www.elsevier.com/locate/ssi
Received 20 December 2004; received in revised form 11 April 2005; accepted 12 April 2005
Abstract
Poly(oxyethylene) (POE)/siloxane-based materials incorporating magnesium triflate (Mg(CF3SO3)2) were synthesized by the sol – gel
process. The host Class II hybrid matrix (di-ureasil) employed is composed of a siliceous framework to which short POE chains are
covalently bonded through urea linkages. Ormolytes with salt composition n (molar ratio of oxyethylene moieties per Mg2+ ion) ranging
from V to 1 were investigated. The nanohybrid with n = 20, which is thermally stable up to 360 -C, exhibits the highest conductivity (e.g.,
approximately 4.0 10 6 and 6.7 10 5 S cm 1 at 35 and 104 -C, respectively). The redox stability domain of this material spans from
3.0 to +2.0 V vs. Mg/Mg2+.
D 2005 Elsevier B.V. All rights reserved.
Keywords: Sol – gel; Di-ureasil; Magnesium triflate; Complex impedance; Cyclic voltammetry
conventional macromolecules, avoiding ‘‘salting out.’’ anode material [28]. The use of Mg for the fabrication of
Thin and flexible ormolyte (organically modified silicate rechargeable solid state batteries also looks very promising
electrolyte) films are readily produced through the sol – gel [29]: (1) its natural abundance makes it cheaper than Li; (2)
process [14]. Two types of hybrids may be produced [13]: it is non-toxic and thus environmentally friendly; (3) it is
Class I hybrids, in which weak interactions (van der less reactive than Li towards oxygen and humid atmos-
Waals contacts, hydrogen bonding, or electrostatic inter- pheres, and thus hazards in open air are minimized; and (4)
actions) are established between both components (one the ionic radii of Li+ and Mg2+ are comparable in
acts as host network and the other as entrapped species), magnitude, meaning that magnesium batteries may use
and Class II hybrids, in which at least a proportion of the insertion compounds that have been developed for lithium
organic and inorganic components are bonded by means cells.
of strong chemical interactions (covalent or iono-covalent In the present work, we will investigate POE/siloxane
bonds). ormolytes doped with magnesium triflate (Mg(CF3SO3)2).
The number of studies of electrolytes containing Mg2+ The host structure of these materials, which contains POE
ions is relatively limited. Some PEs [15 – 22] and gel chains with approximately 40.5 repeat units, belongs to
polymer electrolytes (GPEs) [23 –26] incorporating mag- the class of di-ureasils [30 – 32], a family of Class II
nesium salts have been characterized. The synthesis of hybrids in which the organic and inorganic components
Mg2+-doped ormolytes prepared via sol – gel has only are bonded through urea groups. This study will be
been reported quite recently by Mitra and Sampath [27]. divided into two parts: Part 1 will be devoted to the
These authors describe a Class I matrix derived from synthesis and characterization of the structure, morphol-
tetraethoxyortosilane and poly(ethylene glycol) to which ogy, thermal properties, and electrochemical behaviour of
magnesium perchlorate and magnesium chloride were a series of di-ureasil xerogels with a wide range of
added [27]. Mg(CF3SO3)2 concentration; in Part 2 [33], an in-depth
The development of Mg2+-based systems assumes infrared and Raman spectroscopic analysis of the same set
significant importance in solid state electrochemistry. With of samples will be reported to characterize the local cation
an electrode potential of 2.37 V vs. SHE, and an electro- and anion environments, and to explain the dependence of
chemical equivalence of 2.2 A h g 1, Mg is an attractive the ionic conductivity with salt content.
2. Experimental details
2.1. Materials
2.2. Synthesis
The Mg2+-based di-ureasils were prepared according to the method described in detail elsewhere for the Eu3+-based [34,35]
and Li+-based [12] analogues. Globally, the synthetic procedure involved grafting a POE-based diamine to the ICPTES
precursor, to yield the di-urea cross-linked hybrid precursor molecule:
O O
CH3CH2O OCH2CH3
CH3CH2O Si-CH2-CH2-CH2-N C N-CHCH2-(OCHCH2)a(OCH2CH2)40.5(OCH2CH)c-N C N-CH2-CH2-CH2-Si OCH2CH3
CH3CH2O OCH2CH3
H H CH3 CH3 CH3 H H
a+c = 2.5
which was subsequently hydrolyzed and condensed in the sol –gel stage to induce the growth of the siloxane network.
