Compositional introduction of lithium ions into conductive polyoxovanadate-surfactant hybrid crystals

Article abstract of DOI:10.1039/c7ce00595d

Polyoxovanadate-surfactant hybrid layered crystals were successfully synthesized as single crystals by employing a primary alkylammonium cation, octylammonium ([C₈H₁₇NH₃]⁺, C₈NH₃). Two types of hybrid crystals with the formulae [C₈H₁₇NH₃]₆[V₁₀O₂₈]·2H₂O (C₈NH₃-V₁₀) and [C₈H₁₇NH₃]₄Li₂[V₁₀O₂₈]·4C₂H₅OH??6H₂O (C₈NH₃-Li-V₁₀) were obtained by different synthetic procedures. Changing the synthetic conditions enabled the precise introduction of lithium cations into the polyoxovanadate-surfactant hybrid crystals according to compositional control. C₈NH₃-V₁₀ contained a discrete [V₁₀O₂₈]^6- anion, while C₈NH₃-Li-V₁₀ was composed of a [V₁₀O₂₈]^6- anion associated with two lithium cations formulated as {[Li(H₂O)₃]₂[V₁₀O₂₈]}^4-. The conductivities of C₈NH₃-V₁₀ and C₈NH₃-Li-V₁₀ were investigated under anhydrous conditions at intermediate temperatures.

Full text of DOI:10.1039/c7ce00595d

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Compositional introduction of lithium ions into
conductive polyoxovanadate–surfactant hybrid
crystals†
Cite this: DOI: 10.1039/c7ce00595d
a
a
a
a
Yoshiki Kiyota, Minako Taira, Saki Otobe, Koji Hanyuda,
b
a
Haruo Naruke and Takeru Ito
*
Polyoxovanadate–surfactant hybrid layered crystals were successfully synthesized as single crystals by
+
employing a primary alkylammonium cation, octylammonium ([C
crystals with the formulae [C 28]·2H O (C NH
6H O (C NH –Li–V10) were obtained by different synthetic procedures. Changing the synthetic conditions
8
H
17NH
3
] , C
8
NH
3
). Two types of hybrid
8 3 6
H17NH ] ijV10O
2
8
3
–V10) and [C
8
H17NH
3
]
4
Li 28]·4C OH
2
ijV10
O
2 5
H
·
2
8
3
Received 28th March 2017,
Accepted 3rd May 2017
enabled the precise introduction of lithium cations into the polyoxovanadate–surfactant hybrid crystals
6−
according to compositional control. C
8
NH
3
–V10 contained a discrete [V10
28
O ]
8 3
anion, while C NH –Li–V10
6−
was composed of
a
[V10
28]} . The conductivities of C
drous conditions at intermediate temperatures.
O
28
]
anion associated with two lithium cations formulated as
DOI: 10.1039/c7ce00595d
4−
{
2 3 2
[LiIJH O) ] ijV10O
8
NH –V10 and C NH –Li–V10 were investigated under anhy-
3
8
3
rsc.li/crystengcomm
As inorganic components, polyoxometalate (POM) anions
having characteristic redox properties are suitable for this
Introduction
1
1–13
Innovative battery technology such as lithium-ion batteries is
necessary for sustainable development in our future. Lithium-
ion batteries have been widely used as rechargeable power
sources for several mobile electronics and emergency
purpose.
cations
hybrid single crystals.
POM anions can be hybridized with surfactant
1
4–19
to form stable layered crystals as POM–surfactant
2
0–39
Such ionic crystals are a rare series
of materials, and both POM and surfactant components can
be variously selected to tune the structure and function of in-
1–3
batteries.
The present lithium-ion batteries employ flam-
2
2
mable organic liquid electrolytes, which are necessary to be
substituted by solid electrolytes to overcome safety problems
especially when used at intermediate temperatures (373–573
K). However, lithium-ion conductive solid electrolytes to date
are on their way to being industrialized, and more conducting
organic–organic hybrids. The layered structures in POM–
surfactant hybrid crystals are expected to contribute to the
emergence of conductive properties including proton
2
9,30
conductivity.
