化特性的影响机理,并对非晶合金结构与性能的调控策略进行概述,最后总结并展望本领域的研究现状及未来发展趋势。

1     非晶合金能源材料

1.1     电催化制氢催化剂

电解水制氢是现阶段规模化生产绿氢的有效方式,由两个半反应组成。 其原理如图1所示  CHEN X Y,YANG J,CAO Y F,et al. Design principles for tungsten oxide electrocatalysts for water splitting[J]. ChemElectroChem,2021,8(23):4427-4440.
22
,在阴极端发生氢气析出反应(hydrogen evolution reaction,HER)产生氢气,在阳极端发生氧气析出反应(oxygen evolution reaction,OER)生成氧气。近20年来,非晶合金在电催化水分解催化剂领域具有非凡的应用潜力,在HER或OER反应中均展示了优异的催化特性。

图1     电解水制氢生产过程示意图
Fig. 1     Schematic diagram of hydrogen production process by water electrolysis  CHEN X Y,YANG J,CAO Y F,et al. Design principles for tungsten oxide electrocatalysts for water splitting[J]. ChemElectroChem,2021,8(23):4427-4440.
22

非晶合金作为HER或OER催化剂具有以下优势:1)大量随机取向的悬挂键,以及不饱和配位点有利于反应物的吸附,从而提供更多的活性位点; 2)高度缺陷的结构和无序的原子排列有利于离子扩散和电子转移,这可以提高催化动力学; 3)柔性和亚稳态结构在催化过程中可以自发地自我重构,具有良好的反应适应性。早在2016年,汪卫华院士团队就将Pd40Ni10Cu30P20非晶合金用于HER电解水催化剂。如图2(a,b)所示,该非晶态合金催化剂有着优异的催化活性与稳定性,达到10 mA/cm2的电流密度仅需76 mV的过电位,且催化稳定性优于商用Pt/C催化剂  HU Y C,WANG Y Z,SU R,et al. A highly efficient and self-stabilizing metallic-glass catalyst for electrochemical hydrogen generation[J]. Advanced Materials,2016,28(46):10293-10297.
23
。他们还发现,制得的Pd40Ni10Cu30P20非晶态合金催化剂在析氢过程中有着“自优化”的特点。 如图2(c)所示,Pd40Ni40Cu30P20以循环伏安法循环1000次后过电位有所降低,从76 mV 降低到48.5 mV,这也是非晶态合金催化剂相较于普通晶态催化剂的最大优点。

图2     (a) Pd40Ni10Cu30P20非晶态合金的线性扫描伏安(linear sweep voltammetry,LSV)曲线; (b) 商用Pt/C催化剂的LSV曲线; (c) 催化稳定性
Fig. 2     LSV curve of (a) Pd40Ni10Cu30P20 amorphous alloy and (b) commercial Pt/C catalyst; (c) Catalytic stability  HU Y C,WANG Y Z,SU R,et al. A highly efficient and self-stabilizing metallic-glass catalyst for electrochemical hydrogen generation[J]. Advanced Materials,2016,28(46):10293-10297.
23

由于贵金属原料价格高且资源稀缺,研究人员希望摆脱催化剂材料对贵金属的依赖。Wang等采用化学合成法开发了一种全新的不含贵金属的五元FeCoMoPB非晶态合金,该非晶态合金具有优异的碱性OER催化能力,在500 mA/cm2 大电流密度下过电位为331 mV。其中的Mo元素会诱发电子离域行为,促进电子在其周围区域重新分布,从而易失去或获取电子。同时,五元非晶态合金的化学复杂性形成了多种活性位点,能够大大降低OER过程的自由能  WANG Q Q,JIA Z,LI J Q,et al. Attractive electron delocalization behavior of FeCoMoPB amorphous nanoplates for highly efficient alkaline water oxidation[J]. Small,2022,18(46):2204135.
24

Cu基催化剂同样展现出了优异的氢电还原反应催化性能。近期,简希颖等  JIAN X Y,ZHANG W B,YANG Y X,et al. Amorphous Cu–W alloys as stable and efficient electrocatalysts for hydrogen evolution[J]. ACS Catalysis,2024,14(5):2816-2827.
25
通过磁控溅射法,成功研制出一系列成分跨度较广的CuW非晶态合金[见图3(a)]。这种Cu与W的无序结合,产生了显著的协同作用,提升了CuW非晶态合金在析氢反应中的固有催化活性和持久性。在10 mA/cm2的电流密度条件下,其过电位仅为65 mV[图3(b,c)]。而在100 mA/cm2的电流密度下,该合金仍能持续催化200 h以上[图3(d,e)]。根据密度泛函理论(density functional theory,DFT)的计算结果,CuW非晶态合金之所以具有高催化活性,是因为其氢吸附吉布斯自由能接近0 eV,而其出色的催化稳定性则归功于W元素的稳定性和优异的抗腐蚀性能。

图3     CuW非晶态合金的(a) XRD图、(b) LSV曲线、(c)化学成分与过电位的关系; (d) Cu50W50非晶态合金与商业Pt/C的循环稳定曲线对比; (e) CuW非晶态、晶态合金的HER活性与稳定性对比
Fig. 3     (a) XRD patterns,(b) LSV curves,and (c) relationship between chemical composition and overpotential of the CuW amorphous alloys; (d) Comparison of cyclic stability curves of Cu50W50 amorphous alloy and commercial Pt/C; (e) Comparison of HER activity and stability of CuW amorphous and crystalline alloys  JIAN X Y,ZHANG W B,YANG Y X,et al. Amorphous Cu–W alloys as stable and efficient electrocatalysts for hydrogen evolution[J]. ACS Catalysis,2024,14(5):2816-2827.
25

