pubs.acs.

org/JPCC Article

Effect of Vanadium Oxide on the Structure and Li-Ion Conductivity

of Lithium Silicate Glasses
Anuraag Gaddam,* Amarnath R. Allu, Sudheer Ganisetti, Hugo R. Fernandes, George E. Stan,
Catalin C. Negrila, Atul P. Jamale, François Mear, Lionel Montagne, and José M. F. Ferreira*
Cite This: J. Phys. Chem. C 2021, 125, 16843−16857 Read Online

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ABSTRACT: The commercially ubiquitous liquid electrolytes for lithium-ion batteries have
several shortcomings in terms of safety. Therefore, development of solid electrolytes,
especially those that are glass-based, has been gaining increasing interest in recent times.
However, the fundamental understanding of the changes in the glass structure and the
corresponding changes in the properties due to the addition of dopants is necessary for the
development of glasses. Therefore, here, we report a study on the role of vanadium on the
glass structure, ionic conduction, crystallization behavior, and other properties of lithium
silicate-based glasses (23Li2O−2.64K2O−2.64Al2O3−71.72SiO2) as a solid electrolyte for
high-temperature Li-ion battery applications. Furthermore, we proposed a mathematical model to describe/quantify the ion-
conducting channels’ connectivity in glasses. The experimental glass structures were assessed using 29Si, 51V, 27Al nuclear magnetic
resonance, Fourier transform infrared, and ultraviolet−visible spectroscopy techniques. The ionic conductivity was measured by
impedance spectroscopy, and the crystallization behavior was studied by optical microscopy and X-ray diffraction. Furthermore,
molecular dynamics simulations were also used to gain structural insights of the glasses. In the designed compositions, the addition
of vanadium decreased the overall concentration of Li+ ions. However, the results revealed that the ionic conductivity improved with
the addition of vanadium in spite of a decrease in the number of charge carriers. This suggests that vanadium makes the pathways
easier for the conducting ions. Thus, we conclude that vanadium modifies the conduction channels to promote better hoping of the
ions from one site to another.

■ INTRODUCTION
Lithium-ion batteries are of great technological interest due to
structure, which in turn depends on the chemical composi-
tion.9,10
their high energy density with a reduced weight. However, the The ionic conduction in glasses can be understood based on
volatile liquid electrolytes used in the batteries being their intermediate-range structure.11 Therefore, the study of
flammable present potential fire hazards. Very recently, solid the glass structure is of paramount importance, not only for
electrolyte materials have gained enormous attention over their predicting the ionic conductivity but also for understanding
liquid counterparts as they exhibit protection from leakage, other glass properties and processes such as relaxation and
volatilization, or flammability.1−4 The main drawback of the crystallization. The well-known study by Zachariasen12 was
one of the first to address the atomic-level structure of glasses.
current organic liquid electrolytes is their restriction to lower
It proposed a model that is now commonly known as the
working temperatures. The higher temperatures experienced
continuous random network model of the glass. It states that
by Li-ion batteries could cause damage to the electronic
glass is constructed of oxygen polyhedra that are connected
components, or in a worst-case scenario, an explosion.5 The
randomly throughout the entire network. This would imply
current technologies for the production of solid electrolytes
that the network modifiers are distributed randomly
use powder routes, resulting in unavoidable porosity that
throughout the entire network. Later, Greaves13 proposed
lowers the mechanical properties, electrical performance, and
the modified random network (MRN) model of glasses,
thereby, the stability and safety of the materials.6,7 On the
according to which the network modifiers microsegregate to
other hand, amorphous solid electrolyte materials have
form channel-like regions in the glass network. This MRN
significant technological applications, especially for lithium-
based energy storage systems.8 Melt-quenched amorphous
glasses are intrinsically nonporous and can be easily molded to Received: June 8, 2021
required shapes. Furthermore, the chemical compositions of Revised: July 8, 2021
the glasses can be tailored to obtain desired properties such as Published: July 26, 2021
high ionic conductivity. This can be achieved based on the
composition−structure−property relationships since the prop-
erties of the glasses are intrinsically dependent on their

