MnO2@ZnO/C 复合材料的制备及电化学性能

doi:10.12066/j.issn.1007-2861.2012

摘要/Abstract

摘要：

金属有机骨架 (metal-organic frameworks, MOFs) 化合物是一类由金属离子和通过配位键连接在一起的有机配体组成的晶体材料. 作为一种具有立体空间结构的功能材料, 凭借其较大的比表面积、较高的孔隙率及品种的多样性, 引起了各领域研究者的广泛关注. 以 $\beta $-MnO₂ 纳米棒为模板制备出 MnO₂@ZIF-8 杂化纳米结构, 在惰性气氛中分步煅烧处理, 得到 MnO₂@ZnO/C 复合材料. ZIF-8 中的有机配体由于高温煅烧发生裂解而产生孔道, 进而为锂离子的嵌入和脱出提供更多离子传输路径. 同时, 由于高温裂解伴随着碳的产生, 因此当使用这种复合结构物质作为电极材料时, 可以提高材料的导电率. MnO₂@ZnO/C 纳米复合材料的首次放电比容量为 1 873 mA$\cdot$h$\cdot$g^-1, 在电流密度为 100 mA/g 的条件下完成 100 次充放电后比容量维持在658 mA$\cdot$h$\cdot$g^-1, 展现出了优良的电化学储能特性.

关键词: 金属有机骨架化合物, MnO₂, ZnO/C, 锂离子电池

Abstract:

Metal-organic frameworks (MOFs) compounds are compounds formed by bonding metal centers and organic ligands through coordination bonds. As a new type of porous material, it has drawn much attention of researchers in various fields due to its large specific surface area, high porosity and variety of species. In this study, MnO₂@ZnO/C hybrids are rationally synthesized by using MnO₂@ZIF-8 core-shell nanowires as templates. Owing to its structural and compositional characteristics, namely, the synergistic effects between components and the conductive carbon coating, the resultant MnO₂@ZnO/C hybrids exhibit good electrochemical performance as an anode material in Li-ion batteries with a first discharge specific capacity of 1 873 mA$\cdot$h$\cdot$g^-1 and a specific capacity of 658 mA$\cdot$h$\cdot $g^-1 at a current density of 100 mA/g for 100 cycles.

Key words: metal-organic framework compounds, MnO₂, ZnO/C, lithium ion batteries

中图分类号:

O614.7$^+$11

罗志刚, 李琦, 陈大勇, 黄守双, 胡张军, 陈志文. MnO₂@ZnO/C 复合材料的制备及电化学性能[J]. 上海大学学报(自然科学版), 2020, 26(1): 132-142.

Zhigang LUO, Qi LI, Dayong CHEN, Shoushuang HUANG, Zhangjun HU, Zhiwen CHEN. Preparation and electrochemical properties of MnO₂@ZnO/C composite[J]. Journal of Shanghai University（Natural Science Edition）, 2020, 26(1): 132-142.