1.2     储氢材料

Mg基储氢合金作为一种新型高密度储氢材料,其氢化物MgH2的潜在储氢能力可达到7.6%(质量储氢密度),同时具备出色的循环储氢可逆性。加之Mg资源丰富,这类材料被视为极具潜力的储氢选择  朱敏,欧阳柳章. 镁基储氢合金动力学调控及电化学性能[J]. 金属学报,2021,57(11):1416-1428.
26
。不过,Mg基储氢材料需在较高温度下才能实现可逆储氢,这一特性对其应用范围产生了显著影响。近年来,国内外学者陆续研制了多种新型Mg系非晶态储氢合金。与传统晶体合金相比,非晶态合金的原子排列更为均匀,化学成分更加丰富,从而具有更广阔的储氢性能调整空间。得益于其长程无序的原子结构,部分Mg系非晶态合金展现了更高的储氢能力和更快的储氢动力学特性  LIN H J,HE M,PAN S P,et al. Towards easily tunable hydrogen storage via a hydrogen-induced glass-to-glass transition in Mg-based metallic glasses[J]. Acta Materialia,2016,120:68-74.
27

林怀俊等  LIN H J,HE M,PAN S P,et al. Towards easily tunable hydrogen storage via a hydrogen-induced glass-to-glass transition in Mg-based metallic glasses[J]. Acta Materialia,2016,120:68-74.
 ZHANG C,WANG H,OUYANG L Z,et al. Effect of Cu on dehydrogenation and thermal stability of amorphous Mg-Ce-Ni-Cu alloys[J]. Progress in Natural Science:Materials International,2017,27(5):622-626.
27-28
提出了一种创新方法,即利用元素混合焓进行微合金化,以此优化Mg基非晶态合金的储氢性能。他们成功研发出一种新型Mg基非晶态储氢合金,其储氢温度降至150 ℃,储氢量超过5%,且储氢性能易于调整。图4(a,b)展示了Mg基非晶态合金及氢化物的高分辨电子显微镜(high resolution transmission electron microscope,HRTEM)图像,揭示了吸氢后发生的玻璃态转变。引入5%(质量分数)的Ti,Ni,Co,Ag,Zn和Cu等元素,使脱氢温度显著降低[见图4(c)],特别是Mg65Ce10Ni20Cu5氢化物的脱氢温度下降了约200 ℃。图4(d)展示了合金化元素与氢的混合焓,证实了通过混合焓可以有效调整Mg基非晶态合金的储氢温度。另外,研究人员采用多靶磁控共溅射技术制备了不同厚度的Mg基非晶态合金薄膜  HAN B,YU S B,WANG H,et al. Nanosize effect on the hydrogen storage properties of Mg-based amorphous alloy[J]. Scripta Materialia,2022,216:114736.
29
,厚度范围在50 nm至500 nm之间,如图4(e)所示。随着纳米尺寸的减小,氢原子的扩散距离缩短,吸、放氢动力学显著增强。在纳米尺度下,Mg基非晶态合金在120 ℃即可实现完全可逆的吸、放氢,这一特性与块体非晶态合金截然不同[图4(f)]。纳米化非晶态合金在储氢循环中能够完全恢复其原子结构,证实了其作为一类完全可逆新型储氢材料的潜力。

图4     (a,b) Mg80Ce10Ni10非晶态合金和氢化物的HRTEM图; (c) Mg65Ce10Ni20X5非晶态合金氢化物的脱氢曲线; (d)合金化元素与氢的混合焓与脱氢温度之间的关系;(e,f) 300 nm和250 nm的Mg基非晶态合金薄膜的截面SEM图和循环脱氢动力学曲线
Fig. 4     (a,b) HRTEM images of Mg80Ce10Ni10 amorphous alloy and hydride; (c) Dehydrogenation curve of Mg65Ce10Ni20X5 amorphous alloy hydride; (d) Dehydrogenation temperature and mixing enthalpy of alloying elements and hydrogen  LIN H J,HE M,PAN S P,et al. Towards easily tunable hydrogen storage via a hydrogen-induced glass-to-glass transition in Mg-based metallic glasses[J]. Acta Materialia,2016,120:68-74.
27
; (e,f) Cross-sectional SEM images and cyclic dehydrogenation kinetic curves of 300 nm and 250 nm Mg-based amorphous alloy films  HAN B,YU S B,WANG H,et al. Nanosize effect on the hydrogen storage properties of Mg-based amorphous alloy[J]. Scripta Materialia,2022,216:114736.
29

1.3     太阳能电池

太阳能电池或光伏电池是一种基于半导体的器件,通过光伏效应将阳光直接转化为电能,已有研究证明了非晶合金在背接触硅太阳能电池中应用的优势。在这种特殊类型的太阳能电池中,Ag膜电极和Si发射极彼此接触,并通过由氧化物玻璃(oxide glasses,OG)和一些有机材料组成的导电黏合剂黏合在一起。然而,OG相对较差的导电性和劣化的钝化层严重影响了电池的效率。非晶合金因其高导电性和非晶态结构,被证明是OG的可行替代品。Kim等  KIM S Y,JEE S S,LIM K R,et al. Replacement of oxide glass with metallic glass for Ag screen printing metallization on Si emitter[J]. Applied Physics Letters,2011,98(22):222112.
30
使用Cu-Zr-Al非晶合金粉末代替OG,在Ag电极和Si发射极之间引发Si-Cu-Ag共晶反应。因此,在Si晶片上形成的Ag晶体呈现出倒三角金字塔形状[图5(a,b)]。这种结构设计显著提高了Ag电极和Si发射极之间的接触质量,从而增强了两个电极之间的结合,并提高了电导率。Kim等对多种Al基非晶合金的物理性能进行全面比较后,发现Al85Y8Ni5Co2非晶合金具有最佳的光电转换性能  KIM S J,KIM S Y,PARK J M,et al. Exploiting metallic glasses for 19.6% efficient back contact solar cell[J]. Applied Physics Letters,2012,101(6):064106.
31
。当与Ag粉混合并与Si晶片组装成交叉背接触电池时,在标准光照条件(1 sun)下实现了19.6%的光伏转换效率[图5(c)]。