In agreement with the terminology adopted in previous publications [12,34,35], the ormolytes were identified using the
notation d-U(2000)n Mg(CF3SO3)2, where d-U(2000) represents the host di-ureasil framework (d stands for di, U denotes the
urea group, and 2000 corresponds to the average molecular weight of the starting organic precursor), and n (salt composition)
indicates the number of ether oxygen atoms per Mg2+ cation. For example, the di-ureasil xerogel d-U(2000)20Mg(CF3SO3)2
contains an amount of Mg(CF3SO3)2 such that the OPOE/Mg2+ molar ratio is equal to 20.
S.C. Nunes et al. / Solid State Ionics 176 (2005) 1591 – 1599 1593
The content of Mg(CF3SO3)2 in the samples and other relevant information is given in Table 1. The xerogels with n > 1 were
obtained as transparent, flexible monoliths with a yellowish hue, whereas the material with n = 1 is a white solid.
2.3.1. NMR
29
Si magic angle spinning (MAS) and 13C cross-polarization (CP) MAS NMR spectra were recorded on a Brüker Avance
400 (9.4 T) spectrometer at 79.49 and 100.62 MHz, respectively. 29Si MAS NMR spectra were recorded with 2 As (equivalent
to 30-) rf pulses, a recycle delay of 60 s, and at a 5.0 kHz spinning rate. 13C CP/MAS NMR spectra were recorded with 4 As of
1
H 90- pulse, 2 ms of contact time, a recycle delay of 4 s, and at a spinning rate of 8 kHz. Chemical shifts (d) are quoted in
parts per million from TMS.
2.3.2. XRD
The X-ray diffraction (XRD) measurements were performed at room temperature (RT) with a Rigaku Geigerflex D/max-c
diffractometer system using monochromated CuKa radiation (k = 1.54 Å) over the 2h range of between 4- and 80- at a
resolution of 0.05-. The xerogel samples, analyzed as films (except that with n = 1) were not submitted to any thermal pre-
treatment.
Table 1
Details of the synthetic procedure of the d-U(2000)n Mg(CF3SO3)2 di-ureasils
n = O/Mg2+ m(Mg(CF3SO3)2) Si/Mg2+ Si/Mg2+
(mol mol 1) (g) (mol mol 1
) (g g 1)
V – – –
200 0.0816 9.8765 7.5769
100 0.1632 4.9383 3.7884
80 0.2040 3.9506 3.0307
60 0.2721 2.9630 2.2728
40 0.4081 1.9753 1.5154
20 0.8162 0.9876 0.7577
10 1.6324 0.4938 0.3788
5 3.2648 0.2469 0.1894
1 16.324 0.0494 0.0379
1594 S.C. Nunes et al. / Solid State Ionics 176 (2005) 1591 – 1599
(a) (b)
n = 10
n = 20
n
3
T 200 180 160 140 120 100
2 10
T
n
1
T
10
20
20
80
80
0 -20 -40 -60 -80 -100 -120 200 180 160 140 120 100 80 60 40 20 0
δ (ppm) δ (ppm)
29 13
Fig. 1. Si MAS (a) and C CP/MAS (b) NMR spectra of selected d-U(2000)n Mg(CF3SO3)2 di-ureasils.
