现代化工

现代化工 ›› 2025, Vol. 45 ›› Issue (9) : 54-58. DOI: 10.16606/j.cnki.issn0253-4320.2025.09.011

技术进展

可应用于锌空气电池的三维纳米催化材料结构设计研究进展

刘笑盈 ¹ ,
张浩栋 ¹ ,
王亚铭 ¹ ,
范扬 ¹ ,
宋海欧 ² ,
居学海 ¹ ,
张树鹏 ¹^,^*

作者信息 +

Research progress on structural design of three-dimensional nanocatalytic materials applicable for zinc-air batteries

Author information +

文章历史 +

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摘要

围绕锌空气电池(ZABs)的析氧反应(OER)和氧还原反应(ORR)电催化性能提升,从三维纳米结构角度综述了空心、多面体、核壳、蜂窝状、三明治结构和其他三维结构的形貌构建策略和性能调控机制,并分析了这些材料在ZABs中的电化学应用,最后总结了提升三维结构催化剂电化学性能的科学策略,并对ZABs的未来研究方向进行了展望。

Abstract

Focusing on enhancing the electrocatalytic performance of zinc-air batteries (ZABs) in oxygen evolution reaction (OER) and oxygen reduction reaction (ORR),this paper reviews the morphology construction strategies and performance regulation mechanism for hollow,polyhedral,core-shell,honeycomb,sandwich and other three-dimensional structure from the perspective of three-dimensional nanostructure,and analyzes their electrochemical applications in ZABs.Finally,the scientific strategies to improve the electrochemical performance of the catalysts with a three-dimensional structure are summarized,and the research directions regarding to ZABs in the future are prospected.

Graphical abstract

关键词

锌空气电池 / 三维结构 / 氧还原

Key words

zinc-air batteries / three-dimensional structure / oxygen reduction reaction

Author summay

刘笑盈(2000-),女,硕士生。

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School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China), AuthorCompanyExt(id=1241416600152142392, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240720141232599289, companyId=1241416600143753782, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1.南京理工大学化学与化工学院,江苏南京 210094)])])] 刘笑盈,张浩栋,王亚铭,范扬,宋海欧,居学海,张树鹏. 可应用于锌空气电池的三维纳米催化材料结构设计研究进展[J]. , 2025, 45(9): 54-58 DOI:10.16606/j.cnki.issn0253-4320.2025.09.011

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传统化石燃料燃烧产生的废气会对环境造成不利影响,因此需要寻找更清洁、可持续且可再生的能源以满足未来的能源需求^[1]。锌-空气电池(ZABs)具有低成本、高安全性、高理论能量密度(1 084 Wh/kg)、稳定的放电电压(1.2~1.4 V)等优点,有望成为新一代能源转换和储存装置^[2]。然而,其充放电过程中的析氧反应(OER)和氧还原反应(ORR)缓慢的动力学阻碍了ZABs的商业化^[3]。因此,研发出具有低成本、高活性和稳定性的ORR/OER催化剂,有助于推动ZABs在便携式电子设备、电动汽车等领域的应用。

碳基材料中,一维碳纳米管和二维石墨烯等,通过杂原子掺杂或缺陷工程等调控策略,可以诱导电荷转移从而调节催化性能,有望成为贵金属催化剂的替代品^[4-6]。近年来,三维结构材料在促进离子迁移和氧气扩散方面效果显著,这有助于加快ORR/OER的动力学过程^[7]。多孔碳材料因丰富的孔隙率、良好的生物相容性、可调的框架结构等优势,被认为是有前途的催化剂载体^[8]。过渡金属(如Fe、Co、Ni、Mn)具有多变的晶体结构和活性缺陷位点可调节等优势^[9],通过合理设计多孔碳材料的三维结构以提高过渡金属活性位点的利用率,对ZABs的发展具有极其重要的意义。

本文中综述了三维中空、多面体、核壳、蜂窝状、三明治结构及其他三维结构,比较了各类材料设计策略和优势,并探讨了它们的ORR/OER催化性能及在ZABs中的应用。最后,对ORR/OER电催化剂以及ZABs的未来发展方向进行了展望。

1 空心结构

空心结构以高孔隙率和大比表面积等特性脱颖而出,促进了反应中间体的快速传输^[10]。通过模板辅助、刻蚀等技术手段制备的中空结构的催化剂,在提升活性位点的裸露度以及优化ORR/OER反应中三相界面物质传输效率展现出显著优势,被认为是很有潜力的提高ORR/OER催化性能的方法。

1.1 模板辅助

目前,模板辅助法主要集中在SiO₂、ZnO等模板材料上,其中,最常见的当属SiO₂。Pan等^[11]利用SiO₂为模板,通过一锅法合成N、S共掺杂的Fe原子分散的分级多孔材料FeS/FeN-NC-X₄,如图1所示,聚多巴胺结构中的功能基团赋予材料黏附性能,有效防止了热解过程中金属的团聚。S原子的掺杂有助于形成Fe-S、噻吩硫、氧化硫等有效活性位点,FeS/FeN-NC-X₄组装的ZABs展现出了优异的稳定性,最大功率密度达到156 mW/cm²,并且能够在5 mA/cm²电流密度下连续工作400 h。