图5     (a,b) Si晶片上具有Ag晶粒的Al85Y8Ni5Co2非晶合金的高角环形暗场图像和HRTEM图像; (c)电流-电压(I-V)曲线和电池参数
Fig. 5     (a,b) HAADF image and HRTEM image of Al85Y8Ni5Co2 amorphous alloy with Ag grains on Si wafer; (c) I-V curves and battery parameters  KIM S Y,JEE S S,LIM K R,et al. Replacement of oxide glass with metallic glass for Ag screen printing metallization on Si emitter[J]. Applied Physics Letters,2011,98(22):222112.
 KIM S J,KIM S Y,PARK J M,et al. Exploiting metallic glasses for 19.6% efficient back contact solar cell[J]. Applied Physics Letters,2012,101(6):064106.
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1.4     锂离子电池和锂金属电池

锂离子电池是目前商业化最广泛的储能系统。 在锂离子电池阳极中,锂和电解质的过度消耗会形成不稳定的固体-电解质界面(solid electrolyte interphase,SEI)和死锂,导致电池循环性能下降。使用亲锂非晶合金作为Si,Li阳极的替代品是一种有效的方法。目前,Al-Si-Ni和Al-Si-Mn非晶合金被认为是硅基和锂金属阳极的有效替代品  ZHANG L P,SONG X P,WANG F,et al. The electrochemical properties of Al-Si-Ni alloys composed of nanocrystal and metallic glass for lithium-ion battery anodes[J]. Journal of Solid State Electrochemistry,2012,16:2159-2167.
 SCHNABEL M,LIN T C,ARCA E,et al. Stable SEI formation on Al-Si-Mn metallic glass Li-ion anode[J]. Journal of the Electrochemical Society,2021,168(10):100521.
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。此外,基于非晶ZnP2通过高能球磨法制备的多组分复合材料ZnP2/Zn3(PO42/P/C,展现出优异的快速充放电性能。该材料的多孔结构和各向同性特性显著,提升了锂离子扩散动力学,在5 A/g的高电流密度下循环2200次后容量保持率高达92.3%  LIU L W,XIE H X,ZHENG Y S,et al. Multicomponent anodes based on amorphous ZnP2 for fast-charging/discharging lithium-ion batteries[J]. Advanced Energy Materials,2025,15(17):2404900.
34
。无阳极锂离子电池(anode-free lithium-ion batteries,AFLB)被认为是传统锂离子电池一种有前景的替代品。Kim等  KIM J G,GU D,CHO K H,et al. Exploiting zirconium-based metallic glass thin films for anode-free lithium-ion batteries and lithium metal batteries with ultra-long cycling life[J]. Small,2023,19(37):2301207.
35
使用磁控溅射工艺在AFLB的裸铜集电器上沉积了厚度为12 nm的Zr53Cu31Ni11Al5非晶合金薄膜(简写为Zr-MG)。在第一次充电循环中,Zr-MG为Li镀层提供了具有大量Li插入位点的均匀环境,这降低了成核过电位,并显示出比裸铜更致密的锂沉积[图6(a~d)]。以LiFePO4为阴极材料构建的全电池显示出125.9 mAh/g的高首次放电容量。在100次循环后,它还表现出令人满意的容量保持率(63.6%)和库仑效率(99.6%)[图6(e)]。

图6     (a~d) Zr-MG涂层铜集电器和裸铜集电器的顶面和横截面SEM图像; (e)电池的循环性能
Fig. 6     (a~d) Top surface and cross-sectional SEM images of Zr-MG coated copper current collector and bare copper current collector; (e) Battery cycling performance  KIM J G,GU D,CHO K H,et al. Exploiting zirconium-based metallic glass thin films for anode-free lithium-ion batteries and lithium metal batteries with ultra-long cycling life[J]. Small,2023,19(37):2301207.
35

脱合金法处理非晶合金可以提升非晶合金在锂离子电池中的性能。深圳大学沈军教授课题组使用特定浓度的HF对商用CuZr合金粉末进行脱合金处理,获得花瓣状CuZr非晶合金涂覆的Cu核壳结构粉末(CuZr-D*)  XIE Z Y,YE P F,LV J L,et al. A scalable slurry process to fabricate CuZr amorphous alloy with hybrid lithiophilic oxides for lithium metal anode[J]. Journal of Alloys and Compounds,2023,965:171326.
36
。然后将所得粉末制成浆料,并涂覆在铜箔表面,作为电池的阳极。CuZr-D*粉末表面富含亲锂氧化物,这些氧化物通过协同作用稳定SEI并防止锂枝晶过度生长。该阳极与LiFePO4阴极组装成一个完整的电池,测试表明:基于CuZr-D*的全电池具有良好的循环性能,首次放电容量为145 mAh/g。200次循环后,其容量保持率为87.5%,平均库仑效率为99.5%。

非晶合金也可以作为锂离子电池的阴极添加剂。Sung等  SUNG K J,CHOI H J,YI S,et al. Electrochemical properties of a Cu-base metallic glass matrix composite containing LiCoO2 cathode materials[J]. Materials Science and Engineering:A,2007,449-451:257-259.
37
使用气体雾化制备了Cu54Ni6Zr22Ti18非晶合金粉末,随后使用机械研磨将其与钴酸锂(LiCoO2)和炭黑粉末混合,测试结果表明,在阳极中添加非晶合金粉末可显著提高电极容量和循环耐久性。