3. Results and discussion sites, where R is CH2CH3 or H (Table 2). The calculated
relative population for the three Si environments confirms
3.1. Structure and morphology that, in both samples, the sites present are essentially T 3 (close
to 60%) and T 2 (almost 40%) (Table 2), suggesting a branched
The 29Si MAS and 13C CP/MAS NMR spectra of nature for the polycondensed structures. This result correlates
selected d-U(2000)n Mg(CF3SO3)2 ormolytes are repro- well with the magnitude of the polycondensation rates c
duced in Fig. 1(a) and (b), respectively. The position and (where c = 1 / 3 (%T 1 + 2%T 2 + 3%T 3)) derived for the same
attribution [12,36 –46] of the resonance peaks are listed in Mg2+-doped di-ureasils (around 86%), which are significantly
Table 2. higher than the value reported for the non-doped framework
The 29Si MAS NMR spectra of the d-U(2000)n Mg (75%) [46]. The empirical formula deduced for the three d-
(CF3SO3)2 xerogels with n = 80, 20, and 10 exhibit three U(2000)n Mg(CF3SO3)2 Mg2+-doped nanohybrids (Table 2)
signals at ca. 52, 58, and 66 ppm (Fig. 1(a)). On the basis indicates that a minor number of OCH2CH3 or OH groups
of the conventional T m silicon (Si) notation (m = 1, 2, and 3, attached to the Si atoms persist.
where m 1 is the number of Si atoms bonded to O – Si units), The most significant feature of the 13C CP/MAS NMR
these peaks are ascribed, respectively, to T 1 (CH2 –Si(OR)2 spectra of the di-ureasils with n = 80, 20, and 10 represented
(OSi)), T 2 (CH2 – Si(OR)(OSi)2), and T 3 (CH2 – Si(OSi)3) in Fig. 1(b) is a peak at about 70 ppm, attributed to the
resonance of the dominating OCH2CH2O moieties of d-
1
The classical notation T n has been changed to T m to avoid any U(2000) (Table 2). The remaining functional groups of this
confusion with the notation n used for salt composition throughout the text. hybrid matrix, which are considerably less abundant, give
S.C. Nunes et al. / Solid State Ionics 176 (2005) 1591 – 1599 1595
Table 2
29 13
Si MAS and C CP/MAS NMR data (in ppm) of selected d-U(2000)n Mg(CF3SO3)2 di-ureasils
29
Si MAS [12,46]
n T1 (CH2 – Si(OSi)(OR)2) T 2 (CH2 – Si(OSi)2(OR)) T 3 (CH2 – Si(OSi)3) c (%) Empirical formula
Population (%) Population (%) Population (%)
80 51.0 2.0 58.5 39.1 66.3 59.0 86 RV0.5Si (OR)0.45(O)1.3
20 53.4 2.1 58.5 38.9 66.4 58.9 85 RV0.5Si (OR)0.45(O)1.3
10 52.0 1.8 58.0 36.3 66.0 61.9 87 RV0.5Si (OR)0.40(O)1.3
13
C CP/MAS
n Attribution
[12,36 – 45]
V 80 20 10
160 CfO
75 75.2 74.9 75.1 OCH2CH(CH3)
72 – 70 70.6 70.2 70.4 OCH2CH2O
61 – – – OCH2CH3
47 – 41 – – – CH2CH2CH2Si
25 – 22 – – – CH2CH2Si
18 18.4 18.3 18.4 OCH2CH3
17 17.4 17.0 17.3 OCH2CH(CH3)
15 – 10 – – – CH2Si
Note: RV= – (CH2)3 – NH – C(fO) – NH – (CH(CH3)CH2 – (OCH(CH3)CH2)a V– (OCH2CH2)40.5 – (OCH(CH3)CH2)b V– NH – C(fO) – NH – (CH2)3 – RfH or
CH2CH3.
rise to very weak signals (Fig. 1(b)). We note that the urea series of well-defined peaks, which do not correspond to the
CfO resonance expected at 160 ppm appears as a weak characteristic peaks of Mg(CF3SO3)2 (Fig. 2). This result
event in the spectra of the Mg(CF3SO3)2-doped composites induces us to propose that a crystalline POE/Mg(CF3SO3)2
(insert of Fig. 1(b)). As demonstrated in Table 2, the 13C CP/
MAS NMR data confirm that the grafting reaction gave rise
to the formation of the urea group and was not accompanied n
by the rupture of bonds in the Si-propyl segments or
oligopolymer groups. In agreement with the conclusions
drawn from the 29Si MAS NMR data, the 13C CP/MAS 0
NMR spectra support the suggestion that the hydrolysis
reaction was incomplete, as unreacted OCH2CH3 groups
remain in the materials.
