On the Correlation between Mechanical Flexibility, Nanoscale Structure, and Charge Storage in Periodic Mesoporous CeO2 Thin Films

被引:133
作者
Brezesinski, Torsten [1 ,3 ]
Wang, John [2 ]
Senter, Robert [1 ]
Brezesinski, Kirstin [3 ]
Dunn, Bruce [4 ]
Tolbert, Sarah H. [1 ,4 ]
机构
[1] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA
[2] Univ Calif Los Angeles, Dept Mat Sci & Engn, Los Angeles, CA 90095 USA
[3] Univ Giessen, Inst Phys Chem, D-35392 Giessen, Germany
[4] Univ Calif Los Angeles, Calif NanoSyst Inst, Los Angeles, CA 90095 USA
关键词
mesoporous materials; ceria; CeO2; electrochemical charge storage; supercapacitors; pore flexibility; block copolymer templating; nanostructured materials; ENHANCED THERMAL-STABILITY; SOL-GEL; ELECTROCHEMICAL CAPACITORS; LITHIUM BATTERIES; ROOM-TEMPERATURE; CERIA; ARCHITECTURE; EXPANSION; BEHAVIOR; OXIDE;
D O I
10.1021/nn9007324
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
In this work, we report the synthesis and characterization of highly ordered mesoporous CeO2 thin films with crystalline walls. While this article focuses on electrochemical studies of CeO2 with periodic nanoscale porosity, we also examine the mechanical properties of these films and show how pore flexing can be used to facilitate intercalation of lithium ions. Mesoporous samples were prepared by dip-coating using the large diblock copolymer KLE as the organic template. We establish that the films have a mesoporous network with a biaxially distorted cubic pore structure and are highly crystalline at the atomic scale when heated to temperatures above 500 degrees C. Following a previously reported approach, we were able to use the voltammetric sweep rate dependence to determine quantitatively the capacitive contribution to electrochemical charge storage. The net result is that mesoporous CeO2 films exhibit reasonable levels of pseudocapacitive charge storage and much higher capacities than samples prepared without any polymer template. Part of this increased capacity stems from the fact that these films are able to expand normal to the substrate upon intercalation of lithium ions by flexing of the nanoscale pores. This flexing relieves stress from volume expansion that normally inhibits charge storage. Overall, the results described in this work provide fundamental insight into how nanoscale structure and mechanical flexibility can be used to increase charge storage capacity in metal oxides.
引用
收藏
页码:967 / 977
页数:11
相关论文
共 47 条
[1]  
[Anonymous], 1999, ELECTROCHEMICAL SUPE
[2]   Nanostructured materials for advanced energy conversion and storage devices [J].
Aricò, AS ;
Bruce, P ;
Scrosati, B ;
Tarascon, JM ;
Van Schalkwijk, W .
NATURE MATERIALS, 2005, 4 (05) :366-377
[3]  
Bard A.J, 2002, Student Solutions Manual to accompany Electrochemical Methods: Fundamentals and Applicaitons, V2e
[4]   Thin film of CeO2-SiO2:: a new ion storage layer for smart windows [J].
Berton, MAC ;
Avellaneda, CO ;
Bulhoes, LOS .
SOLAR ENERGY MATERIALS AND SOLAR CELLS, 2003, 80 (04) :443-449
[5]  
Brett C., 1993, Electrochemistry: Principles, Methods, and Applications
[6]  
Brezesinski T, 2005, STUD SURF SCI CATAL, V156, P243
[7]   Self-assembled metal oxide bilayer films with "single-crystalline" overlayer mesopore structure [J].
Brezesinski, Torsten ;
Antonietti, Markus ;
Smarsly, Bernd M. .
ADVANCED MATERIALS, 2007, 19 (08) :1074-1078
[8]   Evaporation-induced self-assembly (EISA) at its limit: Ultrathin, crystalline patterns by templating of micellar monolayers [J].
Brezesinski, Torsten ;
Groenewolt, Matthijs ;
Gibaud, Alain ;
Pinna, Nicola ;
Antonietti, Markus ;
Smarsly, Bernd M. .
ADVANCED MATERIALS, 2006, 18 (17) :2260-+
[9]   Templated Nanocrystal-Based Porous TiO2 Films for Next-Generation Electrochemical Capacitors [J].
Brezesinski, Torsten ;
Wang, John ;
Polleux, Julien ;
Dunn, Bruce ;
Tolbert, Sarah H. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (05) :1802-1809
[10]  
Brinker CJ, 1999, ADV MATER, V11, P579, DOI 10.1002/(SICI)1521-4095(199905)11:7<579::AID-ADMA579>3.3.CO