锂金属电池(如锂硫电池和锂硒电池)因其更高的理论能量密度(锂硫电池理论比容量达1675 mAh/g,锂硒电池理论比容量达675 mAh/g)备受研究者青睐  MA S,RUAN Q L,LIU X C,et al. Insight into lithium-sulfur batteries performance enhancement:from metal nanoparticles to metal nanoclusters to single metal atoms[J]. Tungsten,2024,6(3):504-521.
 MA S,WAN G Y,YAN Z Y,et al. Eco-friendly aqueous binder derived from waste ramie for high-performance Li-S battery[J]. Chinese Chemical Letters,2025,36(5):109853.
 GU X X,KUANG L Y,LIN J,et al. Highly porous nitrogen-doped biochar nanosheets for high-performance Li-Se batteries[J]. Rare Metals,2023,42(3):822-829.
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。这些电池体系具有环境友好性和低成本优势,展现出广阔的应用前景。然而,锂硫电池中,硫的低导电性、多硫化物的穿梭效应以及硫电极的体积膨胀等问题严重影响了电池的循环稳定性和库仑效率  MA S,RUAN Q L,LIU X C,et al. Insight into lithium-sulfur batteries performance enhancement:from metal nanoparticles to metal nanoclusters to single metal atoms[J]. Tungsten,2024,6(3):504-521.
 MA S,WAN G Y,YAN Z Y,et al. Eco-friendly aqueous binder derived from waste ramie for high-performance Li-S battery[J]. Chinese Chemical Letters,2025,36(5):109853.
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。锂硒电池虽然在导电性和体积容量方面优于锂硫电池,但也存在多硒化物的溶解和体积变化等问题  GU X X,KUANG L Y,LIN J,et al. Highly porous nitrogen-doped biochar nanosheets for high-performance Li-Se batteries[J]. Rare Metals,2023,42(3):822-829.
40
。为解决这些问题,研究人员实施了多种策略,包括设计新型电极材料、优化电解液成分以及引入功能化隔膜等。Lü等  LYU Y,SU Q M,ZHANG K,et al. Crystalline/amorphous heterostructure CoNi/MoO3-x as an bidirectional catalyst for polysulfide reaction to enable high-sulfur-loading lithium-sulfur battery[J]. Sustainable Materials and Technologies,2025,43:e01307.
41
报道了一种CoNi/MoO3-x@CC非晶/晶态异质结构,在锂硫电池中表现出优异的性能。该结构通过协同效应显著提高了多硫化物的吸附和催化转化能力,使得电池在高硫负载(8.07 mg/cm2)下仍能实现1060 mAh/g的高可逆容量,并在500个循环后保持0.071%的低容量衰减率。这种非晶结构不仅提高了电池的硫利用率,还有效抑制了多硫化物的穿梭效应。

1.5     水系锌离子电池

水系锌离子电池因其高安全性、低成本和环境友好性,被认为是未来储能领域的有力候选技术之一。锌金属负极具有理论容量高(820 mAh/g)、氧化还原电位低以及资源丰富的优势,同时水系电解液的低挥发性和不可燃性进一步提升了电池的安全性和稳定性。然而,水系锌离子电池的应用仍面临以下挑战:一是锌负极的枝晶生长问题,导致电池内部短路和容量快速衰减; 二是锌负极表面的析氢腐蚀会加剧锌的消耗并降低电池的库仑效率  WANG Q,XU B H,DU Y X,et al. A cost-effective pyrrole additive for realizing highly stable Zn anode[J]. Rare Metals,2025,44(1):209-217.
 XIONG Y,CHENG H R,JIANG Y K,et al. A novel water-reducer-based hydrogel electrolyte for robust and flexible Zn-I2 battery[J]. Energy Storage Materials,2025,74:103981.
 KUANG L Y,XU B H,ZHANG L,et al. Zincophilic and hydrophobic bifunctional PFA-COOH-CNT artificial SEI film for highly stable Zn anode[J]. Nano Research,2025,18(2):94907156.
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。近年来,非晶合金被引入水系锌离子电池中,用于解决上述问题。例如,Zheng等  ZHENG J X,WU Y C,XIE H X,et al. In situ alloying sites anchored on an amorphous aluminum nitride matrix for crystallographic reorientation of zinc deposits[J]. ACS Nano,2023,17(1):337-345.
45
提出了一种基于非晶铝氮化物(AlN)基质的保护层(AlN/Ag)。 通过在锌负极表面原位合金化形成AgZn3合金位点,诱导锌沉积沿(002)晶面择优生长,从而显著抑制枝晶的形成。实验表明,采用AlN/Ag保护层的锌负极在1 mA/cm2和1 mAh/cm2的条件下实现了超过2600 h超长循环寿命。此外,基于AlN/Ag保护层的全电池(Zn||Mn1.4V10O24·nH2O)在5 A/g的高电流密度下经过8000次循环后,容量保持率仍可达51%,表现出优异的循环稳定性和抗腐蚀性能。非晶合金通过调节锌离子的沉积行为、抑制枝晶生长以及缓解析氢腐蚀,为水系锌离子电池的性能提升提供了新的解决方案。

1.6     超级电容器

非晶合金在超级电容器中的应用目前集中在柔性电极技术。 由于非晶合金本身不是主要的活性物质,通常需要制备纳米多孔金属或金属氧化物作为主体材料,而非晶合金主要充当柔性基板的作用。秦春玲等通过对Ni40Zr60和Ni45Ti20Zr25Al10非晶合金进行脱合金处理,为超级电容器开发了两种不同的三明治状结构柔性电极  ZHENG D H,ZHAO F,LI Y Y,et al. Flexible NiO micro-rods/nanoporous Ni/metallic glass electrode with sandwich structure for high performance supercapacitors[J]. Electrochimica Acta,2019,297:767-777.
 SUN X H,ZHENG D H,PAN F D,et al. 3D nanoporous Ni@NiO/metallic glass sandwich electrodes without corrosion cracks for flexible supercapacitor application[J]. Applied Surface Science,2021,545:149043.
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。在Ni45Ti20Zr25Al10非晶合金脱合金过程中,研究人员创新性地采用了一种连续O2辅助蚀刻的流动方法,促使材料的表面结构演变为规则的六边形柱状结构,形貌如图7(a)所示。 该电极在0.5 A/cm3时显示出745.3 F/cm3的高体积比电容[图7(b)]。在对Ni40Zr60非晶合金进行脱合金处理时,研究人员通过调节蚀刻溶液(HF)的浓度,成功地调节了样品的表面形态,从而形成了3D纳米多孔无裂纹结构,如图7(c)所示。该电极在0.5 A/cm3时具有640 F/cm3的高比电容[图7(d)]。同时,由于非晶合金具有优异的弹性和柔韧性,当电极弯曲180°时,仍能保持91.0%的高电容保持率。