In these POM–surfactant hybrid crystals, small counter
4–6
+
+
materials are demanded.
cations such as Na or H have been introduced under mild
2
0,24–29
The emergence of high conductivity in solid electrolytes
requires precise control of the composition and structure. A
promising strategy is to employ inorganic and organic molec-
ular components and to construct inorganic–organic hybrid
conditions without severe heating,
and the composi-
tion can be easily controlled by simply changing the kind of
+
+
+
coexisting cation. The monovalent metal cations Na , K , Cs ,
+
and Ag were introduced into the POM–surfactant hybrid
7
–10
materials.
Inorganic–organic hybrid solid electrolytes en-
crystals through the isomerization of octamolybdate
2
4–27
+
able controlling the structure flexibly due to the organic moi-
ety and increasing the stability owing to the inorganic moi-
anions.
However, Li cation-containing POM–surfactant
hybrid crystals have not been realized to date.
1
0
ety.
The precise and selective introduction of lithium
Among several types of POMs, the decavanadate
6
−
cation(s) into such hybrid materials can lead to another class
of lithium-ion conductors.
([V10
O
28] ,
V
10
)
anion tends to be associated with
4
0–45
+
46
proton(s)
and Li cation(s). Therefore, V –surfactant
1
0
+
hybrid crystals are promising for Li cation-containing mate-
rials, while only two hybrid crystals of V10 associated with sur-
factants with a long alkyl chain (number of carbon atoms ≥8)
a
Department of Chemistry, School of Science, Tokai University, 4-1-1 Kitakaname,
Hiratsuka 259-1292, Japan. E-mail: takeito@keyaki.cc.u-tokai.ac.jp;
Fax: +81 463 58 9543; Tel: +81 463 58 1211 ex. 3737
20,29
have been reported.
b
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta,
+
We report here the syntheses and structures of Li cation-
Midori-ku, Yokohama 226-8503, Japan
containing hybrid crystals by using V10 anions and primary
†
CCDC 1540311 and 1540312. For crystallographic data in CIF or other
+
electronic format see DOI: 10.1039/c7ce00595d
alkylammonium cations, n-octylammonium ([C H NH ] ,
8
17
3
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+
+
C NH ). Two types of crystals with and without Li cations,
absorption analysis confirmed the presence of Li cations in
8
3
C NH –V (1) and C NH –Li–V (2), were obtained as single
the crystals of 2. Ethanol molecules of crystallization were
easily removed under ambient atmosphere. Anal. calcd for
C H N Li V O (%): C, 24.02; H, 5.79; N, 3.50. Found: C,
24.01; H, 5.58; N, 3.43. Melting point: 423 K. IR (KBr, ν/cm ):
985m, 944s, 817m, 742m, 603m, 537m, 466w, 450w, 414w.
8
3
10
8
3
10
crystals. Precise control of the synthetic procedure enables
+
the introduction of Li cations by compositional control. This
32
92
4
2 10 34
+
−1
Li cation-containing hybrid crystal is the first POM–surfac-
+
tant crystal with introduced Li cations.
