Article(id=1321490194700812735, tenantId=1146029695717560320, journalId=1220038251117760515, issueId=1321490128967675980, articleNumber=null, orderNo=null, doi=10.11868/j.issn.1001-4381.2024.000248, pmid=null, cstr=32421.14.j.issn.1001-4381.2024.000248, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1712073600000, receivedDateStr=2024-04-03, revisedDate=null, revisedDateStr=null, acceptedDate=1718294400000, acceptedDateStr=2024-06-14, onlineDate=1792997414516, onlineDateStr=2026-10-26, pubDate=1768838400000, pubDateStr=2026-01-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792997414516, onlineIssueDateStr=2026-10-26, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792997414516, creator=13701087609, updateTime=1792997414516, updator=13701087609, issue=Issue{id=1321490128967675980, tenantId=1146029695717560320, journalId=1220038251117760515, year='2026', volume='54', issue='1', pageStart='1', pageEnd='259', issueExtLink='null', onlineDate='null', pubDate='1768838400000', pubDateStr='2026-01-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1792997398845, creator='13701087609', updateTime=1792997398845, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext=null, issueFiles=null, downloadFileDto=null}, startPage=241, endPage=249, ext={EN=ArticleExt(id=1321490196445643200, articleId=1321490194700812735, tenantId=1146029695717560320, journalId=1220038251117760515, language=EN, title=Metal-organic framework derived ZnSe@rGO nanocomposites and their application in supercapacitors, columnId=1220689384450478826, journalTitle=Journal of Materials Engineering, columnName=RESEARCH ARTICLE, runingTitle=null, highlight=null, articleAbstract=

Supercapacitors,as a new type of energy storage device between traditional capacitors and secondary batteries,show broad application prospects in many fields. In this study,graphene oxide (GO) is prepared by the Hummers method,and ZIF-8 with a regular dodecahedral structure is grown in-situ. Then,the ZnSe@rGO nanocomposite is successfully prepared via the chemical vapor deposition (CVD) method. SEM images show that the ZnSe@rGO nanocomposite has a regular dodecahedral structure. ZnSe grows along a layer of yarn-like rGO surface and exhibits good crystallization performance. BET tests indicate that the specific surface area of ZnSe@rGO is 57.36 m²·g-1,which is larger than that of ZIF-8@GO. Electrochemical performance tests of the samples show that,in 3 mol·L-1 KOH solution,the ZnSe@rGO nanocomposite has a high specific capacitance of 971.4 F·g-1 at a current density of 1 A·g-1,confirming the material has good pseudocapacitive behavior. Moreover,at a current density of 2 A·g-1,the ZnSe@rGO nanocomposite still maintains 74.49% of its initial capacitance and nearly 100% Coulombic efficiency after 5000 cycles,demonstrating excellent cycling stability. When assembled into an asymmetric supercapacitor (ZnSe@rGO∥AC),the device achieves a specific capacitance of 112.5 F·g-1 at a current density of 1.0 A·g-1. It also delivers an energy density of 40.0 Wh·kg-1 at a power density of 2057.1 W·kg-1,making ZnSe@rGO a promising candidate material for asymmetric supercapacitors.