图/表 10

图1

图2

图3

图4

图5

图6

图7

图8

图9

表1

参考文献 36

[1]	Graham-Rowe E, Gardner B, Abraham C , et al. Mainstream consumers driving plug-in battery-electric and plug-in hybrid electric cars: a qualitative analysis of responses and evaluations[J]. Transportation Research Part A: Policy and Practice, 2012,46(1):140-153.
[2]	Yu A P, Chen Z W, Maric R , et al. Electrochemical supercapacitors for energy storage and delivery: advanced materials, technologies and applications[J]. Applied Energy, 2015,153:1-2.
[3]	Fernão P V, Romero-Cadaval E, Vinnikov D , et al. Power converter interfaces for electrochemical energy storage systems—a review[J]. Energy Conversion and Management, 2014,86:453-475.
[4]	Li X F, Wang C L . Engineering nanostructured anodes via electrostatic spray deposition for high performance lithium ion battery application[J]. Journal of Materials Chemistry A, 2013,1(2):165-182.
[5]	Sun W W, Wang Y . Graphene-based nanocomposite anodes for lithium-ion batteries[J]. Nanoscale, 2014,6(20):11528-11552.
[6]	Xia X H, Zhang Y Q, Chao D L , et al. Solution synjournal of metal oxides for electrochemical energy storage applications[J]. Nanoscale, 2014,6(10):5008-5048.
[7]	Wang X F, Lu X H, Liu B , et al. Flexible energy-storage devices: design consideration and recent progress[J]. Advanced Materials, 2014,26(28):4763-4782.
[8]	Zhang X J, Shi W H, Zhu J X , et al. High-power and high-energy-density flexible pseudocapacitor electrodes made from porous CuO nanobelts and single-walled carbon nanotubes[J]. ACS Nano, 2011,5(3):2013-2019.
[9]	Witt J A, Mumm D R, Mohraz A . Microstructural tunability of co-continuous bijel-derived electrodes to provide high energy and power densities[J]. Journal of Materials Chemistry A, 2016,4(3):1000-1007.
[10]	Li H, Richter G, Maier J . Reversible formation and decomposition of LiF clusters using transition metal fluorides as precursors and their application in rechargeable Li batteries[J]. Advanced Materials, 2003,15(9):736-739.
[11]	Zhao D, Qin J W, Zheng L R , et al. Amorphous vanadium oxide/molybdenum oxide hybrid with three dimensional ordered hierarchically porous structure as a high-performance Li-ion battery anode[J]. Chemistry of Materials, 2016,28(12):4180-4190.
[12]	Zhao Y, Li X F, Yan B , et al. Recent developments and understanding of novel mixed transition-metal oxides as anodes in lithium ion batteries[J]. Advanced Energy Materials, 2016,6(8):1502175.
[13]	Liu J, Liu W, Chen K F , et al. Facile synjournal of transition-metal oxide nanocrystals embedded in hollow carbon microspheres for high-rate lithium-ion-battery anodes[J]. Chemistry-A European Journal, 2013,19(30):9811-9816.
[14]	Wang R, Feng L L, Yang W R , et al. Effect of different binders on the electrochemical performance of metal oxide anode for lithium-ion batteries[J]. Nanoscale Research Letters, 2017,12:575.
[15]	Kong S F, Dai R L, Li H , et al. Microwave hydrothermal synjournal of Ni-based metal-organic frameworks and their derived yolk-shell NiO for Li-ion storage and supported ammonia borane for hydrogen desorption[J]. ACS Sustainable Chemistry & Engineering, 2015,3(8):1830-1838.
[16]	李莹, 张红星, 闫柯乐 , 等. 金属有机骨架材料 (MOFs) 的合成及应用研究[J]. 广州化工, 2016,44(15):24-27.
	Li Y, Zhang H X, Yan K L , et al. Study on synjournal methods and applications of metal-organic frameworks material (MOFs)[J]. Guangzhou Chemical Industry, 2016,44(15):24-27.
[17]	李海莹, 刘峥, 李庆伟 . 金属-有机骨架化合物在电化学中的应用研究进展[J]. 化工新型材料, 2017,45(3):10-12.
	Li H Y, Liu Z, Li Q W . Electrochemical application of metal-organic frameworks[J]. New Chemical Materials, 2017,45(3):10-12.
[18]	姚显芳, 李映伟 . MOFs 作为牺牲模板制备纳米多孔碳材料的方法及其应用[J]. 科学通报, 2015,60(20):1906-1914.
	Yao X F, Li Y W . MOFs as sacrificial templates for preparation of nanoporous carbon materials and their applications[J]. Chinese Science Bulletin, 2015,60(20):1906-1914.