普鲁士蓝类似物(PBA)因易合成、金属成分和空位可调的优点在ORR/OER催化剂方面展现出广阔的应用前景^[12]。Jang等^[13]以NiFe-PBA为模板成功制备了具有中空结构的OER/OER催化剂NiFe/W_0.3C@NC,经过热解还原得到嵌入NiFe合金和碳化钨(WC)纳米颗粒的氮掺杂的碳壳,WC与NiFe之间的协同作用改变了局部电子结构,从而显著提高了ORR/OER的固有催化活性。

1.2 刻蚀

金属有机框架(MOFs)通过刻蚀可以在内部创建中空/大孔孔隙并且不改变母体晶体框架,这些孔结构有助于加速反应过程中物质的传递^[14]。Zhu等^[15]通过选择性刻蚀和离子交换策略设计并合成Hf掺杂的CoP空心纳米立方体,利用酸性二甲酚橙溶液对ZIF-67的(211)晶面进行刻蚀,得到独特的钟状结构,随后经过Hf⁴⁺掺杂和磷化处理制备空心纳米立方体材料Hf/XO-CoP,纳米立方体活性位点的暴露以及Hf⁴⁺掺杂调节电子结构使得该材料在OER催化过程中表现出292 mV的过电位和优异的稳定性。

2 MOFs多面体结构

MOFs的有序晶体结构、丰富孔隙率、规则外观等优点被认为是合成多面体催化剂的良好前驱体^[16]。Wang等^[17]利用铜箔避免Fe²⁺氧化制备具有截断菱形十二面体结构FeCu-ZIF,如图2所示,经热解处理后得到Fe、Cu配位ZIF衍生碳骨架 Cu@Fe-N-C,材料保持了初始的截断菱形十二面体形状,Cu@Fe-N-C因双金属活性位点、大表面积、高氮掺杂水平和导电碳骨架,从而具有优异的ORR性能。在碱性介质中的半波电位为0.892 V,并具有优异的稳定性和甲醇抗干扰能力,在酸性介质中的性能与Pt催化剂相当,组装ZABs后Cu@Fe-N-C的峰值功率密度为92 mW/cm²,优于Pt/C。Han等^[18]利用MOF-5超高的比表面积和立方体多孔结构,通过简单的物理过程将FePc负载到碳化的MOF-5上,制备了FePc@C-MOF5催化剂,归因于MOF-5的分级孔道工程,FePc@C-MOF5电催化剂显示出高含量的Fe(质量分数5.68%)和多个暴露的活性位点,在0.1 mol/L KOH中表现出0.915 V的半波电位,在锌空气液流电池(ZAFBs)应用中,FePc@C-MOF5的最大功率密度为146 mW/cm²,经过200 h后的充电/放电循环后仍具有优异的稳定性。

3 核壳结构

核壳结构材料因纳米级尺寸效应、可调的结构而备受瞩目。将高效材料组装成核壳结构能够增强不同组分间的强相互作用,从而提高材料的整体性能^[19]。Bai等^[20]首先合成了ZIF-8@ZIF-67核壳结构,随后通过部分硫化-热解策略制备了均匀锚定在N、S共掺杂碳材料表面的Co/Co₉S₈异质结材料Co/Co₉S₈@NSC,如图3所示,界面诱导电场效应有利于界面电荷的重新分布,改善了Co—S键的共价性,有效促进了电荷转移,优化了ORR和OER过程中氧中间体的吸附。在电化学测试中,该材料展现出0.88 V的ORR半波电位和137 mV的OER过电位,组装的ZABs最大功率密度达到267.83 mW/cm²,并且在10 mA/cm²电流密度下具有超过1 000 h的循环稳定性。

将聚合物包裹在前驱体外侧是合成核壳结构的常用方法。Zhang等^[21]通过固相合成法将Fe-酞菁共轭微孔聚合物(Fe-Phth-CMP)包覆ZIF-67(Fe-Phth-CMP@ZIF-67),经碳化后转化为高度分散的FeCo合金和Fe/Co-N嵌入氮掺杂多孔碳材料 P₂Z₃-900,对ORR/OER表现出卓越的催化活性和耐久性,P₂Z₃-900的半波电位为0.81 V,极限电流密度为5.56 mA/cm²,在10 mA/cm²时的起始电位为1.60 V。

4 蜂窝状结构

蜂窝状纳米结构因出色的机械稳定性、低扩散阻力以及片层内大的暴露面积而受到广泛关注^[22]。这些特性不仅能提高反应效率,还能增强催化剂的稳定性,使得这类材料在ZABs的应用领域展现出巨大的潜力。Li等^[23]通过一步热解法,将分离的Co和VN纳米颗粒包裹在介孔氮掺杂碳纳米片中,合成了三维蜂窝状结构材料(Co-VN-NC)。这种3D蜂窝纳米结构具有高比表面积(433.20 m²/g),有助于活性位点在电解液中与反应物充分接触,钴和钒氮化物纳米粒子之间的高效电子转移能力,以及氮掺杂碳层使得材料在碱性和酸性溶液中均展现出优异的ORR性能,并且具有优异的稳定性。