, authors=Meipan ZHOU, Zhiqiang WEI, Ling LI, Meijie DING, Jiwei ZHAO, authorsList=Meipan ZHOU, Zhiqiang WEI, Ling LI, Meijie DING, Jiwei ZHAO, authorCompany=null, correspAuthors=Zhiqiang WEI, 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=1321490198249193939, articleId=1321490194700812735, tenantId=1146029695717560320, journalId=1220038251117760515, language=CN, title=金属有机骨架衍生ZnSe@rGO纳米复合材料在超级电容器的应用, columnId=1220689384622445292, journalTitle=材料工程, columnName=研究论文, runingTitle=null, highlight=null, articleAbstract=

超级电容器作为一种介于传统电容器与二次电池之间的新型储能装置,具有广阔的应用前景。本工作用Hummers法制备氧化石墨烯(GO),原位生长正十二面体结构的ZIF-8,再用CVD法成功制备纳米复合材料ZnSe@rGO。SEM照片显示,ZnSe@rGO纳米复合材料为正十二面体结构,ZnSe沿着一层纱似的rGO表面生长,且结晶性能良好。BET测试表明,ZnSe@rGO的比表面积为57.36 m2·g-1,相比较ZIF-8@GO具有更大的比表面积。对样品进行电化学性能测试,结果表明,在3 mol·L-1 KOH溶液中,ZnSe@rGO纳米复合材料在电流密度为1 A·g-1下的比电容高达971.4 F·g-1,说明该材料具有良好的赝电容行为,并且在2 A·g-1的电流密度下,循环5000次后仍具有74.49%的电容保持率以及接近100%的库仑效率,具有良好的循环稳定性。组装成非对称电容器ZnSe@rGO∥AC,电流密度为1.0 A·g-1时,比电容为112.5 F·g-1;功率密度为2057.1 W·kg-1时,能量密度为40.0 Wh·kg-1,为非对称超级电容器提供了良好的候选材料。

, authors=周美盼, 魏智强, 李羚, 丁梅杰, 赵继威, authorsList=周美盼, 魏智强, 李羚, 丁梅杰, 赵继威, authorCompany=null, correspAuthors=魏智强, authorNote=null, correspAuthorsNote=
魏智强(1973—),男,教授,博士,研究方向为纳米材料,联系地址:甘肃省兰州市七里河区彭家坪北路36号兰州理工大学彭家坪校区(730050),E-mail:
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(a)ZIF-8;(b)ZIF-8@GO;(c)rGO,ZnSe,and ZnSe@rGO

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(a)ZIF-8;(b)GO;(c)ZIF-8@GO前驱体;(d)ZnSe@rGO;(e),(f)ZIF-8@GO

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(a)ZIF-8;(b)ZIF-8@GO;(c)ZnSe@GO

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(c)CV curves at different scan rates(2-50 mV·s-1);(d)GCD curves at different current densities(1-20 A·g-1)

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(c)在不同扫描速率(2~50 mV·s-1)下的CV曲线;(d)在不同电流密度(1~20 A·g-1)下的GCD曲线

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金属有机骨架衍生ZnSe@rGO纳米复合材料在超级电容器的应用
