Lithium difluoro(oxalate)borate-based novel nanocomposite polymer electrolytes for lithium ion batteries

被引:23
作者
Aravindan, Vanchiappan [1 ]
Vickraman, Palanisamy [1 ]
Krishnaraj, Kaliappa [2 ]
机构
[1] Gandhigram Rural Univ, Dept Phys, Gandhigram 624302, India
[2] Cent Leather Res Inst, Ctr Leather Apparels & Accessories, Dev Div, Madras 600020, Tamil Nadu, India
关键词
nanocomposite polymer electrolytes; LiDFOB; PVdF-HFP; mechanical stability; Raman spectroscopy;
D O I
10.1002/pi.2430
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
BACKROUND: HF formation and poor thermal stability found in commercial lithium ion batteries comprising LiPF6 (and other salts) have hampered the replacement of LiPF6. Therefore, a new kind of electrolyte salt is necessary to replace the one commercially available. RESULTS: A novel lithium difluoro(oxalate)borate (LiDFOB)-based nanocomposite polymer electrolyte has been prepared in a matrix of poly[ (vinylidene fluoride)-co-(hexafluoropropylene)] (PVdF-HFP). The electrolyte contains ethylene carbonate and diethyl carbonate as plasticizers and nanoparticulate Sb2O3 as a filler. Membranes obtained by a solution casting technique were characterized by AC impedance, thermogravimetry and tensile strength measurements and morphological studies. Membranes with 5 wt% Sb2O3 exhibit a room-temperature conductivity of 0.298mS cm(-1), and are thermally stable up to ca 130 degrees C. Furthermore, the nanocomposite membranes show a 125% increase in mechanical stability as compared to filler-free membranes. The structural change from a to beta phases was confirmed by Raman studies. CONCLUSION: One of the important advantages of using LiDFOB lies in its bulkier DFOB anion, which also acts as solid plasticizer, thus improving the basic requirements of the electrolyte, such as mechanical and thermal stabilities, as well ionic conductivity and with a lower filler content. The overcharge tolerance of LiDFOB salt at higher temperature is also to be noted, because of the oxalate moieties. Preliminary investigations confirmed the possibility of using Sb2O3 nanoparticle-filled membranes in industry in the near future. (c) 2008 Society of Chemical Industry.
引用
收藏
页码:932 / 938
页数:7
相关论文
共 42 条
[11]  
GREGORIO R, 1994, J POLYM SCI POL PHYS, V32, P859, DOI 10.1002/polb.1994.090320509
[12]   Electrochemical and physical properties of composite polymer electrolyte of poly(methyl methacrylate) and poly(ethylene glycol diacrylate) [J].
Kim, HS ;
Kum, KS ;
Cho, WI ;
Cho, BW ;
Rhee, HW .
JOURNAL OF POWER SOURCES, 2003, 124 (01) :221-224
[13]  
Kraus G., 1965, REINFORCEMENT ELASTO
[14]   Effect of electrolyte additives in improving the cycle and calendar life of graphite/Li1.1[Ni1/3Co1/3Mn1/3]0.9O2 Li-ion cells [J].
Liu, Jun ;
Chen, Zonghai ;
Busking, Sara ;
Belharouak, Ilias ;
Amine, Khalil .
JOURNAL OF POWER SOURCES, 2007, 174 (02) :852-855
[15]   Lithium difluoro(oxalato)borate as a functional additive for lithium-ion batteries [J].
Chemical Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439, United States .
Electrochem. Commun., 2007, 3 (475-479) :475-479
[16]   ISOTHERMAL CRYSTALLIZATION OF POLY(VINYLIDENE FLUORIDE) IN THE PRESENCE OF HIGH STATIC ELECTRIC-FIELDS .1. PRIMARY NUCLEATION PHENOMENON [J].
MARAND, HL ;
STEIN, RS ;
STACK, GM .
JOURNAL OF POLYMER SCIENCE PART B-POLYMER PHYSICS, 1988, 26 (07) :1361-1383
[17]   Influence of annealing and chain defects on the melting behaviour of poly(vinylidene fluoride) [J].
Marega, C ;
Marigo, A .
EUROPEAN POLYMER JOURNAL, 2003, 39 (08) :1713-1720
[18]   A study on the state of PWA in PVDF-based proton conducting membranes by Raman spectroscopy [J].
Martinelli, A. ;
Matic, A. ;
Jacobsson, P. ;
Borjesson, L. ;
Navarra, M. A. ;
Munao, D. ;
Panero, S. ;
Scrosati, B. .
SOLID STATE IONICS, 2007, 178 (7-10) :527-531
[19]   Development of oriented structure and properties on drawing of poly(vinylidene fluoride) by solid-state coextrusion [J].
Nakamura, K ;
Nagai, M ;
Kanamoto, T ;
Takahashi, Y ;
Furukawa, T .
JOURNAL OF POLYMER SCIENCE PART B-POLYMER PHYSICS, 2001, 39 (12) :1371-1380
[20]   Enhanced ionic conductivity of polymer electrolytes containing nanocomposite SiO2 particles -: art. no. 266104 [J].
Nan, CW ;
Fan, LZ ;
Lin, YH ;
Cai, Q .
PHYSICAL REVIEW LETTERS, 2003, 91 (26)