图7     Ni45Ti20Zr25Al10非晶合金脱合金后的(a) SEM图像,(b)充放电曲线; Ni40Zr60非晶合金带脱合金后(c) SEM图像,(d)充放电曲线
Fig. 7     (a) SEM image and (b) charge/discharge curve of Ni45Ti20Zr25Al10 amorphous alloy after dealloying; (c) SEM image and (d) charge/discharge curve of Ni40Zr60 amorphous strip alloy after dealloying  ZHENG D H,ZHAO F,LI Y Y,et al. Flexible NiO micro-rods/nanoporous Ni/metallic glass electrode with sandwich structure for high performance supercapacitors[J]. Electrochimica Acta,2019,297:767-777.
 SUN X H,ZHENG D H,PAN F D,et al. 3D nanoporous Ni@NiO/metallic glass sandwich electrodes without corrosion cracks for flexible supercapacitor application[J]. Applied Surface Science,2021,545:149043.
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1.7     核能材料

核反应堆材料长期处在高温、高压、强中子辐照的环境下,这对服役材料的结构和性能提出了很高的要求。由于非晶合金具有长程无序的原子结构,与晶态合金相比,其不存在位错、层错、孪晶、晶界等缺陷,因此可以减少辐照条件下晶体缺陷诱导的辐射损伤。近年来,Fe基、Ni基和Zr基非晶合金展示了优异的抗离子辐照性能,吸引了不少核能材料领域研究人员的关注  卞西磊,王刚. 非晶合金的离子辐照效应[J]. 物理学报,2017,66(17):359-368.
 张舒研,高洋洋,张志彬,等. 新型高熵非晶合金的功能性能研究进展[J]. 稀有金属,2021,45(6):717-727.
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表1总结了上述非晶合金在能源储存和转换应用领域的性能表现、优势和挑战。

表1     非晶合金应用于能源储存和转换领域的性能对比
Table 1     Performance comparison of amorphous alloys in applications of energy storage and conversion
应用领域 非晶合金类型 性能表现 优势 挑战 文献
电催化制氢催化剂 Pd40Ni10Cu30P20非晶合金 过电位76 mV(10 mA/cm2),稳定性优于商用Pt/C催化剂 悬挂键和不饱和配位点提供丰富活性位点,柔性和亚稳态结构有利于催化动力学 贵金属催化剂成本高,资源稀缺  HU Y C,WANG Y Z,SU R,et al. A highly efficient and self-stabilizing metallic-glass catalyst for electrochemical hydrogen generation[J]. Advanced Materials,2016,28(46):10293-10297.
23
FeCoMoPB非晶合金 过电位331 mV(500 mA/cm2 化学复杂性形成多种活性位点,降低OER自由能 需进一步优化非贵金属催化剂的稳定性  WANG Q Q,JIA Z,LI J Q,et al. Attractive electron delocalization behavior of FeCoMoPB amorphous nanoplates for highly efficient alkaline water oxidation[J]. Small,2022,18(46):2204135.
24
CuW非晶合金 过电位65 mV(10 mA/cm2) 200 h以上稳定 Cu与W协同作用提升催化活性和稳定性,氢吸附吉布斯自由能接近0 eV 需进一步降低成本和提高大规模制备可行性  JIAN X Y,ZHANG W B,YANG Y X,et al. Amorphous Cu–W alloys as stable and efficient electrocatalysts for hydrogen evolution[J]. ACS Catalysis,2024,14(5):2816-2827.
25
储氢材料 Mg基非晶合金 储氢量超过5%,储氢温度150 ℃,纳米化后在120 ℃完全可逆吸放氢 原子排列均匀,化学成分丰富,储氢动力学快 高温储氢限制应用范围,需进一步降低储氢温度  LIN H J,HE M,PAN S P,et al. Towards easily tunable hydrogen storage via a hydrogen-induced glass-to-glass transition in Mg-based metallic glasses[J]. Acta Materialia,2016,120:68-74.
 ZHANG C,WANG H,OUYANG L Z,et al. Effect of Cu on dehydrogenation and thermal stability of amorphous Mg-Ce-Ni-Cu alloys[J]. Progress in Natural Science:Materials International,2017,27(5):622-626.
 HAN B,YU S B,WANG H,et al. Nanosize effect on the hydrogen storage properties of Mg-based amorphous alloy[J]. Scripta Materialia,2022,216:114736.
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太阳能电池 Cu-Zr-Al非晶合金 光伏转换效率19.6%(1 sun) 高导电性和非晶态结构替代传统氧化物玻璃,提升电极接触质量 需进一步优化材料的长期稳定性和成本  KIM S Y,JEE S S,LIM K R,et al. Replacement of oxide glass with metallic glass for Ag screen printing metallization on Si emitter[J]. Applied Physics Letters,2011,98(22):222112.
30
锂离子电池和锂金属电池 Al-Si-Ni非晶合金 提供均匀Li插入位点,降低成核过电位 亲锂性提升锂沉积均匀性,抑制锂枝晶生长 需解决锂金属阳极的体积膨胀和界面稳定性问题  ZHANG L P,SONG X P,WANG F,et al. The electrochemical properties of Al-Si-Ni alloys composed of nanocrystal and metallic glass for lithium-ion battery anodes[J]. Journal of Solid State Electrochemistry,2012,16:2159-2167.
32
CuZr-D*非晶合金 首次放电容量在145 mAh/g下200次循环后容量保持率87.5% 富含亲锂氧化物可稳定SEI层,防止锂枝晶过度生长 需进一步提升材料的循环寿命和倍率性能  XIE Z Y,YE P F,LV J L,et al. A scalable slurry process to fabricate CuZr amorphous alloy with hybrid lithiophilic oxides for lithium metal anode[J]. Journal of Alloys and Compounds,2023,965:171326.
36
水系锌离子电池 AlN/Ag非晶合金保护层 超过2600 h循环寿命(1 mA/cm2);在 5 A/g下8000次循环后容量保持率51% 抑制锌枝晶生长,缓解析氢腐蚀 需进一步优化材料的机械强度和成本  ZHENG J X,WU Y C,XIE H X,et al. In situ alloying sites anchored on an amorphous aluminum nitride matrix for crystallographic reorientation of zinc deposits[J]. ACS Nano,2023,17(1):337-345.
45
超级电容器 Ni45Ti20Zr25Al10非晶合金 体积比电容745.3 F/cm3(0.5 A/cm3); 弯曲180°后电容保持率91.0% 高比表面积和催化活性,优异柔韧性和弹性 需进一步提升材料的能量密度和循环稳定性  SUN X H,ZHENG D H,PAN F D,et al. 3D nanoporous Ni@NiO/metallic glass sandwich electrodes without corrosion cracks for flexible supercapacitor application[J]. Applied Surface Science,2021,545:149043.
47
核能材料 Fe基、Ni基、Zr基非晶合金 优异抗离子辐照性能,减少辐照损伤 长程无序原子结构减少晶体缺陷诱导的辐射损伤 需进一步验证材料在极端条件下的长期稳定性  卞西磊,王刚. 非晶合金的离子辐照效应[J]. 物理学报,2017,66(17):359-368.
 张舒研,高洋洋,张志彬,等. 新型高熵非晶合金的功能性能研究进展[J]. 稀有金属,2021,45(6):717-727.
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2     非晶合金能源材料结构与性能的调控策略