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周美盼 , 魏智强 , 李羚 , 丁梅杰 , 赵继威
材料工程 | 研究论文 2026,54(1): 241-249
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材料工程 |研究论文 2026 , 54 (1) : 241 -249
金属有机骨架衍生ZnSe@rGO纳米复合材料在超级电容器的应用
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周美盼, 魏智强 , 李羚, 丁梅杰, 赵继威
作者信息
  • 兰州理工大学 理学院 有色金属先进加工与回收国家重点实验室,兰州 730050
通讯作者:
魏智强(1973—),男,教授,博士,研究方向为纳米材料,联系地址:甘肃省兰州市七里河区彭家坪北路36号兰州理工大学彭家坪校区(730050),E-mail:
Metal-organic framework derived ZnSe@rGO nanocomposites and their application in supercapacitors
Meipan ZHOU, Zhiqiang WEI , Ling LI, Meijie DING, Jiwei ZHAO
Affiliations
  • State Key Laboratory of Advanced Processing and Recycling of Nonferrous Metals,School of Science,Lanzhou University of Technology,Lanzhou 730050,China
出版时间: 2026-01-20 doi: 10.11868/j.issn.1001-4381.2024.000248
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超级电容器作为一种介于传统电容器与二次电池之间的新型储能装置,具有广阔的应用前景。本工作用Hummers法制备氧化石墨烯(GO),原位生长正十二面体结构的ZIF-8,再用CVD法成功制备纳米复合材料ZnSe@rGO。SEM照片显示,ZnSe@rGO纳米复合材料为正十二面体结构,ZnSe沿着一层纱似的rGO表面生长,且结晶性能良好。BET测试表明,ZnSe@rGO的比表面积为57.36 m2·g-1,相比较ZIF-8@GO具有更大的比表面积。对样品进行电化学性能测试,结果表明,在3 mol·L-1 KOH溶液中,ZnSe@rGO纳米复合材料在电流密度为1 A·g-1下的比电容高达971.4 F·g-1,说明该材料具有良好的赝电容行为,并且在2 A·g-1的电流密度下,循环5000次后仍具有74.49%的电容保持率以及接近100%的库仑效率,具有良好的循环稳定性。组装成非对称电容器ZnSe@rGO∥AC,电流密度为1.0 A·g-1时,比电容为112.5 F·g-1;功率密度为2057.1 W·kg-1时,能量密度为40.0 Wh·kg-1,为非对称超级电容器提供了良好的候选材料。

ZnSe  /  石墨烯  /  电化学性能  /  超级电容器  /  非对称

Supercapacitors,as a new type of energy storage device between traditional capacitors and secondary batteries,show broad application prospects in many fields. In this study,graphene oxide (GO) is prepared by the Hummers method,and ZIF-8 with a regular dodecahedral structure is grown in-situ. Then,the ZnSe@rGO nanocomposite is successfully prepared via the chemical vapor deposition (CVD) method. SEM images show that the ZnSe@rGO nanocomposite has a regular dodecahedral structure. ZnSe grows along a layer of yarn-like rGO