Close analysis of the XRD patterns of the d-
U(2000)n Mg(CF3SO3)2 samples illustrated in Fig. 2 allows
us to conclude that the composites with n = 40, 20, and 10 1
Intensity (a. u.)
complex is formed at this salt concentration. On the basis of also retrieved from DSC experiments. As this interaction
a previous study of the conventional POEn Mg(CF3SO3)2 restricts the local motion of polymer chains, an increase of
system [20], we feel tempted to further suggest that the the glass temperature (T g), which may be monitored in the
stoichiometry of the crystalline compound found in the d- thermograms, results [2]. The variation of the T g of the d-
U(2000) medium is 8. We will seek in Part 2 of this series of U(2000)n Mg(CF3SO3)2 electrolytes with composition, rep-
papers [33] spectroscopic evidences of the formation of this resented in Fig. 3(b), clearly shows that the T g of the POE
POE/Mg(CF3SO3)2 complex in the d-U(2000) medium. chains of d-U(2000) ( 54 -C) [12] remains practically
The DSC curves of the d-U(2000)n Mg(CF3SO3)2 nano- unaffected by the inclusion of increasing amounts of guest
hybrids represented in Fig. 3(a) corroborate the XRD data: salt in samples with n 60. This strongly suggests that
only the samples with 40 n 10 give rise to thermograms either the POE chains of the di-ureasil matrix do not bond
typical of amorphous materials. The pair of low-temper- to the Mg+ ions within this salt composition range, or the
ature, weak-melting peaks visible in the DSC traces of the number of cross-links between the guest species and the
di-ureasils with 200 n 60 (Fig. 3(a)) substantiates the POE chains of the d-U(2000) matrix is insufficient to alter
presence of a minor component of crystalline POE domains the physical behaviour of the polymer within this range of
[34]. The origin of the series of endotherms found between concentration. The further incorporation of guest salt
100 and 200 -C in the DSC curves of the xerogels with n = 5 (n = 40 and 20) leads, however, to a slight T g rise (Fig.
(weak and broad) and n = 1 (well resolved and strong) is 3(b)), an indication that, in both samples, the alkaline-earth
uncertain. They might be associated with the fusion of the ions interact with the ether oxygen atoms of the polymer
POE/Mg(CF3SO3)2 complex identified by means of XRD segments. The T g upshift is particularly dramatic at higher
and with degradation reactions. Acosta and Morales [20] salt concentrations (about 36 and 55 -C, at n = 10 and 5,
showed that the crystalline POE8Mg(CF3SO3)2 complex respectively). The role of the polyether chains in the
melts at 214 -C. As the POE chains of d-U(2000) are coordination process of the cations in the d-U(2000)n
significantly shorter than those of the POE employed by the Mg(CF3SO3)2 hybrids will be one of the main issues to be
above authors (5 106 g mol 1) [20], the melting temper- investigated in Part 2 [33].
ature of the complex occurring in the ormolyte material is The TGA curves of representative d-U(2000) n
expected to be much lower. We will return to the discussion Mg(CF3SO3)2 di-ureasils are depicted in Fig. 4. Samples
of these thermal events below. with 200 n 20 undergo a single weight loss. Close
Valuable information regarding the coordination of the analysis of the TGA curves of the more diluted composites
cations with the host macromolecule in PE systems may be leads us to conclude that Mg(CF3SO3)2 exerts a remarkable
(a) (b)
n
0
1000
1
10
Exo
0
5
-10
Heat flux (mWg-1)
7
Tg (°C)
-20
10 -30
20
-40
40
Endo
-50
60
80 -60
400 100 100 80 60 40 20 0
n
200
100 n = 20
3.2. Ionic conductivity and electrochemical stability
60 200
60 requiring little solvation) [2]. The Mg2+ ion and the hard
40 CF3SO3 base used in the present work fulfill these
20
40 7 requirements. Nevertheless, while strong cation –polymer
5
1
bonds are necessary for PE formation, labile bonds are
20 essential for cation mobility. Thus, in principle, diffusion of
a divalent cation in POE would be expected to be impeded.
