Vibrational Spectroscopy 44 (2007) 197200 www.elsevier.

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Short communication

Vibrational spectroscopic and conductimetric studies of lithium battery electrolyte solutions

Abstract Extremely high concentrated solutions of lithium perchlorate in formamide and acetonitrile equimolar mixture were investigated by spectroscopic and conductimetric techniques. The spectral changes observed in the characteristic bands of the solvents, the appearance of the band at 939 cm1 and the slight increase of conductivity in all solutions were interpreted in terms of a solvent separated ion pairs model. In fact, the mixture of solvents with considerable differences in the donoracceptor characters allows to prepare electrolytic solutions where the contact ion pairs formation seems uncertain. # 2006 Elsevier B.V. All rights reserved.
Keywords: Vibrational spectroscopy; Conductimetry; LiClO4; Acetonitrile; Formamide

1. Introduction The importance of studies on ion association and solvation phenomena in lithium battery electrolytic solutions needs no emphasis. The different interactions which take place in a solution often determine the battery performance [1]. The basic requirements of an electrolytic solution for electrochemical devices can be seen in a recent review of Xu [2]. Although progress has been made in enhancing the conductivity of solid electrolytes, liquid electrolytes are still used the most in electrochemical systems [3]. In general, all solvents used in lithium battery electrolytic solutions are Lewis bases that preferentially interact with cations [4]. On the other hand, anions are poorly solvated [5] and as so a high degree of ion pairing in concentrated solutions is observed. This decreases the conductivity and the lithium ion transference in electrochemical systems. Since the concentration of most electrolytes for Libased systems is almost always at least 1.0 mol L1 and, more commonly, between 1.5 and 3.0 mol L1, an investigation of extremely high concentrated solutions become important. In this communication, vibrational spectroscopic and conductimetric results indicate the formation of stable solvates, in a wide
* Tel.: +55 21 26822807; fax: +55 21 26822807. E-mail addresses: waa@ufrrj.br, wag@iq.ufrj.br. 0924-2031/$ see front matter # 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.vibspec.2006.10.005

concentration range, to the LiClO4/formamide:acetonitrile system. The equimolar mixture of solvents with considerable differences in the donoracceptor characters allows to prepare electrolytic solutions where the contact ion pairs formation seems uncertain. 2. Experimental Raman spectra were obtained with Nicolet FT-Raman 950 using the 1064 nm line of the Nd:YAG laser at 1300 mW of power and InGaAs detector operating at room temperature. The samples were inserted in 5 mm diameter tubes. The infrared spectra were recorded on a Nicolet FT-IR Magna 760 spectrophotometer using NaCl windows. Both infrared and Raman spectra were obtained with 1 cm1 resolution at the temperature of 24 2 8C. The conductivity was measured at 10 kHz ac using an LCR meter (AG-4311, Ando Electric) at 25 8C. A Kraus-type glass cell (constant equal at 0.1) with platinized Pt electrodes was used for the measurements. Formamide (Merck) was distilled at reduced pressure, discarding the rst and last portions of distillate and maintained under a N2 atmosphere. Acetonitrile (Vetec) was dried using thermally activated 3 A molecular sieves. Lithium perchlorate (Vetec) was dried by heating under vacuum at 150 8C. All concentrations are expressed as molarities (mol L1) and the

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spectral components were obtained by tting Lorentzian proles using ORIGIN MICROCAL 6.1 software [6]. 3. Results and discussion Formamide (FA) can coordinate with both Li+ and ClO4 ions due to its two polar groups (CO and NH2 sites) [7,8]. Moreover, FA has a high relative permittivity (111 at 25 8C) [9] and a high viscosity (3.3 102 P at 25 8C) [10]. The former property helps to dissociate the dissolved salt, but the latter is disadvantageous for the ion transport. These are the main reasons that practical batteries use mixed solvents systems (e.g. a high permittivity solvent and a low viscosity solvent) [1]. In this case, acetonitrile (ACN) was used as cosolvent (viscosity equal at 0.3 102 P at 25 8C) [11]. In addition, the CBBN group is a very sensitive probe for interactions of this solvent with cations [12] and other acidic centers [13,14]. The Raman bands of FA show little change of frequency or shape on addition of LiClO4, except for the carbonyl band (Fig. 1A). In