[19]	Li H, Liang M, Sun W W , et al. Bimetal-organic framework: one-step homogenous formation and its derived mesoporous ternary metal oxide nanorod for high-capacity, high-rate, and long-cycle-life lithium storage[J]. Advanced Functional Materials, 2016,26(7):1098-1103.
[20]	Cho J H, Lee S M, Shin J W , et al. Structural transformation and gas adsorption properties of interpenetrated IRMOF-8[J]. Bulletin of the Korean Chemical Society, 2014,35(3):949-952.
[21]	Ganguly S, Pachfule P, Bala S , et al. Azide-functionalized lanthanide-based metal-organic frameworks showing selective CO₂ gas adsorption and postsynthetic cavity expansion[J]. Inorganic Chemistry, 2013,52(7):3588-3590.
[22]	Kim H R, Yoon T U, Kim S I , et al. Beyond pristine MOFs: carbon dioxide capture by metal-organic frameworks (MOFs)-derived porous carbon materials[J]. RSC Advances, 2017,7(3):1266-1270.
[23]	Das M C, Xiang S C, Zhang Z J , et al. Functional mixed metal-organic frameworks with metalloligands[J]. Angewandte Chemie International Edition, 2011,50(45):10510-10520.
[24]	Meyer L V, Schöenfeld F, Müeller-Buschbaum K . Lanthanide based tuning of luminescence in MOFs and dense frameworks-from mono- and multimetal systems to sensors and films[J]. Chemical Communications, 2014,50(60):8093-8108.
[25]	Ren J W, Ledwaba M, Musyoka N M , et al. Structural defects in metal-organic frameworks (MOFs): formation, detection and control towards practices of interests[J]. Coordination Chemistry Reviews, 2017,349:169-197.
[26]	Chaikittisilp W, Ariga K, Yamauchi Y . A new family of carbon materials: synjournal of MOF-derived nanoporous carbons and their promising applications[J]. Journal of Materials Chemistry A, 2013,1(1):14-19.
[27]	Pei X K, Chen Y F, Li S Q , et al. Metal-organic frameworks derived porous carbons: syntheses, porosity and gas sorption properties[J]. Chinese Journal of Chemistry, 2016,34(2):157-174.
[28]	Qie L, Chen W M, Wang Z H , et al. Nitrogen-doped porous carbon nanofiber webs as anodes for lithium ion batteries with a superhigh capacity and rate capability[J]. Advanced Materials, 2012,24(15):2047-2050.
[29]	Deng S Z, Li Z T . Nitrogen-doped graphene oxide coated ZnO nanohybrid for lithium-ion batteries anode[J]. Integrated Ferroelectrics, 2017,182(1):10-20.
[30]	An Y L, Zhang Z, Fei H F , et al. Ultrafine TiO₂ confined in porous-nitrogen-doped carbon from metal-organic frameworks for high-performance lithium sulfur batteries[J]. ACS Applied Materials & Interfaces, 2017,9(14):12400-12407.
[31]	Zheng F C, Yang Y, Chen Q W . High lithium anodic performance of highly nitrogen-doped porous carbon prepared from a metal-organic framework[J]. Nature Communications, 2014,5:5261.
[32]	Hu L, Huang Y M, Zhang F P , et al. CuO/Cu₂O composite hollow polyhedrons fabricated from metal-organic framework templates for lithium-ion battery anodes with a long cycling life[J]. Nanoscale, 2013,5(10):4186-4190.
[33]	Guo W X, Sun W W, Wang Y . Multilayer CuO@NiO hollow spheres: microwave-assisted metal organic-framework derivation and highly reversible structure-matched stepwise lithium storage[J]. ACS Nano, 2015,9(11):11462-11471.
[34]	Hu H, Guan B, Xia B , et al. Designed formation of Co₃O₄/NiCo₂O₄ double-shelled nanocages with enhanced pseudocapacitive and electrocatalytic properties[J]. J Am Chem Soc, 2015,137(16):5590-5595.
[35]	Zhang H, Wang Y S, Zhao W Q , et al. MOF-derived ZnO nanoparticles covered by N-doped carbon layers and hybridized on carbon nanotubes for lithium-ion battery anodes[J]. ACS Applied Materials & Interfaces, 2017,9:37813-37822.
[36]	Zhu D Q, Zheng F C, Xu S H , et al. MOF-derived self-assembled ZnO/Co₃O₄ nanocomposite clusters as high-performance anodes for lithium-ion batteries[J]. Dalton Transactions, 2015,44:16946-16952.