A comparison of the cation transference numbers of POE-
0 100 200 300 400 500
based PEs doped with metallic cations and the water
T (°C)
exchange rates around the aqueous cations suggests that
Fig. 4. TGA curves of selected d-U(2000)n Mg(CF3SO3)2 di-ureasils. Mg2+ is an immobile ion [2]. Consequently, PEs based on
magnesium salts should be essentially anionic conductors.
stabilizing effect on d-U(2000). While the non-doped matrix The examination of the Arrhenius conductivity plots of
starts to decompose at about 305 -C [12], the di-ureasils the Mg2+-doped ormolytes with n 5 illustrated in Fig. 5(a)
with n = 60, 40, and 20 are thermally stable up to 361 -C reveals that, above 25 -C, the most conducting ormolyte is
(Fig. 4). In the case of the salt-rich compounds with d-U(2000)20Mg(CF3SO3)2. This amorphous compound
7 n 1, degradation takes place in three stages: a slight exhibits 4.0 10 6, 1.0 10 5, and 6.74 10 5 S cm 1
weight loss (around 10%) occurs at about 52 -C, which at 35, 50, and 104 -C, respectively. At n = 5, a marked
proceeds with two abrupt changes at about 310 and 440 -C reduction in conductivity is observed (Fig. 5(a)). The graph
(Fig. 4). It is noteworthy that the major degradation of the of the conductivity isotherms shown in Fig. 5(b) confirms
most concentrated di-ureasil examined (n = 1) occurs in the that the conductivity maximum of this di-ureasil system
third stage (Fig. 4). These data allow us to assign the appears distinctly at n = 20. The moderate conductivity
endotherms evident in the DSC thermograms of the hybrids exhibited by the essentially amorphous, non-doped hybrid
with n = 5 and 1 to the coupled effect of thermal decom- structure between 25 and 100 -C (approximately 1 10 8
position and fusion of the crystalline POE8Mg(CF3SO3)2 to 2 10 7 S cm 1) was correlated with proton hopping
complex. between neighbouring urea groups [30 –32].
(a) (b)
T /°C
110 100 80 70 60 50 40 30 20 13
10-3
n
∞
200 10-3
T / °C
10-4 100
25
80
30
60 10-4 40
40
50
20
10-5 10
60
7
10-5 70
-1
80
-1
σ / Scm
5
σ / Scm
90
100
10-6 10-6
10-7
-7
10
10-8
10-8
10-9
∞ 200 100 80 60 40 20 0
n
10-9
2.6 2.7 2.8 2.9 3.0 3.1 3.2 3.3 3.4 3.5
1000/T(K-1)
Fig. 5. Arrhenius conductivity plot (a) and isotherms of the ionic conductivity vs. composition (b) of the d-U(2000)n Mg(CF3SO3)2 di-ureasils.
1598 S.C. Nunes et al. / Solid State Ionics 176 (2005) 1591 – 1599
0.16
It is of interest to determine whether the modification of
the POE architecture carried out in the present work by 0.12
means of the hybrid approach is beneficial from the
standpoint of ionic conductivity. 0.08
I (µAcm-2)
reported in the literature for improved PEs doped with the
same magnesium salt. The only value found in the literature 0.00
for the conventional POEn Mg(CF3SO3)2 system relates to
-0.04
the sample with n = 8 [20]. As this sample corresponds to a
crystalline complex, it conducts poorly (e.g., 3.21 10 8 S -0.08
cm 1 at 50 -C) [20] and, consequently, cannot be used for
the purpose of comparison. As expected, the ambient -0.12
-4 -3 -2 -1 0 1 2 3 4
temperature conductivity displayed by the d-U(2000)20 2+
Mg(CF3SO3)2 maximum is significantly lower than that E (V vs Mg/Mg )
exhibited by other systems proposed previously: (1) electro- Fig. 6. RT cyclic voltammogram of the d-U(2000)20Mg(CF3SO3)2 di-
lyte samples composed of Mg(CF3SO3)2, propylene carbo- ureasil (fifth cycle, sweep rate = 10 mV s 1) obtained with a SS/Mg
nate (PC) and ethylene carbonate (EC) included in a photo- ormolyte/SS cell.