surface and exhibits good crystallization performance. BET tests indicate that the specific surface area of ZnSe@rGO is 57.36 m²·g-1,which is larger than that of ZIF-8@GO. Electrochemical performance tests of the samples show that,in 3 mol·L-1 KOH solution,the ZnSe@rGO nanocomposite has a high specific capacitance of 971.4 F·g-1 at a current density of 1 A·g-1,confirming the material has good pseudocapacitive behavior. Moreover,at a current density of 2 A·g-1,the ZnSe@rGO nanocomposite still maintains 74.49% of its initial capacitance and nearly 100% Coulombic efficiency after 5000 cycles,demonstrating excellent cycling stability. When assembled into an asymmetric supercapacitor (ZnSe@rGO∥AC),the device achieves a specific capacitance of 112.5 F·g-1 at a current density of 1.0 A·g-1. It also delivers an energy density of 40.0 Wh·kg-1 at a power density of 2057.1 W·kg-1,making ZnSe@rGO a promising candidate material for asymmetric supercapacitors.

ZnSe  /  graphene  /  electrochemical performance  /  supercapacitor  /  asymmetric
周美盼, 魏智强, 李羚, 丁梅杰, 赵继威. 金属有机骨架衍生ZnSe@rGO纳米复合材料在超级电容器的应用. 材料工程, 2026 , 54 (1) : 241 -249 . DOI: 10.11868/j.issn.1001-4381.2024.000248
Meipan ZHOU, Zhiqiang WEI, Ling LI, Meijie DING, Jiwei ZHAO. Metal-organic framework derived ZnSe@rGO nanocomposites and their application in supercapacitors[J]. Journal of Materials Engineering, 2026 , 54 (1) : 241 -249 . DOI: 10.11868/j.issn.1001-4381.2024.000248
近几十年来,现代文明对储能设备的需求日益增长,导致煤炭、化石燃料等地球自然能源资源迅速枯竭,这是全球性的重大问题,且化石燃料燃烧破坏生态系统、引发温室效应与全球变暖[1]。因此,开发可替代化学能源与清洁能源、兼具高功率密度和高能量密度的新型储能器件成为关键[2]。锂离子电池、超级电容器、铅酸电池等储能装置遂成为研究热点[2-3]。其中,超级电容器是一种新型的电化学储能装置,相比较传统的可充电电池和普通电解电容器而言,具备充放电速率快、功率密度高、循环寿命长、安全性高、环境友好等优势,在电动车、电子设备、医疗设备、可再生能源存储等领域应用广泛,其快速充放电特性与长寿命使其成为高性能储能解决方案的重要组成[4-5]。目前,探索一种高性能的超级电容器的电极材料成为重要的攻克目标[6-7]
金属有机框架(MOFs)由金属节点与有机配体构成,合成简单、孔隙可调、比表面积大,在电化学储能领域用途广泛[8-10]。然而,自身容量低、导电性能差等弱点极大限制了其在电化学储能和电化学应用中的直接应用转换[11-12]。为了解决MOFs存在的弱点,通常会将MOFs前驱体作为模板,制备多孔碳、金属硫化物、金属硒化物、金属氧化物等衍生物,这些衍生物既能保留MOFs部分优势,又能提升导电性,提供更丰富的活性位点[13]。目前,已有MOFs衍生金属氧化物、过渡金属硫化物的报道,但MOFs衍生过渡金属硒化物的研究较少。