综上,非晶合金在电催化水分解催化剂、储氢材料、锂离子电池材料、太阳能电池关键材料、超级电容器等能源材料领域已有优异的应用表现。为了进一步提升非晶合金在本领域的性能,研究人员发展了多种结构与性能的调控策略和技术,如构筑非晶-纳米晶复合结构、利用去合金化设计纳米多孔非晶合金、对非晶合金的能量进行调控、发展新型高熵非晶合金和纳米化非晶合金等。下面对这些调控策略进行介绍和评述。

2.1     构筑非晶-纳米晶复合结构

由于在界面处的原子排列很容易产生协同效应,因此构筑非晶-纳米晶复合结构可以有效提升材料的能源储存或转换性能。自20世纪90年代以来,国内外许多科研人员通过快速凝固技术直接制备非晶-纳米晶双相合金,或利用非晶合金作为前驱体间接诱导制备非晶-纳米晶复合材料,使其获得优异的吸放氢性能。如Spassov  SPASSOV T,KÖSTER U. Hydrogenation of amorphous and nanocrystalline Mg-based alloys[J]. Journal of Alloys and Compounds,1999,287(1-2):243-250.
50
、Yartys  DENYS R V,POLETAEV A A,SOLBERG J K,et al. LaMg11 with a giant unit cell synthesized by hydrogen metallurgy:Crystal structure and hydrogenation behavior[J]. Acta Materialia,2010,58(7):2510-2519.
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、武英  WU Y,HAN W,ZHOU S X,et al. Microstructure and hydrogenation behavior of ball-milled and melt-spun Mg-10Ni-2Mm alloys[J]. Journal of Alloys and Compounds,2008,466(1-2):176-181.
 WU Y,LOTOTSKY M V,SOLBERG J K,et al. Microstructural evolution and improved hydrogenation-dehydrogenation kinetics of nanostructured melt-spun Mg-Ni-Mm alloys[J]. Journal of Alloys and Compounds,2011,509(S2):S640-S645.
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、张庆安  ZHANG Q A,LIU D D,WANG Q Q,et al. Superior hydrogen storage kinetics of Mg12YNi alloy with a long-period stacking ordered phase[J]. Scripta Materialia,2011,65(3):233-236.
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、朱敏  LIN H J,OUYANG L Z,WANG H,et al. Hydrogen storage properties of Mg-Ce-Ni nanocomposite induced from amorphous precursor with the highest Mg content[J]. International Journal of Hydrogen Energy,2012,37(19):14329-14335.
 LIN H J,ZHANG C,WANG H,et al. Controlling nanocrystallization and hydrogen storage property of Mg-based amorphous alloy via a gas-solid reaction[J]. Journal of Alloys and Compounds,2016,685:272-277.
55-56
、张羊换  ZHANG Y H,HUANG G,YUAN Z M,et al. Electrochemical hydrogen storage behaviors of as-cast and spun RE-Mg-Ni-Co-Al-based AB2-type alloys applied to Ni-MH battery[J]. Rare Metals,2020,39(2):181-192.
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等课题组在此方面开展了大量的研究。通过构筑新型的非晶-纳米复合结构,同时在材料中引入有效催化剂(包括过渡金属、氧化物、卤化物等),可以有效地改变氢扩散路径,提高储氢材料的吸/放氢动力学。 非晶-纳米晶复合材料有利于材料在吸放氢循环过程中保持结构稳定,从而达到提升储氢循环寿命的效果  李谦,孙璇,罗群,等. 镁基材料中储氢相及其界面与储氢性能的调控[J]. 金属学报,2023,59(3):349-370.
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。此外,非晶-纳米晶复合结构在多种电化学能源存储和转化应用中也展示了优异的性能,包括HER反应、OER反应、超级电容器、锂离子电池和锂硫电池等  JIN Y C,ZHANG M X,SONG L,et al. Research advances in amorphous‐crystalline heterostructures toward efficient electrochemical applications[J]. Small,2023,19(10):2206081.
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2.2     利用去合金化设计纳米多孔非晶合金

