J. Phys. Chem.

B 2005, 109, 15161-15164 15161

Spectroscopic Measurements of Ionic Association in Solutions of LiPF6

Christopher M. Burba and Roger Frech*

Department of Chemistry and Biochemistry, UniVersity of Oklahoma, 620 Parrington OVal, Rm 208,
Norman, Oklahoma 73019
ReceiVed: February 8, 2005

Ionic association in nonaqueous electrolytes containing LiPF6 was investigated with infrared absorption
spectroscopy. The spectral intensity of the nondegenerate ν1 mode of the PF6- anion was found to be sensitive
to ion pairing. Although the ν1 mode of an isolated PF6- anion is only Raman active, coordination of Li+ to
PF6- destroys the octahedral symmetry of the anion and results in ν1 becoming simultaneously IR and Raman
active. When the dielectric constant of the solvent is increased, the IR-intensity of the ν1 band decreases
because ion pairing is not favored in high dielectric solvents. Spectroscopic studies of solutions containing
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LiPF6 in diglyme show that ion pairing is also affected by specific cation-solvent interactions. The diglyme-
containing solutions contain significantly fewer ion pairs than expected on the basis of the solvent’s dielectric
constant. It is thought that diglyme:LiPF6 solutions consist mostly of “spectroscopically free” PF6- anions
because the sixfold coordination of Li+ by two diglyme molecules hinders Li+‚‚‚PF6- ion pairing.

Introduction simultaneously Raman and IR active and hence observable in

an infrared transmission measurement. The modification of
Lithium hexafluorophosphate dissolved in aprotic solvents
symmetry-based selection rules through ion-ion interactions
has become a standard electrolyte for secondary lithium ion
would offer an alternative spectroscopic method for examining
batteries.1 A major focus of the research on these electrolyte
fundamental questions of ionic association in electrolyte solu-
systems has been devoted to optimizing the conductivity of
tions. It is known that ionic association decreases with increasing
mixed solvent solutions for practical battery applications.2-9 The
solution dielectric constant.18,27 Therefore, to test this hypothesis,
literature covering this field of research is vast, and it is not in
infrared spectra were measured in a series of solutions whose
the interest of this communication to provide a full literature
solvents have dielectric constants that span a range of values.
review of the subject. Ionic association in electrolytes can affect
the conductivity of a solution by producing low mobility
aggregates or reducing the number of charge carriers in solution Experimental Methods
through the formation of neutral ion pairs.10 Therefore, it is
Lithium hexafluorophosphate was dissolved in the following
important to understand on a molecular level how LiPF6 behaves
solvents (dielectric constants in parentheses): diethyl carbonate
in nonaqueous solvents.
(2.8), dimethyl carbonate (3.1), ethyl acetate (6.0), 2-methoxy-
Vibrational spectroscopic techniques are extremely useful for
ethyl ether [diglyme] (7.3), 2-pentanone (13.48), 2-hexanone
probing ionic associations in many electrolytes.11-18 Early work
(15.45), acetone (20.7), dimethyl sulfoxide (46.7), and propylene
focused on solutions of LiClO412,19 or LiCF3SO313,15 and utilized
carbonate (64.4). All of the solvents were stored over 4 Å
frequency shifts of nondegenerate modes in the Raman spec-
molecular sieves. These solvents were chosen because they do
trum. Later work also examined frequency shifts of nondegen-
not have spectral features in the region of interest (∼740 cm-1)
erate modes in the infrared spectrum.20,21 Several researchers
and they cover a wide range of dielectric constants. In general,
have demonstrated that LiXF6 salts (X ) P, As, or Sb) form
solutions were prepared by dissolving the appropriate amount
ion pairs in aprotic solvents by investigating the infrared-active
of LiPF6 to make a 20:1 (solvent:LiPF6) mole ratio solution.
modes of the XF6- anion.22-26 Most of these studies have
Some lower concentration solutions were also prepared to
focused on the ν3(F1u) and ν4(F1u) vibrations. The symmetry
labels designate the point group irreducible representations of investigate ion-solvent interactions. All of the solutions were
ν3 and ν4 in the isolated anion. Ion-ion interactions perturb made under an argon atmosphere, and each sample was stirred
the octahedral symmetry of the XF6- ion and break the 3-fold for at least 1 h to ensure sample homogeneity.
degeneracy of ν3 and ν4, producing multiple bands in the spectral Infrared absorption spectra of the solutions were recorded
regions containing these vibrations. on a Bruker IFS 66v spectrometer equipped with a KBr beam
During recent infrared transmission studies of LiPF6-based splitter and a DTGS detector. The solutions were sandwiched
electrolytes, bands were observed in the spectral region where between two KBr windows (25 mm in diameter) and were
the ν1 mode is expected (approximately 740 cm-1). According measured under a dry air purge. The resolution of the spec-
to theory, the ν1 mode of isolated PF6- anions is only Raman trometer was set to 1 cm-1, and each spectrum consisted of 64
active. However, the working hypothesis of this paper is that scans averaged together. Raman spectra were measured with
ion-ion interactions between Li+ and PF6- result in ν1 being an ISA Jobin Yvon T64000 spectrometer in the triple subtractive
mode. Spectra were collected in a 90° scattering geometry using
* To whom correspondence should be addressed. Phone: 1-405-325- a Spectra Physics Millennium Vs laser set at 80 mW and a CCD
3831; fax: 1-405-325-6111; e-mail: [email protected]. detector. The excitation wavelength was 532 nm. The samples
10.1021/jp058045f CCC: $30.25 © 2005 American Chemical Society
Published on Web 07/14/2005
15162 J. Phys. Chem. B, Vol. 109, No. 31, 2005 Burba and Frech