气凝胶作为一种三维网络结构的介孔材料,以高比表面积和高电导率,在电催化领域展现出重要的应用潜力^[24]。Wu等^[25]通过定向冷冻铸造和热解策略构建了3D蜂窝状材料FeP/Fe₂O₃@NPCA,如图4所示,该材料能够实现快速气体/离子扩散,作为自支撑阴极组装ZABs,在电流密度为20 mA/cm²时的比容量为648 mAh/g,在柔性ZABs中表现出良好的柔韧性和稳定性。

5 三明治结构

三明治状结构材料因能有效防止活性中心的聚集和迁移,在ORR/OER电催化领域展现出显著的研究价值和应用潜力。Palanisamy等^[26]首先将 FeNi-MOF进行碳化处理,得到NiFe₂O₄/TiO₂纳米晶体,然后与2D MXene纳米片复合,并在350℃下进行热处理,形成了三明治状结构材料NiFe₂O₄/TiO₂@Ti₃C₂。Ti₃C₂ MXene层极大地提高了材料的导电性和耐用性。得益于混合材料独特的物理化学性质和结构特征,其ORR/OER催化性能得到显著加强,使得材料在ZABs中展现出较好的功率密度、倍率性能和循环稳定性。

氮化硼(BN)因大比表面积、热稳定性以及类石墨烯纳米片等优点,在催化发展中发挥着重要作用^[27]。Yu等^[28]以碳纳米管为导电材料,采用络合还原法构建了Ag-BN/C三明治状纳米结构。如图5所示,Ag、h-BN和碳纳米管的共同作用有助于在ORR/OER电催化过程中实现4e^-过程。Ag-BN/C的ORR/OER活性与商用Pt/C和RuO₂相当,并且在碱性电解质中展现出优异的稳定性。

6 其他三维结构

构建具有大的比表面积和高催化活性的三维结构催化剂是提升ORR/OER催化活性的有效策略。Zhou等^[29]合成了一种嵌入一维氮掺杂碳纳米管修饰的三维十字型结构的ORR/OER/HER催化剂CoFeN-NCNT s//CCM。如图6所示,得益于Co_5.47N/Co₇Fe₃界面共轭作用以及一维/三维分级结构所提供的大比表面积,该催化剂展现出优异的电催化性能,ORR的半波电位达到0.84 V,OER的过电位为320 mV,HER的过电位为-151 mV。此外,组装的ZABs展现出145 mW/cm²的高功率密度和445 h的循环稳定性。

MOFs结构的可调性为合成多样化的三维结构提供了便利。Gopalakrishnan等^[30]通过配体优化策略,巧妙地利用联吡啶和4-氨基二乙酸对苯二甲酸来调节MOF的结构,制备出具有ORR/OER双功能活性、出色的稳定性的蒲公英花状材料Co₉S₈/Co-N_x/CoNi/Ni₃S₂@CNS-4。材料中丰富的CoNi合金和N、S杂原子掺杂在部分石墨化的碳质基质中确保了高效的电子/电荷传输。使用Co₉S₈/Co-N_x/CoNi/Ni₃S₂@CNS-4组装的ZABs展现出了206.9 mW/cm²的高功率密度,此性能远远超过了Pt/C+RuO₂的116.1 mW/cm²。

7 总结与展望

ZABs中,ORR和OER动力学缓慢是ZABs商业化的主要挑战之一。提高ORR和OER材料的催化活性主要从2个方面入手,一方面是提高单个活性位点的内在活性,另一方面是增加活性位点的密度。本文中通过对催化剂的三维结构入手,从这2个方面分析材料的催化性能和在ZABs中的应用,总结如下。

(1)催化剂骨架引入杂原子。N、P、S等原子可以很好地改善材料的导电性,同时稳定金属位点,提高活性位点催化能力,从而提高ZABs的性能。

(2)合理控制材料的三维结构。利用MOFs合成多面体结构、通过添加模板或者刻蚀得到中空结构和制备具有蜂窝结构的材料对增大活性位点的暴露程度有重要意义;构建异质界面如核壳结构、三明治结构等不仅能够提高比表面积,同时不同界面之间的异质结构对ORR/OER有着较好的催化能力。

(3)三维结构(如蒲公英状、花状等)通过合理调控活性位点位置和纳米材料形状,增大与电解液接触面积,从而提高ZABs的综合性能。

对于锌空气电池未来的研究发展可以从以下几点思考。

(1)利用低成本的合成方法,减少制备性能优异的催化剂材料过程中的高温煅烧。

(2)对催化活性位点的形成过程和实际催化机理进行明确的解释。

(3)ZABs的商业化还需解决黏合剂、隔膜材料、电解液泄露等问题。

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