以非晶合金作为前驱体,通过可控去合金化处理,可以制备纳米多孔非晶合金材料,该材料在能源存储和转换中有着广阔的应用。焦维等通过选择性相溶解制备了Zr基纳米多孔非晶合金。 由于纳米多孔结构具有大比表面积,且非晶合金具备高氢扩散率,因此该材料展示出非常优异的吸氢性能。 在同样吸氢条件下,其吸氢动力学较块体非晶合金和多孔结晶合金提升约两个数量级  JIAO W,LIU P,LIN H J,et al. Tunable nanoporous metallic glasses fabricated by selective phase dissolution and passivation for ultrafast hydrogen uptake[J]. Chemistry of Materials,2017,29(10):4478-4483.
60
。储非等将Fe78Si9B13合金在2 M NaOH溶液中腐蚀不同时间,制备了Fe78Si9B13纳米多孔合金,合金的表面形成了均匀且丰富的纳米孔(孔径约50~100 nm),该纳米多孔非晶合金在1 M KOH环境中仅需199 mV的过电位便可获得10 mA/cm2的电流密度,而达到相同电流密度的块体非晶合金则需要更高的过电位(386 mV),此外该合金还表现出优异的循环性能  JIAN X Y,LI J,HAN B,et al. Corroded Fe78Si9B13 amorphous alloy as electrocatalyst for oxygen evolution reaction of water splitting[J]. Journal of Non-Crystalline Solids,2023,603:122117.
 CHU F,WU K Y,MENG Y Y,et al. Nanoporous amorphous Fe78Si9B13 alloys for hydrogen evolution in alkaline media[J]. Journal of Non-Crystalline Solids,2021,566:120831.
61-62

除了储氢和制氢领域,纳米多孔非晶合金由于高比表面积和催化活性,在甲醇电催化  徐秀月,李艳辉,张伟. Fe(Pt,Ru)B非晶带材脱合金制备纳米多孔PtRuFe及其甲醇电催化性能[J]. 金属学报,2020,56(10):1393-1400.
63
、锂离子电池  XIE Z Y,YE P F,LV J L,et al. A scalable slurry process to fabricate CuZr amorphous alloy with hybrid lithiophilic oxides for lithium metal anode[J]. Journal of Alloys and Compounds,2023,965:171326.
36
、超级电容器  ZHENG D H,ZHAO F,LI Y Y,et al. Flexible NiO micro-rods/nanoporous Ni/metallic glass electrode with sandwich structure for high performance supercapacitors[J]. Electrochimica Acta,2019,297:767-777.
46
、污水处理  CHEN S Q,LI M,JI Q M,et al. Functional 3D nanoporous Fe-based alloy from metallic glass for high-efficiency water splitting and wastewater treatment[J]. Journal of Non-Crystalline Solids,2021,571:121070.
 ZHANG L C,JIA Z,LYU F C,et al. A review of catalytic performance of metallic glasses in wastewater treatment:Recent progress and prospects[J]. Progress in Materials Science,2019,105:100576.
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等领域也有越来越多的研究和应用。

2.3     非晶合金的原子能量调控

根据能量势垒理论,体系能量状态和流动势垒的变化直接对应于系统动力学性能的变化  汪卫华. 非晶态物质的本质和特性[J]. 物理学进展,2013,33(5):177-351.
66
。研究表明,通过低温退火  潘杰,段峰辉. 非晶合金的回春行为[J]. 金属学报,2021,57(4):439-452.
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、冷热循环  殷更,刘辉,许永康,等. 非晶合金深冷循环处理研究进展[J]. 材料热处理学报,2020,41(7):1-13.
68
、弹性加载  周敬宇,时博. 弹性加载调控Ti基非晶合金非均匀结构及性能研究[J]. 特种铸造及有色合金,2024,44(10):1368-1374.
69
、机械超声  李信,马将. 非晶合金的超声制造与成型[J]. 自然杂志,2020,42(2):125-133.
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、大塑性变形  CHU F,HAN B,EDALATI K,et al. Severe plastic deformed Pd-based metallic glass for superior hydrogen evolution in both acidic and alkaline media[J]. Scripta Materialia,2021,204:114145.
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等技术可调控非晶合金的能量状态,实现对其性能的精确设计。

储非等采用高压扭转法(high pressure torsion,HPT)对Pd40Cu30Ni10P20非晶合金进行剧烈塑性变形处理,将非晶合金样品的能量提高约21.7 J/g,但没有引起结晶。经HPT处理的Pd40Cu30Ni10P20非晶合金在酸性和碱性介质中,其HER性能大幅度提升,其在10 mA/cm2电流密度下,在0.5 M H2SO4和1.0 M KOH中的过电位仅为76 mV和209 mV,远小于相同条件下未经过HPT处理的样品(分别为179 mV和379 mV)。HER性能的改善主要归因于剧烈塑性变形使非晶基体中流动单元的密度显著增加,能量状态得到提升。类似地,通过机械超声处理Fe78Si9B13非晶合金,也可以提升其能量状态,获得优异的HER活性和稳定性  WU K Y,MENG Y Y,LI X,et al. Improved alkaline hydrogen evolution performance of a Fe78Si9B13 metallic glass electrocatalyst by ultrasonic vibrations[J]. Intermetallics,2020,125:106820.
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2.4     新型高熵非晶合金