cross-linked polymer of poly(ethylene glycol) diacrylate
reinforced by a porous propylene membrane (1.7 10 4 S We note that the conduction mechanism in the hybrid di-
cm 1 at 25 -C for 1% mol of Mg(CF3SO3)2) [21]; (2) urea cross-linked medium will probably be substantially
POE8Mg(CF3SO3)2 plasticized with PC, EC and a mixture different from that occurring in the conventional POE-based
of PC and EC (approximately 1 10 3 S cm 1 at 20 -C) matrix. In fact, while in the di-ureasil host structure two
[22]; (3) GPEs consisting of polyacrylonitrile (PAN), PC, types of coordinating locations (the ether oxygen atoms and
EC and Mg(CF3SO3)2 (1.8 10 3 S cm 1 at 20 -C for an the carbonyl oxygen atoms) may be active, in the latter
optimal molar PAN:PC:EC:Mg(CF3SO3)2 ratio of 1:2:2:0.4) situation, only the ether oxygen atoms have the ability to
[24]; and (4) Mg(CF3SO3)2-doped GPEs based on poly(- solvate the cations. The identification of the mobile species
methylmethacrylate) (PMMA) plasticized with PC and EC in the d-U(2000)-based ormolytes will be the objective of
(4.2 10 4 S cm 1 at 20 -C for an optimal molar the Part 2 of this series of papers [33].
PMMA:(PC + EC):Mg(CF3SO3)2 ratio of 1:2:0.5) [26]. The cyclic voltamogram of the amorphous d-U(2000)20
As the nature of the anion is known to have a major Mg(CF3SO3)2 xerogel is reproduced in Fig. 6. The electro-
influence on ionic conductivity, it is important to examine chemical stability window is limited on the anodic side by
the levels of conductivity attained with other magnesium the irreversible oxidation of the CF3SO3 ion. In this
salts. Patrick et al. [15] doped POE with magnesium voltammogram, an obvious increase in the current density
perchlorate (Mg(ClO4)2) and found that the conductivity occurs at potentials higher than + 1.0 V vs. Mg/Mg2+,
of the electrolyte with n = 12 was approximately 5 10 7 similar to the situation observed with a GPE of PMMA
S cm 1 at 20 -C. The electrolytes prepared with POE and doped with Mg(CF3SO3)2 and plasticized with PC and EC
magnesium chloride (MgCl2) by Yang et al. [16,17] [26]. However, it should be also stressed that the measured
exhibit very poor conductivity at RT (between 10 10 current density values are very low (on the order of 10 2 AA
and 10 9 S cm 1). More recently, a RT conductivity of cm 2), suggesting that the di-ureasil ormolyte with n = 20
ca. 1.9 10 5 S cm 1 was reported for complexes can be considered electrochemically stable over a wide
synthesized from a low-molecular-weight poly(ethylene potential range (from approximately 3.0 to +2.0 V vs.
glycol) and a highly crystallographic disordered form of Mg/Mg2+).
MgCl2 (designated as y-MgCl2) [19]. We should also
comment on the only previously published results
describing the ionic conductivity of sol – gel-derived 4. Conclusions
Mg2+-doped electrolytes [27]. At RT, the most conducting
Class I ormolytes of Mitra and Sampath [27] attain 10 7 Poly(oxyethylene) (POE)/siloxane-based materials incor-
and 10 5 S cm 1 in the presence of MgCl2 and porating magnesium triflate (Mg(CF3SO3)2) were synthe-
Mg(ClO4)2, respectively. sized by the sol –gel process. The host Class II hybrid
The levels of ionic conductivity observed with the sol – matrix (di-ureasil) employed is composed of a siliceous
gel-derived electrolytes proposed here are modest. However, framework to which short POE chains are covalently
it is important to emphasize that the system described in this bonded through urea linkages. Ormolyte films with
paper represents the first characterization of novel materials V > n 1 (where n, salt composition, is the molar ratio of
and the performance may be improved through optimization oxyethylene moieties per Mg2+ ion) were studied. While
of the organic segment length, the choice of the guest salt, or materials with n 60 contain crystalline POE regions,
the nature of the organic– inorganic linkage unit. xerogels with 40 n 10 are entirely amorphous. At
S.C. Nunes et al. / Solid State Ionics 176 (2005) 1591 – 1599 1599
n = 1, a crystalline POE/Mg(CF3SO3)2 complex is formed. [16] L.L. Yang, A.R. McGhie, G.C. Farrington, J. Electrochem. Soc. 133
Samples with 200 > n 20 are thermally stable up to 360 -C. (1) (1986) 1380.
