Transport properties Of V2O5/polypyrrole nanocomposite prepared by a sol-gel alkoxide route

被引:51
作者
Huguenin, F
Girotto, EM
Torresi, RM
Buttry, DA
机构
[1] Univ Sao Paulo, Inst Quim Sao Carlos, BR-13560970 Sao Carlos, SP, Brazil
[2] Univ Wyoming, Dept Chem, Laramie, WY 82071 USA
来源
JOURNAL OF ELECTROANALYTICAL CHEMISTRY | 2002年 / 536卷 / 1-2期
基金
巴西圣保罗研究基金会; 美国国家科学基金会;
关键词
V2O5; polypyrrole; nanocomposite; Lli ion battery; sol-gel method;
D O I
10.1016/S0022-0728(02)01188-9
中图分类号
O65 [分析化学];
学科分类号
070302 ; 081704 ;
摘要
Nanocomposites of V2O5 xerogel and polypyrrole (Ppy) were prepared from a vanadyl tris(isopropoxide) precursor and pyrrole monomer by in situ oxidative polymerization of the pyrrole in the sot stage followed by gelation. Unlike previous sot-gel nanocomposite synthetic routes, the gel forms a stable solution from which thin homogeneous films can be cast. The nanocomposite was characterized by XRD, FTIR and electrochemical measurements. Three different thin film types with different spatial arrangements were used to characterize the compensation of charge. X-ray diffraction reveals that the Ppy chains are intercalated within the interlayer region of the V2O5, leading to an increase in the d-spacing from 11.85 Angstrom for V2O5 to 13.8 Angstrom for the nanocomposite. Electrogravimetric results showed that electroneutrality during charging and discharging is achieved predominantly by Li+ transport. EQCM studies of a bilayer film arrangement with the nanocomposite cast over an electropolymerized film of Ppy revealed that the nanocomposite is an effective barrier for anion transport. The nanocomposite showed a higher specific capacity (283 A h kg(-1)) than that of V2O5 (236 A h kg(-1)). This result was attributed to differences in structure between the two materials. The galvanostatic intermittent titration technique (GITT) was used to obtain the diffusion coefficients of Li+ in the nanocomposite and the V2O5 xerogel. These values range from 2 x 10(-11) to 3 x 10(-13) cm(2) s(-1), decreasing as the amount of intercalated Li+ is increased. For V2O5 the Li+ diffusion coefficient ranged from 1 x 10(-12) to 8 X 10(-14) cm(2) s(-1), also decreasing as the amount of intercalated Li+ increased. In situ resistance measurements revealed a very high conductivity over the potential range of 0.4 to -0.7 V (vs. Ag/AgNO3) for the nanocomposite, more than a factor of five larger than that for V2O5. (C) 2002 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:37 / 45
页数:9
相关论文
共 49 条
[31]   HIGH-FREQUENCY IMPEDANCE ANALYSIS OF QUARTZ-CRYSTAL MICROBALANCES .1. GENERAL-CONSIDERATIONS [J].
NOEL, MAM ;
TOPART, PA .
ANALYTICAL CHEMISTRY, 1994, 66 (04) :484-491
[32]   Electrochromic and conductivity properties:: a comparative study between melanin-like/V2O5•nH2O and polyaniline/V2O5•nH2O hybrid materials [J].
Oliveira, HP ;
Graeff, CFO ;
Brunello, CA ;
Guerra, EM .
JOURNAL OF NON-CRYSTALLINE SOLIDS, 2000, 273 (1-3) :193-197
[33]  
OSAKA T, 1999, INTERFACE, V8, P9
[34]   Lithium ion insertion in porous metal oxides [J].
Owens, BB ;
Passerini, S ;
Smyrl, WH .
ELECTROCHIMICA ACTA, 1999, 45 (1-2) :215-224
[35]   Composites of V2O5 aerogel and nickel fiber as high rate intercalation electrodes [J].
Parent, MJ ;
Passerini, S ;
Owens, BB ;
Smyrl, WH .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1999, 146 (04) :1346-1350
[36]   V2O5 XEROGEL FILMS AS INTERCALATION HOSTS FOR LITHIUM .1. INSERTION STOICHIOMETRY, SITE CONCENTRATION, AND SPECIFIC ENERGY [J].
PARK, HK ;
SMYRL, WH ;
WARD, MD .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1995, 142 (04) :1068-1073
[37]   V2O5 XEROGEL FILMS AS INTERCALATION HOSTS FOR LITHIUM [J].
PARK, HK ;
SMYRL, WH .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1994, 141 (03) :L25-L26
[38]   XAS and electrochemical characterization of lithium intercalated V2O5 xerogels [J].
Passerini, S ;
Smyrl, WH ;
Berrettoni, M ;
Tossici, R ;
Rosolen, M ;
Marassi, R ;
Decker, F .
SOLID STATE IONICS, 1996, 90 (1-4) :5-14
[39]   ELECTROCHEMICAL PROPERTIES OF CATHODIC MATERIALS SYNTHESIZED BY LOW-TEMPERATURE TECHNIQUES [J].
PEREIRARAMOS, JP .
JOURNAL OF POWER SOURCES, 1995, 54 (01) :120-126
[40]   VERWENDUNG VON SCHWINGQUARZEN ZUR WAGUNG DUNNER SCHICHTEN UND ZUR MIKROWAGUNG [J].
SAUERBREY, G .
ZEITSCHRIFT FUR PHYSIK, 1959, 155 (02) :206-222