高熵合金的概念始于2004年  YEH J W,CHEN S K,LIN S J,et al. Nanostructured high‐entropy alloys with multiple principal elements:novel alloy design concepts and outcomes[J]. Advanced Engineering Materials,2004,6(5):299-303.
73
。研究表明,当多种元素以(近)等原子比例混合后得到的合金形成简单的固溶体结构,而非复杂的金属间化合物,这打破了传统合金以混合焓为主的设计理念,为新材料的研发打开了一个广阔的成分设计空间  李天昕,王书道,卢一平,等. 高熵合金材料研究进展与展望[J]. 中国工程科学,2023,25(3):170-181.
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高熵化和非晶化协同策略,可以提升材料在能源存储和转化领域的性能。贾喆等报道了PdPtCuNiP等原子比高熵非晶合金在碱性和酸性条件下优异的HER性能  JIA Z,NOMOTO K,WANG Q,et al. A self-supported high-entropy metallic glass with a nanosponge architecture for efficient hydrogen evolution under alkaline and acidic conditions[J]. Advanced Functional Materials,2021,31(38):2101586.
17
,PdPtCuNiP高熵非晶合金的表面脱合金产生了具有纳米孔和嵌入纳米晶体的纳米海绵状结构,提供了丰富的活性位点,具有出色的HER活性。在1.0 M KOH和0.5 M H2SO4溶液中,在10 mA/cm2电流密度下获得的过电位分别低至32 mV和62 mV。结合DFT计算结果可知,这是由于晶格畸变和高熵复杂性对电子结构产生强烈的协同效应,进一步稳定了氢质子的吸附/解吸,从而提升了HER活性。卢志源等  LU Z,LI X,KE H B,et al. Effects of amorphization and interlayer on the hydrogen storage properties of multi-component Ti-V-Zr-Nb-M (M=Mg,Al) alloy films[J]. Journal of Alloys and Compounds,2024,1005:176099.
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报道了Ti-V-Zr-Nb-M(M=Mg,Al)高熵非晶合金的储氢性能。 由于高熵化效应,合金在吸、放氢后仍保持非晶态结构,材料无需活化,在室温下的吸氢容量约0.50%,轻元素Mg和Al的加入提高了材料的吸放氢性能。高熵化效应使非晶合金的混合熵升高,可以有效抑制离子辐照引起的结晶,因此非晶合金的抗辐照的特性也得到大幅度提升  张舒研,高洋洋,张志彬,等. 新型高熵非晶合金的功能性能研究进展[J]. 稀有金属,2021,45(6):717-727.
49

2.5     纳米化非晶合金

自1960年以来,大多数非晶合金是通过快速凝固技术制备的,而块体的合金由于比表面积较低,化学活性位点较少,因此在能源存储和转化材料中表面性能不够优异。通过进一步纳米化制备纳米非晶合金(Nanoglass),可以显著提高材料的表面能和催化活性,纳米化非晶合金在储氢合金、电解水催化剂等领域展现出引人注目的性能。徐诚等  XU C,LIN H J,EDALATI K,et al. Superior hydrogenation properties in a Mg65Ce10Ni20Cu5 nanoglass processed by melt-spinning followed by high-pressure torsion[J]. Scripta Materialia,2018,152:137-140.
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通过大塑性变形工艺在Mg基非晶合金基础上制备了新型纳米非晶合金,提升了储氢动力学性能,在同等吸氢条件下Mg基非晶合金无法吸氢,而纳米非晶合金可以不经过活化而快速吸氢。

此外,可以通过磁控共溅射方法制备非晶纳米薄膜,这对于研究纳米尺度下非晶合金的性能非常有效。韩冰等  HAN B,YU S B,WANG H,et al. Nanosize effect on the hydrogen storage properties of Mg-based amorphous alloy[J]. Scripta Materialia,2022,216:114736.
29
利用磁控共溅射方法制备不同厚度的Mg基非晶合金薄膜,厚度从50 nm到500 nm不等。结果表明,随着薄膜厚度的降低,材料的吸、放氢动力学性能显著提升。在纳米尺寸下,Mg基非晶合金还可在120 ℃完全可逆储氢,而Mg基非晶合金在同等条件下无法达到这一效果。

2.6     新型非晶合金

除了以上策略以外,研究人员还发明了互不溶体系非晶合金  JIAN X Y,ZHANG W B,YANG Y X,et al. Amorphous Cu–W alloys as stable and efficient electrocatalysts for hydrogen evolution[J]. ACS Catalysis,2024,14(5):2816-2827.
25
 CHEN L,JIAN X Y,ZHANG P,et al. Low-Pt-loaded Pt-CuW metallic glass as highly efficient catalysts for hydrogen evolution reaction[J]. Journal of Alloys and Compounds,2025,1011:178445.
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、非晶合金的复合调控策略  YU X Q,GONG X H,QIAO H Q,et al. Amorphous‐crystalline heterostructured nanoporous high‐entropy alloys for high‐efficiency pH‐universal water splitting[J]. Small Methods,2024,8(10):2400793.
 范雪茹,凡双玉,谢磊,等. Cu元素添加对Fe基非晶合金结构-性能影响的研究进展[J]. 铜业工程,2023(2):15-27.
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等方法制备新型非晶合金,获得了优异的储氢、储能、电催化效果。

3     总结与展望

本文系统地概述了非晶合金作为电催化水分解催化剂、储氢材料、锂离子电池材料、太阳能电池关键材料、超级电容器等材料和器件的最新研究进展。可见,非晶合金在能源存储和转化材料应用中有着非常优异的表现,非晶态原子结构对能源存储和转化特性具有至关重要的贡献。

非晶合金结构与性能的调控策略包括但不限于构筑非晶-纳米晶复合结构、利用去合金化设计纳米多孔非晶合金、对非晶合金能量进行调控、发展新型高熵非晶合金和纳米化非晶合金等,这些策略对于进一步提升非晶合金在能源存储和转化材料中的性能具有非常有效的指导意义。基于目前的进展,作者认为还有必要从以下几个方面进一步开展研究:

1) 进一步开发廉价、性能优异的非晶合金,比如在催化剂领域,目前含有贵金属的材料仍然具有最优的综合性能,开发无贵金属或贵金属含量低的非晶合金具有非常重要的应用价值;

2) 多种调控策略协同并用有望开拓全新的研究思路,如在非晶合金基体上进一步纳米化、高熵化、设计多孔结构、调控能量状态等,值得进一步探索研究;

3) 结合人工智能模型,可显著提升非晶合金能源存储和转化材料的开发效率,值得进一步投入研发资源;

4) 目前对于非晶合金在能源储存和转化领域的应用还集中在实验室阶段,如何走向产品中试,甚至规模化制备,是科研技术人员值得深思的一个重要命题。

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