Experimental
Crystal structure determination
Materials and general methods
Single crystal X-ray diffraction measurements were performed
using a Rigaku RAXIS RAPID imaging plate diffractometer
with graphite monochromated Mo Kα radiation (λ = 0.71075
Å). Diffraction data were collected and processed with PRO-
All chemical reagents were obtained from commercial
sources (Wako and TCI, the highest grade) and employed
without further purification. Octylammonium chloride
4
7
CESS-AUTO. The structures were solved by the charge flip-
8 3 8 3
([(C H17)NH ]Cl, C NH ·Cl) was prepared by adding equimolar
4
8
ping method and expanded using Fourier techniques. The
refinement procedure was performed by the full-matrix least-
squares method using SHELXL Version 2014/7 (ref. 49)
hydrochloric acid to n-octylamine, and obtained as white pre-
cipitates after filtration. IR spectra (as KBr pellet) were
recorded on a Jasco FT/IR-4200ST spectrometer. CHN elemen-
tal analyses were performed with a LECO CHNS-932 elemen-
tal analyser. Powder X-ray diffraction (XRD) patterns were
measured with a Rigaku MiniFlex300 diffractometer using Cu
Kα radiation (λ = 1.54056 Å) at ambient temperature. Conduc-
tivity measurements were carried out by an alternating cur-
rent (AC) impedance method in the frequency range from 5
Hz to 13 MHz using an Agilent 4192A inductance–capaci-
tance–resistance (LCR) meter. Pelletized powder samples (10
mm in diameter) were sandwiched with Pt electrodes, and
measured under a dry Ar atmosphere. For C NH –V (1), the
5
0
through the CrystalStructure software package. The diffrac-
tion data for 1 recorded at PF-AR (NW2A beamline) of the
High Energy Accelerator Research Organization (KEK) con-
firmed the same crystal structure.
In the refinement procedure, all non-hydrogen atoms of 1
and 2 were refined anisotropically. The C atoms of the etha-
nol molecules in 2 were disordered. The hydrogen atoms on
the C atoms were located in calculated positions, and the H
atoms of the ethanol solvent in 2 were not included in the
refinement.
8
3
10
pelletized sample with a thickness of 0.93 mm was measured
at 403 K, while the sample with a thickness of 0.32 mm was
measured at 413 K for C NH –Li–V (2).
Results and discussion
Syntheses of C NH –V (1) and C NH –Li–V (2)
8
3
10
8
3
10
8
3
10
The as-prepared C NH –V (1) was initially isolated as crys-
8
3
10
Syntheses of compounds
NH –V10 (1). C NH
solid V O (0.40 g, 2.2 mmol) was dispersed in 40 mL of water
talline precipitates from the pH-adjusted V10 solution com-
bined with C NH solution. The IR spectrum of 1 (Fig. 1a) in-
dicates typical peaks for the decavanadate (V ) anion in the
C
8
3
8
3
–V10 (1) was synthesized as follows:
8
3
2
5
10
−
1 40,42
and dissolved by adding LiOH·H O (0.24 g, 5.7 mmol). The
range of 400–1100 cm ,
and the IR spectrum of the sin-
2
solution was adjusted to pH 6.0 with 6 M HCl, and the
resulting orange solution was added at room temperature to
an ethanol solution (15 mL) of C NH ·Cl (0.23 g, 1.4 mmol)
gle crystals of 1 (Fig. 1b) obtained from the recrystallization
process exhibited almost the same peaks as those for the as-
prepared product of 1 (Fig. 1a). In addition, the powder X-ray
8
3
with stirring for 15 min. The obtained yellow-orange crystal-
line precipitates were filtered off and washed with 24 mL of
ethanol to obtain the as-prepared product of 1 (ca. 40%
yield). Yellow rod crystals were obtained from the filtrate or
aqueous solution (10 mL) of 1 (0.010 g) kept at 303 K. Atomic
+
absorption analyses confirmed the absence of Li cations in
both the as-prepared product and single crystals of 1. Anal.
calcd for C H N V O (%): C, 32.48; H, 7.04; N, 4.73.
48
124 6 10 30
Found: C, 32.87; H, 7.58; N, 4.89. Melting point: 423 K. IR
−1
(
KBr, ν/cm ): 986m, 943s, 921vs, 834s, 807s, 736s, 592m,
5
33m, 466w, 453w, 419w.
C NH –Li–V (2). C NH –Li–V (2) was obtained from the
8
3
10
8
3
10
ethanol washing solution of the as-prepared product of 1.