this region, the component at 1685 cm1 is assigned to hydrogen-bonded species forming a chain of FA molecules whereas the component at 1700 cm1 corresponds to FA molecules which have no hydrogen bonds to their carbonyl groups [15,16]. As the concentration of LiClO4 increases from 1.0 to 5.0 mol L1, a new band at 1714 cm1 increases in intensity at the expense of the 1685 cm1 component. This behavior is consistent with the assignment of the new band to complexed FA to the Li+ ions [8]. It is worth noting that the1685 cm1 component is more sensitive to the increasing of the salt concentration. Since the dominant species in liquid FA consist of chains, this behavior is expected. Signicant spectral changes with increasing concentration of lithium cations can also be observed in the CBBN region of ACN (Fig. 1B). The band envelope in the region between 2270 and 2240 cm1 was discussed in details in a recent work [14]. The band at 2253 cm1 corresponds to non-associated ACN molecules whereas the 2257 cm1 band is assigned to a FA ACN adduct. These two components are also accompanied by other two bands at 2250 and 2246 cm1, which are assigned to hot bands. With the addition of LiClO4, a new band at 2275 cm1 appears and its intensity increases with increasing salt concentration. A similar change is observed for the band at 2293 cm1. Another new band at 2306 cm-1 increases in intensity at the expense of the original. The new bands at 2275 and 2306 cm1 are assigned to the CBBN stretching and combination mode, (n3 + n4), of coordinated ACN to the Li+ ions, respectively [12]. Since FA is a stronger Lewis acid than ACN [14], FAanion interactions must be present in this system. Thus, the NH stretching region of FA in the presence of LiClO4 was also investigated. In this region the IR spectrum of the pure solvent shows a broad and very intense absorption with four bands centered at 3190, 3270, 3325 and 3410 cm1. The values in wavenumbers and bands shape are in agreement with the literature [17]. The addition of lithium perchlorate leads to the appearance of a new band at 3568 cm-1 whose the intensity increases with the salt concentration (Fig. 2). Thus, the band at

Fig. 1. Raman spectra of LiClO4 in equimolar FA:ACN mixtures. (A) C O stretching region. (B) CBBN stretching region. Molar concentrations of LiClO4 are: (a) 1.0; (b) 2.0; (c) 3.0; (d) 4.0; (e) 5.0. Dotted lines represent the deconvolution result using Lorentzian proles.

Fig. 2. IR spectra of LiClO4 in equimolar FA:ACN mixtures in the NH stretching region. Molar concentrations of LiClO4 are: (a) 1.0; (b) 3.0; (c) 5.0. Dotted lines represent the deconvolution result using Lorentzian proles.

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3568 cm-1 has been assigned to FA-ClO4 interactions via hydrogen bonding, similarly to the work of Bukowska [7] where the new band was also seen on the high frequency side, using partly deuterated formamide, relative the bulk FA bands. Moreover, the high acceptor number or in others words, the two H-bond donor sites of FA must preferentially interact with negative chemical species [18]. The interpretation to the spectral changes in the N-H stretching region of FA is consistent with FAClO4 interactions via hydrogen bonding. At the same time, for the CO and CBBN stretching regions of FA and ACN, respectively, a competition between the two solvents by Li+ was observed. Thus, it is interesting to investigate the region of the solute since concentration-dependent variations in the spectra of oxyanions are usually interpreted in terms of symmetry perturbations due to contact ion pairs formation [19]. Moreover, the magnitude of the spectral variations increases with the strength of the interaction. The weakly coordinating character of the perchlorate anion, in solution, gives spectral variations limited to n1 and n2 regions alone [20]. In the present system, the n2 mode of this anion is not affected by increasing the salt concentration, but the n1 band presents a slight asymmetry (Fig. 3). As can be seen, the symmetric stretching region of the perchlorate anion contains two components. The positions of the curve-tted bands are in agreement with free ClO4 (934 cm1) and solvent separated ion pairs (939 cm1). Some authors observed the appearance of a third band at 945 cm1, which was assigned to contact ion pairs [2124]. However, this latter band was not seen in these experiments. Conductivity measurements are commonly used in the studies of ion pairs formation. Therefore, this tool will be used to investigate the present system. In general, the conductivity increases with increasing concentration of electrolyte until a maximum is reached. At higher salt concentrations the conductivity decreases along with increasing solution viscosity and this may be explained by the contact ion pairs and ion aggregate formation in solution [1,3]. In contrast, the results presented here show a slight increase of conductivity in all

Fig. 4. Conductivity behavior of LiClO4 in equimolar FA:ACN mixtures as a function of salt concentration.

concentration range studied (Fig. 4). Such fact suggests that the interaction between LiClO4 and molecules of the solvents is strong. In this way, FA and ACN molecules seem not to be replaced by the counterion, in the inner-sphere of Li+, and a decreases in the conductivity is not observed. The spectral modications observed in the characteristic bands of the solvents, the appearance of the band at 939 cm1 and the slight increases of conductivity in all solutions are consistent with the assignment to the stable solvates formation such as solvent separated ion pairs. In a recent paper, Brouillette et al. [25] have presented a study on several stable solvates that were described as solvent separated ion pairs and contact ion pairs. Those authors concluded that systems where the participation of solvent separated ion pairs is majority, have a relatively high conductivity. Therefore, the LiClO4/formamide:acetonitrile system represents an important contribution to the understanding of the mechanisms of ion transport in electrochemical cells. Although the focus of this study is the characterization of ion association and solvation phenomena, a future work using Raman intensity data of the regions presented here as well as a support by quantum chemical calculations will be useful to describe the structures of these solvates. Acknowledgements This work was sponsored by CNPq, FAPERJ and FINEP (project no. 65.953810). References
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Fig. 3. Raman n1 band of perchlorate in equimolar FA:ACN mixtures. Molar concentrations of LiClO4 are: (a) 1.0; (b) 2.0; (c) 3.0; (d) 4.0; (e) 5.0. Dotted lines represent the deconvolution result using Lorentzian proles. The arrow indicates the ACN band that was also used for curve tting.

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