硒为Ⅵ族非金属元素,可与金属反应生成过渡金属硒化物。该类化合物形貌易设计且可控,比容量高、倍率性能优、循环稳定性好,在锂离子电池、超级电容器等储能领域应用前景广阔[14]。由于硒电负性低、带隙窄,电子传导速率快于氧原子与硫原子,故过渡金属硒化物电化学性能优于氧化物与硫化物[15]。ZnSe作为一种宽禁带半导体(室温下禁带宽度约2.67 eV),物理化学与半导体特性优异,在光电转换、催化剂、生物传感器、太阳能电池等领域应用价值显著[16-19]。
活性电极材料对超级电容器性能至关重要,活性炭、碳纳米管、石墨烯及其衍生物(氧化石墨烯GO、还原石墨烯rGO)等碳纳米材料已被广泛研究。石墨烯碳原子以sp²杂化形成二维六方蜂窝晶格,比表面积大、电导率高、化学性质稳定,且力学、电学、热学、光学性能优异,在纳米材料、传感器等领域应用前景广阔[20]。GO表面含羟基、羧基、环氧基等氧官能团,提升了与其他材料的相容性,在涂层、复合材料、能源存储等领域应用广泛;rGO由GO还原制得,去除部分氧官能团后,结构与性能更接近纯石墨烯,保留高导电性、高比表面积与高电化学活性,是超级电容器领域的常用材料。此外,rGO作为载体与半导体结合时,可提供电子迁移通道,促进电子在半导体与rGO间传输,助力电化学反应进行以提升电化学性能,且可通过层间工程与杂原子掺杂优化微观结构和能级,在电子器件、储能材料等领域应用潜力更大[21]。
本工作首先采用Hummers法制备氧化石墨烯(GO)[22],继而通过原位生长法制备出具有正十二面体结构的金属有机框架ZIF-8,并使ZIF-8均匀生长在GO表面上,形成ZIF-8@GO前驱体,这一过程为后续化学气相沉积法转化为ZnSe@rGO奠定了良好基础,有效保障了复合材料结构的规整性与组分的均匀性,随后采用化学气相沉积法反应制备出ZnSe@rGO纳米复合材料,该制备策略不仅保留了ZIF-8衍生的正十二面体结构,更借助rGO“纱状”基底的导电性与稳定性,有效解决了单一ZnSe导电性差、循环易团聚的问题,实现了结构与性能的协同优化。
硝酸锌(Zn(NO3)2·6H2O)、2-甲基迷唑(2-MeIM)、石墨粉、硒粉(Se)、活性炭(AC),均为分析纯,均购自上海阿拉丁试剂有限公司;浓硫酸(纯度98%)、高锰酸钾(KMnO4,分析纯)、过氧化氢(H2O2,纯度30%)、氢氧化钾(KOH,分析纯),均购自百世化工有限公司;氩气(Ar,纯度99.9%),购自兰州裕隆气体有限公司;乙炔黑,购自广东珠光新能源有限公司;无水乙醇,购自光华科技股份有限公司;聚偏氟二乙烯,购自国药集团化学试剂有限公司;丙酮,购自烟台市双双化工有限公司。
(1)氧化石墨烯的制备
以200目的石墨粉为原料,用Hummers法将其进行改进。使用硫酸(H2SO4)和高锰酸钾(KMnO4)作为氧化剂以得到氧化石墨烯(GO),将质量分数为98%的浓硫酸准备好,使用电子天平称取2 g石墨粉,再将两者放入冰水浴中,随后缓慢加入12 g KMnO4到稀释后的H2SO4中,并大力搅拌,将混合物在95 ℃的水浴条件下超声搅拌30 min后,再用少量质量分数为30%的H2O2溶液去除反应剩余的KMnO4,用无水乙醇和去离子水交替洗涤,将其至置于60 ℃的恒温干燥箱中干燥过夜,将所得产物在去离子水中进行超声分散,并将混合物放入离心机中进行悬浮离心,最终得到的GO样品溶解于去离子水备用。
(2)ZIF-8和ZIF-8@GO前驱体的制备
ZIF-8是通过原位生长法制备的,将1.31 g的2-甲基咪唑(2-MeIM)和1.18 g的六水合硝酸锌(Zn(NO3)2·6H2O)分别溶解在50 mL甲醇中,剧烈搅拌1 h,分别记为溶液A、溶液B,将溶液B迅速倒入溶液A中,得到乳白色溶液,室温静置24 h,将上清液倒掉,用无水乙醇多次离心,在真空烘箱中60 ℃干燥即可得到ZIF-8。将A、B溶液混合并加入3 mL 2 mg/mL GO溶液,其他步骤不变即可得到ZIF-8@GO前驱体。
(3)ZnSe@rGO的制备
将500 mg的硒粉和50 mg的ZIF-8@GO前驱体粉末分别放置在管式炉中。通入氢气和氩气的混合气体,两者的体积比为10∶90,升温速率为5 ℃·min-1,到达500 ℃时,保温1 h,即可获得ZnSe@rGO纳米复合材料。将500 mg硒粉和50 mg ZIF-8粉末为原材料,其他步骤不变,即可得到ZnSe。
