Association of paramagnetic species with formation of LiF at the surface of LiCoO2

被引:20
作者
Murakami, Miwa [1 ]
Yamashige, Hisao [1 ]
Arai, Hajime [1 ]
Uchimoto, Yoshiharu [2 ]
Ogumi, Zempachi [1 ]
机构
[1] Kyoto Univ, Off Soc, Acad Collaborat Innovat, Kyoto 6110011, Japan
[2] Kyoto Univ, Grad Sch Human & Environm Studies, Kyoto 6068501, Japan
关键词
Lithium ion battery; Solid-state NMR; LiF; AMPLITUDE CROSS-POLARIZATION; LITHIUM-ION BATTERIES; POSITIVE ELECTRODES; LI-7; SIGNALS; SUPPRESSION; INTERFACE; BEHAVIOR; ALKALI; LAYERS;
D O I
10.1016/j.electacta.2012.05.141
中图分类号
O646 [电化学、电解、磁化学];
学科分类号
081704 ;
摘要
To examine formation of LiF at the surface of LiCoO2, Li-7 and F-19 double-resonance NMR was applied to LiCoO2 electrode samples without any charge/discharge cycles. The two-dimensional (2D) Li-7-F-19 heteronuclear correlation (HETCOR) experiment using cross polarization (CP) shows a large cross peak at (Li-7, F-19) = (ca. 3 ppm, ca. -145 ppm) for the sample without charge/discharge cycles. Since the magnetization build-up curve during F-19 to Li-7 CP shows a characteristic dipolar oscillation observed in pure LiF, the observed cross peak was assigned to LiF formed in the LiCoO2 electrode. For LiF in the LiCoO2 electrode, not only the apparent chemical shift differences from those of pure LiF (ca. -1 ppm, -203 ppm), but also the significant reduction of the spin-lattice relaxation times (T-1 and T-1 rho) were observed. These anomalies are ascribed to the paramagnetic effects. Creation of certain paramagnetic species in associate with the LiF formation on LiCoO2 or the LiF formation at paramagnetic sites at the surface of LiCoO2 was invoked. (C) 2012 Elsevier Ltd. All rights reserved.
引用
收藏
页码:49 / 54
页数:6
相关论文
共 39 条
[1]   Surface characterization of electrodes from high power lithium-ion batteries [J].
Andersson, AM ;
Abraham, DP ;
Haasch, R ;
MacLaren, S ;
Liu, J ;
Amine, K .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 2002, 149 (10) :A1358-A1369
[2]   Recent studies on the correlation between surface chemistry, morphology, three-dimensional structures and performance of Li and Li-C intercalation anodes in several important electrolyte systems [J].
Aurbach, D ;
Zaban, A ;
Ein-Eli, Y ;
Weissman, I ;
Chusid, O ;
Markovsky, B ;
Levi, M ;
Levi, E ;
Schechter, A ;
Granot, E .
JOURNAL OF POWER SOURCES, 1997, 68 (01) :91-98
[4]   An analysis of rechargeable lithium-ion batteries after prolonged cycling [J].
Aurbach, D ;
Markovsky, B ;
Rodkin, A ;
Cojocaru, M ;
Levi, E ;
Kim, HJ .
ELECTROCHIMICA ACTA, 2002, 47 (12) :1899-1911
[5]   THE STUDY OF ELECTROLYTE-SOLUTIONS BASED ON ETHYLENE AND DIETHYL CARBONATES FOR RECHARGEABLE LI BATTERIES .1. LI METAL ANODES [J].
AURBACH, D ;
ZABAN, A ;
SCHECHTER, A ;
EINELI, Y ;
ZINIGRAD, E ;
MARKOVSKY, B .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1995, 142 (09) :2873-2882
[6]   Studies of cycling behavior, ageing, and interfacial reactions of LiNi0.5Mn1.5O4 and carbon electrodes for lithium-ion 5-V cells [J].
Aurbach, Doron ;
Markovsky, Boris ;
Talyossef, Yosef ;
Salitra, Gregory ;
Kim, Hyeong-Jin ;
Choi, Seungdon .
JOURNAL OF POWER SOURCES, 2006, 162 (02) :780-789
[7]   Review on electrode-electrolyte solution interactions, related to cathode materials for Li-ion batteries [J].
Aurbach, Doron ;
Markovsky, Boris ;
Salitra, Gregory ;
Markevich, Elena ;
Talyossef, Yossi ;
Koltypin, Maxim ;
Nazar, Linda ;
Ellis, Brian ;
Kovacheva, Daniella .
JOURNAL OF POWER SOURCES, 2007, 165 (02) :491-499
[8]   Formation of SEI on cycled lithium-ion battery cathodes - Soft X-ray absorption study [J].
Balasubramanian, M ;
Lee, HS ;
Sun, X ;
Yang, XQ ;
Moodenbaugh, AR ;
McBreen, J ;
Fischer, DA ;
Fu, Z .
ELECTROCHEMICAL AND SOLID STATE LETTERS, 2002, 5 (01) :A22-A25
[9]  
Balbuena P.B., 2004, Lithium-Ion Batteries: Solid-Electrolyte Interphase
[10]   SUPPRESSION OF SIGNALS FROM THE PROBE IN BLOCH DECAY SPECTRA [J].
CORY, DG ;
RITCHEY, WM .
JOURNAL OF MAGNETIC RESONANCE, 1988, 80 (01) :128-132