pairs in solution depends on the polarizability of the solvent

molecules. Highly polarizable molecules can solvate the Li+
ions and hinder Li+‚‚‚PF6- ion pair formation more effectively
than molecules that are not very polarizable. The dielectric
constant of a solvent is related to the molecular polarizability
through the Clausius-Mossotti relationship.30 Therefore, more
ion pairs are able to form in low dielectric solvents than in high
dielectric solvents, and the intensity of the ν1(A1) band in the
infrared spectrum increases. In high dielectric solutions, it is
more likely that a Li+ ion is surrounded by a cloud of solvent
molecules and counterions rather than forming a contact ion
pair.
Ion-Solvent Interactions. Lithium ion-solvent coordination
is also expected to influence ionic association in these systems.18
Indeed, it has been demonstrated that Li+ ions can interact
strongly with the carbonyl groups of solvents such as dimethyl
carbonate and diethyl carbonate. Aroca et al. showed that adding
LiPF6 to either diethyl carbonate or dimethyl carbonate signifi-
cantly affects the carbonyl stretching frequency.25 Moreover,
LiAsF6 salts strongly affect the conformational equilibrium of
dimethyl carbonate.24 The effect of lithium-solvent interactions
on ν1 was explored for two different solutions: LiPF6 dissolved
Figure 1. Infrared absorption spectra of LiPF6 dissolved in a series of in ethyl acetate ( ) 6.0) and LiPF6 in diglyme ( ) 7.3). The
aprotic solvents (20:1 composition). solvents were chosen because they have similar dielectric
constants and are important components in practical electrolytes
were contained in glass vials, and each spectrum consisted of for lithium ion batteries.1,31 In addition, diglyme is a useful
10 accumulations (2 minutes each) averaged together. spectroscopic model for poly(ethylene oxide)-based polymer
electrolytes.32
Results and Discussion Crystal structures for P(EO)6LiXF633,34 and (diglyme)2LiXF635,36
Ion-Ion Interactions. Isolated PF6- anions have three (X ) P, As, or Sb) have been reported in the literature. In these
Raman active modes (A1g + Eg + F2g), two IR-active modes systems, the ether oxygen atoms of the solvent molecules fully
(2F1u), and one mode that is neither IR nor Raman active (F2u). coordinate the lithium ions, leaving “free” XF6- anions. For
The coordination of Li+ cations to the PF6- anions reduces the example, in the (diglyme)2LiSbF6 crystals, Li+ cations are
symmetry of the PF6- molecule from Oh to CnV (n ) 2-4). completely wrapped by two diglyme molecules, which produces
The exact symmetry of the ion pair will depend on the a sixfold coordination environment for the Li+ ions. Grondin
coordination geometry. For example, in a bidentate configura- et al. used vibrational spectroscopy to identify free PF6- ions
tion, the Li+ ion interacts with two adjacent fluorine atoms of in (diglyme)2LiPF6 crystals.36 Furthermore, Seneviratne et al.
the PF6- molecule and the symmetry of the Li+‚‚‚PF6- species demonstrated that diglyme:LiSbF6 solutions contain mostly free
would be C2V. The three possible coordination geometries of SbF6- anions.35 By way of comparison, the lithium ion coor-
the Li+‚‚‚PF6- ion pair all destroy the center of symmetry of dination in diglyme:LiPF6 solutions would be expected to be
the PF6- anion and change the symmetry of the ν1 mode from similar to the (diglyme)2LiPF6 crystals and the diglyme:LiSbF6
A1g to A1. Consequently, ν1(A1) for ion-paired PF6- anions will solutions; hence, diglyme:LiPF6 solutions should contain pre-
be simultaneously Raman and IR active. Throughout the dominantly free PF6- anions.
remainder of this paper, ν1(A1) will refer to the ν1 mode of Figure 2 compares Raman and infrared spectra of the ethyl
ion-paired PF6- anions while ν1(A1g) denotes the ν1 vibration acetate:LiPF6 and diglyme:LiPF6 solutions at several different
of “spectroscopically free” PF6- anions. concentrations. The Raman spectra of both systems show a
Figure 1 contains infrared spectra of LiPF6 dissolved in a gradual increase in ν1 scattering intensity (741 cm-1) as the
series of solvents (20:1 mole ratio). As pointed out by Perelygin LiPF6 concentration is increased. The relative Raman scattering
et al., the ν4 band at 558 cm-1 is only marginally affected by intensity of the ν1 mode in these solutions agrees with previously
salt concentration and solvent type;22 therefore, all of the spectra published results for LiPF6 solutions at similar concentrations.25
are scaled with respect to this band. In Figure 1, the band Inspection of the 741 cm-1 band in the infrared spectra indicates
centered at 741 cm-1 gradually decreases in intensity as the that ion pairing is much more prevalent in ethyl acetate:LiPF6
dielectric constant of the solvent increases. The frequency of solutions than in diglyme:LiPF6 solutions. In fact, the diglyme:
this band is nearly identical to the ν1(A1g) mode in Raman LiPF6 solutions essentially lack any IR-activity for ν1(A1) over
spectra of solid KPF6 (751 cm-1)28 and aqueous solutions of this concentration range. Figure 3 further illustrates the unique
NH4PF6 (741 cm-1).29 Accordingly, the observation of this band nature of the diglyme:LiPF6 solutions. Here, an infrared
in the infrared spectra of LiPF6 solutions is attributed to ν1 and spectrum of a 20:1 diglyme:LiPF6 solution is compared to ethyl
is postulated to result from a breakdown in selection rules for acetate:LiPF6 and acetone:LiPF6 solutions at the same concen-
PF6- anions that participate in Li+‚‚‚PF6- ion pairs. tration. The IR-intensity of the ν1(A1) band is much less in the
In high dielectric solvents such as dimethyl sulfoxide and diglyme:LiPF6 solution than the other two solutions even though
propylene carbonate, the ν1 band essentially vanishes. It is useful diglyme has a relatively low dielectric constant.
to think of solvent-cation interactions in terms of the polariz- The degenerate ν3 mode is also sensitive to the presence of
ability of the solvent molecules rather than the macroscopic Li+‚‚‚PF6- ion pairs in solution,22-25 and strong ν3 bands appear
dielectric constant of the solvent because the number of ion in the infrared spectra of both systems between 800 and 900
Spectroscopic Measurements of Ionic Association J. Phys. Chem. B, Vol. 109, No. 31, 2005 15163