样品的晶体结构用XRD(Bruker D8,ADVANCE)表征分析;样品的微观形貌用高分辨率透射电子显微镜(JSM-6710 F)进行表征;样品的元素及其化学态用250 nm波长的XPS(Supra)测试;样品的比表面积用BET(Brunauer-Emmett-Teller)进行测试,使用N2作为吸附气体,将样品放入样品池中,通过加热和真空脱气,去除表面吸附的水分和其他杂质,将样品降温至液氮温度(77 K),逐步引入一定量的N2,记录不同压力下气体的吸附量。
在电化学工作站中,以铂片(1.0 cm×1.0 cm)为对电极,以Ag/AgCl为参比电极,3 mol·L-1 KOH作为电解质溶液,对ZnSe以及ZnSe@rGO进行线性循环伏安(CV)、恒电流充放电(GCD)、电化学阻抗谱(EIS)等测试。用乙炔黑作为导电剂,聚氟乙烯(PVDV)作为黏合剂,将活性物质、乙炔黑、PVDF以质量比为8∶1∶1均匀混合,均匀涂在用丙酮、盐酸、酒精和水反复超声清洗过的泡沫镍上,之后在60 ℃的真空干燥箱中干燥过夜,并使用压力机在10 MPa的压力下均匀压制后进行电化学性能的测试。
将ZnSe@rGO作为混合型超级电容器的正极,活性炭作为超级电容器的负极,组装成混合型超级电容器并将其命名为ZnSe@rGO∥AC。正极和负极活性物质的最佳质量比根据电荷平衡理论[23]计算,如式(1)所示:
m+C+ΔV+=m-C-ΔV-
式中:m+、m-分别为正极与负极活性物质的质量;C+和C-分别为正极和负极的比电容;ΔV+和ΔV-分别为正极和负极的工作电位窗口。能量密度和功率密度计算,如式(2),(3)所示:
E=CΔV22×3.6
P=3600EΔt
图1为ZnSe和ZnSe@rGO纳米复合材料的XRD谱。ZIF-8的XRD如图1(a)所示,在2θ=7.4°、10.4°、12.7°、14.8°、16.5°、18.0°、22.1°、24.5°、25.5°、26.7°、29.5°、30.6°、31.6°、32.5°等处出现了明显尖锐的衍射峰,分别对应(011)、(002)、(112)、(022)、(013)、(222)、(114)、(233)、(224)、(134)、(044)、(334)、(244)、(235)晶面,这与之前报道中所制备的ZIF-8峰值位置相一致[24]。图1(b)为ZIF-8@GO的XRD图谱,GO在ZIF-8@GO复合材料中的含量较低,所以在(002)处其对应的衍射峰可能非常弱,难以在XRD图谱中显现出来。在图1(c)中可以看出ZnSe在27.22°、45.20°、53.57°有3个明显的特征峰,分别对应立方相ZnSe的(111)、(220)、(311)3个晶面,对应ZnSe晶体结构(PDF# 37-1463)。如图1(c)所示,观察到的氧化石墨烯(GO)在2θ =10.8°、20.9°的衍射峰分别对应(001)、(002)晶面。ZnSe@rGO复合材料与上述两种材料的衍射峰位置相同,说明成功制备了ZnSe@rGO纳米复合材料。
图2为ZIF-8、GO、ZIF-8@GO前驱体以及ZnSe@rGO的SEM图谱。从图2(a)中可以看出,ZIF-8尺寸大小较均匀,为表面较光滑正十二面体形状,直径大约为900 nm,图2(b)为氧化石墨烯的微观形貌,可以观察到氧化石墨烯具有较大的比表面积,并呈现出不同程度的褶皱。这些褶皱赋予了氧化石墨烯独特的表面结构,使得氧化石墨烯表面具有更多的活性位点,这些位点有助于吸附和催化反应物质,从而有助于提高电子的转移速率和电催化活性。在图2(c)中,可以看出正十二面体的ZIF-8均匀生长在氧化石墨烯表面,GO表面较为光滑。图2(d)展示了通过CVD法制备的ZnSe@rGO复合材料,经H2和Ar处理后,GO被还原为rGO,ZIF-8也被硒化为ZnSe,复合材料便以ZnSe@rGO的形式存在,可以看到,ZnSe纳米颗粒紧密附着在rGO表面,形成颗粒状复合结构。本工作的制备方法不仅解决了ZnSe在反应过程中的结构膨胀问题,还有效缓解了石墨烯的自堆叠现象,从而增强了ZnSe@rGO纳米复合材料的电化学性能。从图2(e),(f)可以看出ZIF-8的团聚现象较为严重,会导致材料不均匀,从而导电性较差,所以通过构建ZIF-8的衍生物以增强导电性[25]。