Yellow platelet crystals of 2 were formed by keeping the wash-
ing solution of 1 (yellow, 10 mL) at 279 K (ca. 4% yield). The
as-prepared product of 1 insoluble in ethanol was subjected
to the recrystallization process with ethanol/water solutions;
however, suitable single crystals were not obtained. Atomic
Fig. 1 IR spectra of hybrid crystals composed of C
As-prepared product of C NH –V10 (1). b) Single crystal of C
(1). c) Single crystal of C NH –Li–V10 (2).
8
NH
3
and V10. a)
8
3
8
NH –V10
3
8
3
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diffraction (XRD) pattern of the as-prepared product of 1
terminal O atoms of V10 (see below). The powder XRD pattern
of the obtained crystals of 2 (Fig. 2c) was similar to that cal-
culated from the single crystal structure of 2 (Fig. 2d), indi-
cating that 2 was obtained as a single phase. The largest peak
at 2θ = 4.0° in the XRD pattern of 2 (Fig. 2c) exhibited a small
shoulder peak, probably because a desolvated phase of efflo-
rescent 2 was formed during the powder XRD measurements
under ambient conditions.
(
Fig. 2a) was almost the same in terms of the peak positions
as the pattern calculated from the single crystal structure of 1
Fig. 2b). Slight differences in the peak intensity and position
(
of the XRD patterns may be due to the difference in the mea-
surement temperature (powder: ambient temperature; single
crystal: 193 K) and to the preferred orientation derived from
the predominant layered structure of 1. The results of IR and
XRD measurements demonstrate that both molecular and
crystal structures of 1 were retained before and after the re-
crystallization process. The as-prepared product of 1 was
obtained as a single phase, being consistent with the results
Description of crystal structures
8 3 8 3 6 28
C NH –V10 (1). The formula of 1 was [(C H17)NH ] ijV10O ]
of elemental analyses. The synthetic solution contained an
·2H O, revealed by the single crystal X-ray and elemental anal-
2
+
excess amount of Li cations derived from LiOH·H O (see Ex-
yses (Table 1). Six C NH cations (1+ charge) were associated
2
8
3
+
+
perimental). However, any small cations such as Li or H
with one V10 anion (6− charge) due to charge compensation.
were not introduced into 1 by the recrystallization process as
No other small counter cation was included, although the V
1
0
mentioned below.
anion tends to be hybridized with several protons in the
+
40–45
Li cation-containing V10 hybrid crystals of C
8 3
NH –Li–V10
crystals.
The crystal packing consisted of alternating V10
(2) were reproducibly obtained from the ethanol washing so-
inorganic monolayers parallel to the bc plane and C NH sur-
8
3
lution of the as-prepared product of 1. The washing solution
of 1 was yellow-coloured and can be considered as ethanol/
water solution containing 1 and excess amounts of Li cat-
factant organic layers (Fig. 3a). The layer distance was 20.8 Å
for 1.
+
The crystal of 1 contained three crystallographically inde-
pendent C NH cations, one of which had a bent conforma-
ions. Therefore, keeping the washing solution of 1 resulted in
8
3
+
the formation of the Li cation-containing hybrid crystals of
8 3
tion (Fig. 3b). One C–C bond (C1–C2) of C NH had a gauche
2
. However, suitable single crystals of 2 were not obtained by
conformation, while the other C–C bonds had an anti confor-
mation. The octyl chains of the C NH cations in 1 did not ar-
range in a straight interdigitated manner, which is similar to
+
the recrystallization process of 1 under the presence of Li
cations using ethanol/water mixed solvent, being different
from the cases of octamolybdate–surfactant hybrid
crystals.
The IR spectrum of 2 (Fig. 1c) exhibited typical peaks for
the decavanadate (V ) anion in the range of 400–1100 cm ,
as in the case of 1.
in the extent of the peak splitting of the band at around 900–
8
3
those observed in other short surfactant–cluster hybrid
2
4–28
51–53
crystals.