ethers. Consequently, higher concentrations of Li+‚‚‚PF6- ion

pairs may form in those solutions.

Conclusions
Cation-anion interactions (presumably ion pairs) of the PF6-
anion in solutions have been spectroscopically observed via an
unusual mechanism involving the nondegenerate ν1 mode. In
the isolated anion, this mode can be observed only in the Raman
spectrum because of the presence of a center of symmetry. In
LiPF6 solutions, the interaction of Li+ with PF6- destroys the
octahedral symmetry of the anion and results in ν1 becoming
simultaneously IR and Raman active. Ionic association in these
solutions is strongly affected by the dielectric constant of the
solvent. In high dielectric solvents, the solvent molecules can
interact strongly with Li+ cations, and only a small fraction of
the PF6- anions can penetrate the Li+ solvation shell to form
ion pairs. Cation-solvent interactions also influence ionic
association in LiPF6-based electrolytes. The IR-intensity of
ν1(A1) is smaller in diglyme:LiPF6 solutions than in ethyl
Figure 2. Raman scattering and infrared absorption spectra of diglyme: acetate:LiPF6 solutions even though the solvents have compa-
LiPF6 and ethyl acetate:LiPF6 solutions. The dotted lines (‚‚‚) denote rable dielectric constants. It is believed that two diglyme
ν1 vibrations and the lines with alternating dashes and dots (‚-‚) mark molecules wrap Li+ cations in a sixfold coordination environ-
ν3 vibrations. ment, which severely hinders the ability of the PF6- anions to
coordinate with the Li+ cations. Although the IR-intensity of
the ν1(A1) band is proportional to the number of Li+‚‚‚PF6-
ion pairs present in solution, this avenue of quantifying the ion
pairs was not pursued.

Acknowledgment. This work was funded by the U.S.

Department of Defense, Army Research Office under project
number W911NF-04-1-0322.

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