图3为ZIF-8、ZIF-8@GO以及ZnSe@rGO的比表面积测试。从图3(a)~(c)中可以看出,在N2吸附等温曲线中所制备的样品均为典型的H3型回滞环。ZIF-8的比表面积为47.12 m2·g-1,ZIF-8@GO的比表面积为50.99 m2·g-1,ZIF-8@GO的比表面积较ZIF-8的比表面积大,表明GO的引入有效增加表面活性面积,从而提供更多的表面活性位点。同时,ZnSe@rGO的比表面积也显著提高至57.36 m2·g-1,进一步证明了纳米颗粒的引入在石墨烯片层间形成了更多的孔隙结构,有效缓解了自堆叠现象。
图4为ZnSe@rGO样品的XPS谱图。图4(a)为ZnSe@rGO复合材料的全谱图,可以观察到Zn、C、Se元素,表明ZnSe@rGO复合材料成功复合。图4(b)为Zn 2p的分峰,在1021.93、1045.03 eV处可看到明显峰值,分别于低能带的Zn 2p3/2和高能带的Zn 2p1/2相对应,表明Zn在ZnSe@rGO以正二价的形式存在[26]。图4(c)为Se 3d的分峰,Se元素主要在53.50、54.78、55.68 eV处存在特征峰,55.68、53.50 eV处峰分别于自旋轨道Se 3d5/2和3d3/2相对应,而54.78处的峰则对应Zn—Se键,表明两种元素之间存在强相互作用[27]。从图4(d)中C的分峰中可以看到,C以C—C、C̿    O两种键合的形式存在,其中284.73、286.16 eV处对应C—C峰,287.73 eV处对应C̿    O峰[28]。GO的C 1s主要有4个峰,分别对应于C̿    C(284.3 eV)、C—OH(286.3 eV)、C̿    O(288.1 eV)和O—C̿    O(289.4 eV)[29]。在ZIF-8@GO的谱图中,C̿    C峰的强度明显减弱,这表明ZIF-8纳米颗粒与GO表面的氧化基团发生了相互作用,减少了这些基团的数量,同时在ZIF-8@GO材料的C 1s谱图中,285.81、286.38 eV分别对应ZIF-8材料中有机配体二甲基咪唑中的C—N和C̿    N,而ZnSe@rGO中,C̿    C键强度较高,C̿    O键强度较低,说明了还原过程中去除了部分羰基。
循环伏安法(CV)是在电极上施加线性变化的扫描电压并记录电流随电压变化的曲线,以研究电极反应的可逆性、动力学特性及电荷存储机制的电化学测试方法。图5(a)为ZnSe和ZnSe@rGO在扫描速率为50 mV·s-1下的CV曲线,相比较ZnSe而言,氧化还原特征峰强度和闭合曲线的面积较大,电化学性能更好。图5(b)为ZnSe@rGO在不同扫描速率(5~50 mV·s-1)下的CV曲线,在电势窗口-0.1~0.6 V之间出现一组明显对称的法拉第氧化还原峰,可看出随着扫描速率的增加,曲线面积不断增大,形状没有发生明显的畸变,表明该材料电化学性能良好,也充分说明了rGO的引入有效增强了复合材料的导电性能。
恒电流充放电(GCD)是通过记录电极材料在恒定电流充放电过程中电压随时间的变化,以表征其电容特性、电荷存储机制等电化学性能的测试方法。图6展示了ZnSe和ZnSe@rGO电极在电流密度为1.0 A·g-1时的GCD曲线。如图6(a)所示,相较于ZnSe而言,ZnSe@rGO复合材料的放电时间更长,比容量达到971.4 F·g-1,而ZnSe的比容量仅为413.8 F·g-1。此外,ZnSe@rGO的GCD曲线在不同电流密度下均表现出明显对称的充放电电压平台(图6(b)),这也表明该电极材料在充放电过程中法拉第氧化还原反应具有高度可逆性[30]。
为了进一步确定ZnSe@rGO的电导率,对其进行电化学阻抗测试(EIS)。图7为奈奎斯特图,高频区的谱线与实轴的交点表示该电极及溶液在一定的极化电位下的欧姆阻抗(Rs),半圆直径反映了电荷转移电阻(Rct),对应电荷转移限制过程,即电子或离子在界面上传输的难易程度。低频区域的斜线代表Warburg阻抗(Ws),反映了电活性物质的体相扩散行为。为了确定Rs和Rct值,建立与其对应的等效电路图,从图中可以看出ZnSe@rGO的Rs、Rct均小于ZnSe的,根据软件拟合可计算出ZnSe的Rs=0.29 Ω、Rct=0.33 Ω,而ZnSe@rGO复合材料的Rs=0.27 Ω、Rct=0.26 Ω,也进一步说明ZnSe@rGO具有较高的导电性能和较快的离子扩散和传导速率,进一步说明了rGO的引入提升了ZnSe的电化学性能。
为进一步探究该电极材料的循环稳定性,对ZnSe@rGO纳米复合材料进行长循环性能测试,对库仑效率以及容量保持率进行评估,该电极在进行5000次循环充放电之后,比容量能够保持在初始的74.49%,具有良好的容量保持率,而库仑效率近似于100%,这表明该电极具有良好的长循环稳定性。