The inorganic monolayers of 1 were composed of V10 and
water molecules of crystallization, as shown in Fig. 3c. The
V10 anions and water molecules of crystallization were
connected by O–H⋯O hydrogen bonds to form two-
dimensional infinite layers, and the O⋯O distance ranged
from 2.69–2.86 Å (mean: 2.78 Å). The C NH cations with a
−
1
1
0
4
0,42
However, there were slight differences
−
1
1
000 cm
derived from the terminal VO stretching
4
2
+
mode, implying the connection of the Li cation with the
8
3
Table 1 Crystallographic data
Compound
1
2
Chemical formula
Formula weight
Crystal system
Space group
a (Å)
b (Å)
c (Å)
α (°)
β (°)
C
48
H
124
N
6
V O
10 30
40 80 4 2 10 38
C H N Li V O
1774.94
monoclinic
P2 /c
1748.37
monoclinic
P2 /c
1
1
20.882(2)
18.186(2)
10.2629IJ12)
90.0000
94.447(4)
90.0000
3885.7(8)
2
21.9879(9)
19.3316(7)
9.2168(4)
90.0000
101.8640IJ15)
90.0000
3834.0(3)
2
γ (°)
V (Å )
3
Z
−3
ρ
calcd (g cm
)
1.517
1.514
T (K)
μ(Mo Kα) (mm
No. of reflections measured
No. of independent reflections 8904
Rint
No. of parameters
R1 (I > 2σ(I))
2
wR (all data)
193
1.220
60 685
193
1.242
58 945
8758
0.0750
476
−1
)
Fig. 2 Powder X-ray diffraction patterns of the hybrid crystals com-
posed of C
Calculated pattern of C
single-crystal X-ray diffraction. c) Single crystal of C
Calculated pattern of C NH –Li–V10 (2) using the structure obtained by
8
NH
3
and V10. a) As-prepared product of C
NH –V10 (1) using the structure obtained by
NH –Li–V10 (2). d)
8 3
NH –V10 (1). b)
8
3
0.0860
424
0.0565
0.1517
8
3
8
3
0.0703
0.1620
single-crystal X-ray diffraction.
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C8NH3 cation and V10 anion were identical to those in 1
(
Table 1). 2 was formulated to be [(C H )NH ] Li ijV O ]
8 17 3 4 2 10 28
+
2 5 2 8 3
·4C H OH·6H O, and four C NH and two Li cations were as-
sociated with one V10 anion. 2 contained ethanol molecules
as solvents of crystallization (Fig. 5a), and all the water mole-
+
+
cules were coordinated to the Li cation (Fig. 5b). The two Li
cations were connected to terminal O atoms of one V10 anion
4−
to form an anion formulated as {[LiIJH O) ] ijV O ]} (de-
2
3 2 10 28
+
noted as Li
2
V10) (Fig. 5b). The Li cation exhibited tetrahedral
coordination geometry with Li–O distances ranging from 1.92
4
6,55
+
to 1.97 Å (mean value: 1.95 Å).
The Li cations were
straightly aligned along the c axis with a Li⋯Li distance of
4.91 Å in the crystal.
The crystal packing consisted of alternating Li2V10 inor-
ganic monolayers and C NH organic layers (Fig. 5a) with a
8 3
layer distance of 21.5 Å. The Li2V10 inorganic layer was paral-
lel to the bc plane, and the octyl chains of C NH did not ar-
8
3
range in a straight interdigitated manner. These structural
features for 2 were similar to those for 1 including the space
group and cell parameters. The different features except for
+
Fig. 3 Crystal structure of 1 (C: gray, N: blue, O: red; V10 anions in
polyhedral representations). a) Packing diagram along the c axis. H
atoms are omitted for clarity. b) View of crystallographically
the presence of Li cations were the conformation of surfac-
tant chains and the position of the solvent of crystallization.
The crystal of 2 contained two crystallographically indepen-
dent surfactant cations in which all the C–C bonds had an
independent
C
8
NH
3
cations. c) Molecular arrangements in the
inorganic layers. The short contacts derived from O–H⋯O hydrogen
bonds are represented by broken lines.
less bulky hydrophilic head than the trimethylammonium or
pyridinium surfactant partially penetrated into the two-
dimensional V10 layers (Fig. 3a), and located at the dip be-
5
4
tween the V10 anions by forming N–H⋯O hydrogen bonds
N⋯O distance of 2.70–2.90 Å; mean value: 2.82 Å) (Fig. 4).