[17] L.L. Yang, R. Huq, G.C. Farrington, G. Chiodelli, Solid State Ionics
The nanohybrid with n = 20 exhibits the highest conductiv- 18 – 19 (1986) 291.
ity (approximately 4.0 10 6 and 6.7 10 5 S cm 1 at 35 [18] G.C. Farrington, R.G. Linford, in: J.R. MacCallum, C.A. Vincent
and 104 -C, respectively). The electrochemical stability (Eds.), Polymer Electrolyte Reviews, vol. 2, Elsevier, 1989, Chapter 8.
domain of this hybrid spans approximately 5 V (from 3.0 [19] V. Di Noto, S. Savina, D. Longo, M. Vidali, Electrochim. Acta 43
(10 – 11) (1998) 1225.
to + 2.0 V vs. Mg/Mg2+).
[20] J.L. Acosta, E. Morales, Electrochim. Acta 43 (7) (1998) 791.
The encouraging results obtained with the d-U(2000)n [21] S. Ikeda, Y. Mori, Y. Furuhashi, H. Masuda, Solid State Ionics 121
Mg(CF3SO3)2 materials, especially the improved mechan- (1999) 329.
ical properties and the moderate ionic conductivity, induce [22] G. Girish Kumar, N. Munichandraiah, J. Electroanal. Chem. 495
us to state that further research on Mg2+-doped d-U(2000)- (2000) 42.
based di-ureasils is worth pursuing. The substitution of [23] G. Girish Kumar, N. Munichandraiah, Electrochim. Acta 44 (1999)
2663.
Mg(CF3SO3)2 by a more suitable magnesium salt will [24] G. Girish Kumar, N. Munichandraiah, Solid State Ionics 128 (2000)
certainly yield materials with higher values of ionic 203.
conductivity. [25] G. Girish Kumar, N. Munichandraiah, J. Power Sources 91 (2000)
157.
[26] G. Girish Kumar, N. Munichandraiah, Electrochim. Acta 47 (2002)
Acknowledgements 1013.
[27] S. Mitra, S. Sampath, J. Mater. Chem. 12 (2002) 2531.
[28] J.L. Robinson, in: N.C. Cahoon, G.W. Heise (Eds.), The Primary
This work was supported by Fundação para a Ciência e Battery, vol. II, John Wiley, 1976, p. 149.
Tecnologia (POCTI/P/CTM/33653/00, SFRH/BD/13559/ [29] D. Aurbach, Z. Lu, A. Schechter, Y. Gofer, H. Gizbar, R. Turgeman, Y.
03, and POCTI/P/CTM/46780/03). S.C. Nunes acknowl- Cohen, M. Moshkovich, E. Levi, Nature 407 (2000) 724.
[30] M. Armand, C. Poinsignon, J.-Y. Sanchez, V. de Zea Bermudez, U.S.
edges Fundação para a Ciência e Tecnologia for a grant.
Patent 5, 283, 310, 1993.
[31] V. de Zea Bermudez, C. Poinsignon, M.B. Armand, J. Mater. Chem. 7
(9) (1997) 1677.
References [32] V. de Zea Bermudez, D. Baril, J.-Y. Sanchez, M. Armand, C.
Poinsignon, in: A. Hugot-Le Goff, C.-G. Granqvist, C.M. Lampert
[1] C. Berthier, W. Gorecki, M. Minier, M.B. Armand, J.M. Chabagno, P. (Eds.), Proc. SPIE, vol. 1728, 1992, p. 180.
Rigaud, Solid State Ionics 11 (1983) 91. [33] S.C. Nunes, V. de Zea Bermudez, D. Ostrovskii, L.D. Carlos, Solid
[2] F.M. Gray, Polymer electrolytes, RSC Materials Monographs, The State Ion (in press).