为了进一步评估ZnSe@rGO纳米复合材料在实际应用中的电化学性能,将ZnSe@rGO(-0.1~0.6 V vs. Ag/AgCl)作为混合型电容器的正极,活性炭(-1.0~0 V vs. Ag/AgCl)作为混合型电容器的负极,组装电容器器件ZnSe@rGO∥AC进行电化学测试(图9)。图9(a)所示,由电荷平衡理论[24]计算正极材料与负极活性炭的质量,分别为2 mg与5 mg。图9(b)为在50 mV·s-1扫描速率下,电压从1.0 V增至1.8 V时ZnSe@rGO∥AC器件的CV曲线,对混合型电容器来说,电容器的电压与电荷之间的关系呈现出近似矩形的形状。当工作电压为1.8 V时可看出图形有明显形变,说明该器件可靠工作的最大电压为1.6 V。如图9(c)所示,可以看出ZnSe@rGO∥AC器件在2~50 mV·s-1的扫描速率下出现一对明显的氧化还原峰,且随着扫描速率的上升,CV曲线的形状并无明显畸变,这意味着该材料可以快速存储和释放电荷,具有法拉第赝电容的快速充放电特性,并且其可逆性良好。在GCD测试中(图9(d)),电流密度从1.0 A·g-1 增至20.0 A·g-1,充电时间和放电时间几乎等同,这表明了该器件库仑效率较高,化学可逆性良好。计算结果表明,ZnSe@rGO∥AC器件在电流密度为1.0 A·g-1下的比电容为112.5 F·g-1,在功率密度为2057.1 W·kg-1下,能量密度可达到40.0 Wh·kg-1,这些结果表明了ZnSe@rGO∥AC器件作为超级电容器电极材料的潜力。
(1)通过原位生长技术,将正十二面体结构的金属有机框架ZIF-8均匀生长在GO表面上,形成ZIF-8@GO前驱体,采用CVD法转化为ZnSe@rGO。该制备策略不仅保留了ZIF-8衍生的正十二面体结构,更借助rGO“纱状”基底的导电性与稳定性,有效解决了单一ZnSe导电性差、循环易团聚的问题,实现了结构与性能的协同优化。
(2)ZnSe@rGO纳米复合材料具有较好的比容量和循环稳定性能。在三电极体系下,电流密度为1.0 A·g-1时,该ZnSe@rGO纳米复合材料的比容量可达到971.4 F·g-1,即使在循环5000次后,仍保持着74.49%的电容保持率和接近100%的库仑效率。
(3)用ZnSe@rGO作正极,组装成的非对称超级电容器ZnSe@rGO∥AC器件也表现出了优异的电化学性能,在1 A·g-1的电流密度下的比电容为112.5 F·g-1,能提供40.0 Wh·kg-1的能量密度以及2057.1 W·kg-1的功率密度。
  • 国家自然科学基金(52268042)
  • 国家自然科学基金(52468035)
  • 甘肃省自然科学基金(22JR5RA253)
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2026年第54卷第1期
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doi: 10.11868/j.issn.1001-4381.2024.000248
  • 接收时间:2024-04-03
  • 首发时间:2026-10-26
  • 出版时间:2026-01-20
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  • 收稿日期:2024-04-03
  • 录用日期:2024-06-14
基金
国家自然科学基金(52268042)
国家自然科学基金(52468035)
甘肃省自然科学基金(22JR5RA253)
作者信息
    兰州理工大学 理学院 有色金属先进加工与回收国家重点实验室,兰州 730050

通讯作者:

魏智强(1973—),男,教授,博士,研究方向为纳米材料,联系地址:甘肃省兰州市七里河区彭家坪北路36号兰州理工大学彭家坪校区(730050),E-mail:
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2种不同金属材料的力学参数
科
Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)
属
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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