(
5
4
Weak C–H⋯O hydrogen bonds were also formed at the
interface between the V and C NH layers. The C⋯O dis-
tance was in the range of 3.18–3.81 Å (mean value: 3.49 Å).
The bent C NH cation formed several weak hydrogen bonds
1
0
8
3
8
3
through N1 to C5 atoms (Fig. 4). In addition, some C–H⋯O
bonds were present in the vicinity of the gauche C–C bonds.
+
8 3
C NH –Li–V10 (2). Single crystals of 2 were obtained as Li
cation-containing hybrid crystals, while the constituent
Fig. 5 Crystal structure of 2 (C: gray, N: blue, O: red, Li: green; V10
anions in polyhedral representations). a) Packing diagram along the c
axis. H atoms and disordered C atoms are omitted for clarity. Some
ethanol molecules are highlighted. b) View of the crystallographically
8 3
independent C NH cations together with the V10 anion and hydrated
+
+
Fig. 4 N–H⋯O and C–H⋯O hydrogen bonds in 1 (pink dotted lines).
Li . Half a V10 anion and hydrated Li are completed by symmetry
operation (1 − x, 1 − y, 1 − z). c) Molecular arrangements in the
inorganic layers. The short contacts derived from O–H⋯O hydrogen
bonds are represented by broken lines. H atoms are omitted for clarity.
8 3
Selected hydrogen bonds between the V10 anion and C NH cations
are represented (symmetry codes: (i) x, 0.5 − y, 0.5 + z; (ii) 1 − x, 0.5 +
y, 1.5 − z; (iii) x, y, −1 + z; (iv) 1 − x, 1 − y, 1 − z).
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anti conformation (Fig. 5b), while the C NH cation in 1 had
low conductivity of both hybrid crystals. The equivalent cir-
cuit employed here is shown in Fig. 7 (inset), consisting of
the bulk resistance and capacitance (R and C ), the grain
b b
8
3
a bent conformation as mentioned above (Fig. 3b). The ethanol
molecules of crystallization in 2 were placed at the interface be-
tween the Li2V10 and surfactant layers, excluded from the inor-
ganic layers (Fig. 5a). On the other hand, the water molecules
of crystallization in 1 consisted of the inorganic layers together
with V10 through the hydrogen bonds (Fig. 3c).
boundary resistance and capacitance (Rgb and C ), and the
gb
charge transfer resistance (R ) along with the double layer ca-
ct
pacitance (Cdl). The red line in Fig. 7 represents the simu-
lated data based on the equivalent circuit, reproducing the
In 2, the inorganic monolayers were composed of the
experimental impedance spectra. The estimated value of R
was 1.45 × 10 Ω for 1, from which the conductivity of 1 was
b
6
isolated Li
2
V
10 anions, which were connected by O–H⋯O hy-
−
8
−1
drogen bonds between the O atoms of the V moiety and wa-
ter molecules coordinated to the Li cation (Fig. 5c). The
calculated to be 8.2 × 10 S cm . As for 2, the value of R
b
1
0
+
6
and conductivity were estimated to be 3.90 × 10 Ω and 1.1 ×
−
8
−1
O⋯O distance ranged from 2.68–2.96 Å with a mean value of
.81 Å. As in the crystals of 1, the C NH cations having a less
8 3
10 S cm , respectively. The conductivity of 2 was lower
than that of 1. This may be because 2 had more O–H⋯O hy-
drogen bonds in the Li V inorganic layers, which plausibly
2
bulky hydrophilic head partially penetrated into the two-
dimensional Li 10 layers (Fig. 5a), and located at the dip be-
2
10
2
V
prevented the easy movement of conducting carriers such as
+
tween the Li2V10 anions by forming N–H⋯O hydrogen bonds
with N⋯O distances of 2.72–2.91 Å (mean value: 2.80 Å)
Fig. 6).