Royal Society of Chemistry, London, 1997. [34] M.M. Silva, V. de Zea Bermudez, L.D. Carlos, A.P. Passos de
[3] Z. Gadjourova, Y.G. Andreev, D.P. Tunstall, P.G. Bruce, Nature 412 Almeida, M.J. Smith, J. Mater. Chem. 9 (1999) 1735.
(2001) 520. [35] M.M. Silva, V. de Zea Bermudez, L.D. Carlos, M.J. Smith, Electro-
[4] D. Ravaine, M. Armand, Y. Charbouillot, N. Vincens, J. Non-Cryst. chim. Acta 45 (2000) 1467.
Solids 82 (1986) 210. [36] P. Judeinstein, J. Titman, M. Stamm, H. Schmidt, Chem. Mater. 6
[5] M. Popall, M. Andrei, J. Kappel, J. Kron, K. Olma, B. Olsowski, (1994) 127.
Electrochim. Acta 43 (10 – 11) (1998) 1155. [37] F. Ribot, A. Lafuma, C. Eychenne-Baron, C. Sanchez, Adv. Mater. 14
[6] P. Judeinstein, J. Titman, M. Stamm, H. Schmidt, Chem. Mater. 6 (2002) 1496.
(1994) 127. [38] D. Cohn, A. Sosnik, A. Levy, Biomaterials 24 (2003) 3707.
[7] K. Dahmouche, M. Atik, N.C. Mello, T.J. Bonagamba, H. Panepucci, [39] M.C. Gonçalves, V. de Zea Bermudez, R.A. Sá Ferreira, L.D. Carlos,
M.A. Aegerter, P. Judeinstein, J. Sol – Gel Sci. Technol. 8 (1997) D. Ostrovskii, J. Rocha, Chem. Mater. 16 (13) (2004) 2530.
711. [40] S.R. Davis, A.R. Brough, A. Atkinson, J. Non-Cryst. Solids 315
[8] V. de Zea Bermudez, L. Alcácer, J.L. Acosta, E. Morales, Solid State (2003) 197.
Ionics 116 (1999) 197. [41] A.-C. Franville, D. Zambon, R. Mahiou, Y. Troin, Chem. Mater. 12
[9] C. Wang, Y. Wei, G.R. Ferment, W. Li, T. Li, Mater. Lett. 39 (1999) (2000) 428.
206. [42] T.C. Chang, G.P. Wang, H.C. Tsai, Y.S. Hong, Y.S. Chiu, Polym.
[10] J.R. MacCallum, S. Seth, Eur. Polym. J. 36 (2000) 2337. Degrad. Stab. 74 (2001) 229.
[11] K. Nishio, T. Tsuchiya, Sol. Energy Mater. Sol. Cells 68 (2001) 295. [43] E. El Nahhal, M.M. Chehimi, C. Cordier, G. Dodin, J. Non-Cryst.
[12] S.C. Nunes, V. De Zea Bermudez, D. Ostrovskii, M.M. Silva, S. Solids 275 (2000) 142.
Barros, M.J. Smith, L.D. Carlos, J. Rocha, E. Morales, J. Electrochem. [44] S. Hvidt, E.B. Jørgersen, W. Brown, K. Schillén, J. Phys. Chem. 98
Soc. 152 (2) (2005) A429. (1994) 12320.
[13] P. Gomez-Romero, C. Sanchez (Eds.), Functional Hybrid Materials, [45] E.A. Williams, C.L. Sabourin, P.E. Donahue, J.L. Spivack, N.A.
Wiley Interscience, New York, 2003. Marotta, General Electric Research and Development Center, Techni-
[14] C.J. Brinker, G.W. Scherer, Sol – Gel Science: The Physics and cal Information Series (98CRD171), December 1998.
Chemistry OF Sol – Gel Processing, Academic Press, San Diego, [46] L.D. Carlos, R.A. Sá Ferreira, I. Orion, V. de Zea Bermudez, J. Rocha,
CA, 1990. J. Lumin. 87 – 89 (2000) 702.
[15] A. Patrick, M. Glasse, R. Latham, R. Linford, Solid State Ionics [47] L.D. Carlos, V. de Zea Bermudez, R.A. Sá Ferreira, L. Marques, M.
18 – 19 (1986) 1063. Assunção, Chem. Mater. 11 (3) (1999) 581.