MnO₂@ZnO/C 复合材料的制备及电化学性能

Preparation and electrochemical properties of MnO₂@ZnO/C composite

RichHTML

PDF

可视化

摘要/Abstract

引用本文

使用本文

图/表 10

参考文献 36

相关文章 15

编辑推荐

Metrics

本文评价

[1]	武思敏, 胡祖明, 于俊荣, 王彦, 李娜. 锂离子电池用多级ZnO-PMIA纳米纤维隔膜的制备及性能[J]. 上海大学学报(自然科学版), 2025, 31(4): 607-621.
[2]	张博畅1, 2, 3, 4, 高化东1, 2, 3, 4, 徐沈鑫5, 鲍垠桦1, 2, 3, 4, 吕浡 1, 2, 3, 4. 任意方向可弯的锂离子电池压印柔性厚电极[J]. 上海大学学报(自然科学版), 2024, 30(5): 980-988.
[3]	林明钜, 锁要红, 赖光辉, 肖军文. 快充方式下考虑热辐射效应的锂离子电池热-力耦合分析[J]. 上海大学学报(自然科学版), 2023, 29(3): 450-.
[4]	朱明原, 刘文博, 李瑛, 刘杨, 李文献, 张久俊. ALD 反应沉积超薄 TiO₂改性 LiNi_0.8Co_0.1Mn_0.1O₂正极材料及其电化学性能[J]. 上海大学学报(自然科学版), 2023, 29(2): 312-.
[5]	胡瑶, 贡建阳, 尤万里, 刘洪江, 陈国荣, 施利毅, . 原位凝胶体系 LiNi0.8Co0.1Mn0.1O2 的制备及其电化学性能[J]. 上海大学学报(自然科学版), 2023, 29(2): 302-.
[6]	张豪杰, 胡业旻. Sb$_{\mathbf 2}$O$_{\mathbf 3}$/Sb 锂离子电池负极材料的制备及电化学性能[J]. 上海大学学报(自然科学版), 2021, 27(6): 1047-1055.
[7]	程二波, 王尚岱, 黄守双, 陈大勇, 胡张军, 陈志文. MnO@CoMn$_{\textbf{2}}$O$_{\textbf{4}}$/N-C纳米线复合材料的制备及其作为锂离子电池阳极材料的电化学性能[J]. 上海大学学报(自然科学版), 2021, 27(2): 400-410.
[8]	陈恒桥, 吕丽萍, 吴明红. Co-Mn 金属有机骨架衍生的双金属硫化物及其在锂离子电池负极材料中的应用[J]. 上海大学学报(自然科学版), 2021, 27(2): 369-378.
[9]	朱影, 周荻雯, 唐燕, 王浩, 赵攀登, 浦娴娟, 焦正, 程伶俐. SnO$_{\boldsymbol{x}}$S$_{\boldsymbol{y}}$@PANI@rGO 复合材料的制备及其电化学性能[J]. 上海大学学报(自然科学版), 2021, 27(1): 78-85.
[10]	赵攀登, 何永超, 何新华, 冯笑笑, 浦娴娟, 程伶俐, 焦正. 双层壳结构 Co$_{\bf 2.7}\rm {\bf Cu_{0.3}O_{4}}$ 立方体复合材料的制备及锂电性能[J]. 上海大学学报(自然科学版), 2021, 27(1): 117-124.
[11]	朱德伦, 彭雨晴, 白瑞成, 李爱军, 赵添婷, 孙宁霞. 锂离子电池三维多孔硅/银复合材料负极设计及性能[J]. 上海大学学报(自然科学版), 2021, 27(1): 144-153.
[12]	张燕锋, 蔡昌, 谈馨怡, 孙炜伟. 金属有机骨架衍生双金属氧化物的锂离性能[J]. 上海大学学报(自然科学版), 2021, 27(1): 125-132.
[13]	汤旭旭, 杨秦斯, 杨建伟, 孙炜伟. 共价有机骨架衍生的氮掺杂碳/碳纳米管杂化结构的储锂性能[J]. 上海大学学报(自然科学版), 2020, 26(6): 972-979.
[14]	高阳, 蒋永, 焦正. 中空硅球/石墨烯复合材料制备及电化学性能[J]. 上海大学学报(自然科学版), 2020, 26(4): 586-594.
[15]	陈思, 张勇, 张雪倩, 吕丽萍. 锂离子电池负极中一步球磨硅碳材料的应用[J]. 上海大学学报(自然科学版), 2020, 26(4): 578-585.