Li . Although the value of the anhydrous conductivity was not
+
high enough, Li cation-containing POM–surfactant hybrid
(
crystals would pave a way to another class of lithium-ion con-
ductors working at intermediate temperatures.
The straightly aligned C NH cations in 2 had several weak
8
3
C–H⋯O hydrogen bonds, as shown in Fig. 6. These hydrogen
bonds were formed at the interface between the Li 10 and
C NH layers. The C⋯O distance was in the range of 3.15–
2
V
Conclusions
8
3
3
.82 Å (mean value: 3.50 Å), which was similar to that for 1.
Polyoxovanadate–surfactant hybrid layered crystals were syn-
These hydrogen bonds as well as the electrostatic interaction
between the Li2V10 anions and C NH cations would stabilize
thesized using a primary alkylammonium cation, octylamm-
+
onium ([C H NH ] , C NH ). Two types of hybrid crystals
8
3
8
17
3
8
3
the layered crystal structure of the hybrid crystals.
were successfully isolated, having formulae of [C H NH ] -
8
17
3 6
2
ijV10O28]·2H O
(C
8
NH
3
–V10
)
8 3 4 2 28
and [C H17NH ] Li ijV10O ]
·
4C H OH·6H O (C NH –Li–V ). For the first time, precise
2 5 2 8 3 10
8 3 8 3
Conductive properties of C NH –V10 (1) and C NH –Li–V10 (2)
control of the synthetic conditions enabled the realization of
the introduction of lithium cations into the polyoxovanadate–
surfactant hybrid crystals. Although the conductivities of the
obtained C NH –V and C NH –Li–V were rather low, the
The conductive properties of 1 and 2 were investigated by al-
ternating current (AC) impedance spectroscopy under an an-
hydrous atmosphere at the intermediate temperature of 403
or 413 K. As shown in Fig. 7, each spectrum showed a part of
a semicircle in all the frequency regions with a very high im-
8
3
10
8
3
10
hybrid crystals reported here could be applicable to another
6
7
pedance value of the order of 10 to 10 Ω, suggesting the
Fig. 7 Nyquist spectra measured under an anhydrous atmosphere of 1
(open circles, at 403 K) and 2 (open squares, at 413 K). The simulated
spectra (red line) are based on an equivalent electronic circuit in the
figure. The parameters obtained by the fitting (see text) for 1 are as
6
5
4
follows: R
b
= 1.45 × 10 Ω, Rgb = 4.1 × 10 Ω, Rct = 1.0 × 10 Ω, C
b
= 2.2
−
7
−6
−4
Fig. 6 N–H⋯O and C–H⋯O hydrogen bonds in 2 (pink dotted lines).
× 10 F, Cgb = 1.0 × 10 F, and Cdl = 1.0 × 10 F. The parameters
estimated for 2 are as follows: R
+
6
6
Selected hydrogen bonds between V10 anions as well as C
8
NH
3
and Li
b
= 3.90 × 10 Ω, Rgb = 4.1 × 10 Ω, Rct
4
−8
−8
−8
cations are presented (symmetry codes: (i) 1 − x, −0.5 + y, 1.5 − z; (ii) 1
x, 1 − y, 2 − z; (iii) x, 0.5 − y, −0.5 + z).
= 1.0 × 10 Ω, C
b
= 4.0 × 10 F, Cgb = 1.0 × 10 F, and Cdl = 8.0 × 10
−
F.
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class of lithium-ion conductors which works at an intermedi-
ate temperature range. Although several POM–surfactant hy-
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This work was financially supported in part by JSPS KAKENHI
Grant Number JP26410245 and the Research and Study Pro-
ject of Tokai University Educational System General Research
Organization. X-ray diffraction measurements with synchro-
tron radiation were performed at PF-AR (NW2A beamline) of
the High Energy Accelerator Research Organization (KEK)
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