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model has received much praise in describing the glass
structure.14 It also became a foundational model for under-
standing the ionic conduction in glasses.11 During conduction,
the network-modifying ions percolate through these channels.
In our recent studies,10,15 we have further extended the
concept of MRN model, which is called the extended modified
random network model, to account for the disallowance of
Loewenstein’s rule in certain glass compositions.16 Exper-
imentally, to the best of the authors’ knowledge, currently
there are no methods/techniques to detect or quantify these
channels. Nevertheless, from the detailed structural informa-
tion obtained from the molecular dynamics (MD) simulations,
one could easily identify these channels qualitatively. There-
fore, in this study, we propose a model to quantify the
connectivity of these channels in lithium silicate glasses.
Lithium silicate and lithium aluminosilicate glasses have been
considered fast ion conductors and therefore received
significant interest over the past few decades for their practical
application.17,18 Rim et al.19 have reported very recently that
the increasing concentration of lithium cations enhances ionic
conductivity in lithium silicate glasses and therefore proposed
that these glasses could be considered as promising solid
electrolyte materials for Li-ion batteries.20
As mentioned above, the glass structure plays an important
role in determining almost every physical and chemical
property of a glass. Furthermore, the glass structure can be
tuned by appropriately changing the glass composition. It has
been reported that the presence of isolated tetrahedral units,
such as orthophosphate, that exist apart from the network can
enhance the conductivity of Li+ ions.21,22 In glasses, vanadium
in the 5+ oxidation state generally behaves like phosphorus,
forming tetrahedral units. 23 Therefore, based on the
observations made on silico-phosphate glasses,21 it is expected
that the addition of V also increases the association of non-
bridging oxygen (NBO) with V and creates additional
pathways in the silicate network structure, enhancing the
ionic conductivity. Vanadium is typically added to glasses as a
coloring agent.24 Thus, its effect on the optical properties of
the glasses is interesting to many researchers.25 However, its
effect on the structure−property correlations is still not very
well understood. In particular, studies on its influence on the
intermediate-range structure and ionic conductivity are still
lacking.
Owing to the above concerns, in the current study, we have
investigated the influence of V on the structure and ionic
conductivity of a lithium silicate-based parent glass,
23.00Li2O−2.64K2O−2.64Al2O3−71.72SiO2 (mol %), which
exhibits strong mechanical properties, excellent chemical
resistance, and good thermal stability.26−28 The structure and
properties of the parent glass composition were studied in
detail elsewhere.29−31 Furthermore, in the current study, we
proposed a mathematical model to quantify the ion-conducting
channels.
■
EXPERIMENTAL METHODS
The glass compositions investigated in this study, and reported
in Table 1, were prepared from the following precursor
powders: SiO2, Li2CO3, K2CO3, Al2O3, and V2O5 (all with
purity > 99%). The powders (100 g batch size) were first ball-
milled, calcined at 800 °C, further mixed using a mortar and a
pestle, and then transferred to Pt crucibles.
All compositions were melted at 1550 °C for 1 h in air and
cast on brass molds. One piece (∼15 g) of each glass
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Table 1. Nominal Compositions of the Glasses (in mol %)
Li2O K2O Al2O3 SiO2 V2O5
V0.0 23.00 2.64 2.64 71.72 0.00
V0.2 22.95 2.63 2.63 71.58 0.20
V0.5 22.89 2.62 2.62 71.36 0.50
V1.0 22.77 2.61 2.61 71.00 1.00
V2.0 22.54 2.59 2.59 70.29 2.00
composition was subjected to annealing for 1 h at 480 °C to
develop liquid−liquid phase separation (LLPS) and observe
the effect of V on LLPS. To study the crystallization behavior
and phase assemblage, a small piece (approx. 10 mm × 10 mm
× 6 mm) of each glass composition was subjected to heat
treatment at temperatures in the range of 650−800 °C for 1 h.
Differential thermal analysis (DTA) was carried out in air
from room temperature to 900 °C at a heating rate of 10 °C
min−1 on Setaram Labsys and PerkinElmer DTA-7 instru-
ments. The densities of the nonannealed glass samples were
measured using the Archimedes principle by immersing them
in ethylene glycol (density = 1.11 g cm−3).
Glass plates for optical spectroscopy analysis were prepared
by plane-parallel polishing to a mirror finish of both the sides
down to a thinness of 1−2 mm. The spectra were recorded
over a range of 200−1500 nm wavelengths using a Shimadzu
UV−vis−NIR spectrophotometer (model UV-3100).
The Fourier transform infrared (FTIR) spectroscopy
measurements were performed with a PerkinElmer Spectrum
BX II spectrometer in the attenuated total reflectance (ATR)
mode using a PIKE MIRacle accessory with a germanium
crystal plate. The spectra, collected in the 2000−670 cm−1
range, at a resolution of 4 cm−1, represent the average of 32
individual scans.
The magic-angle spinning nuclear magnetic resonance
(MAS-NMR) spectroscopy of 29Si and 27Al of the glasses
was performed using a Bruker ASX 400 MAS-NMR
spectrometer (magnetic field of 9.4 T, Aveiro, Portugal). For
29
Si, the spectrometer was operated at a Larmor frequency of
79.5 MHz, with samples being spun at 5 kHz in 7 mm rotors,
the flip angle was 90°, and the relaxation time was 60 s. For
27
Al, the spectrometer was operated at a Larmor frequency of
104.3 MHz using a 4 mm rotor spinning at 14 kHz with a 10°
flip angle and a 2 s delay relaxation time. 51V MAS-NMR
spectroscopy of the glass samples was performed using a
Bruker Avance I MAS-NMR spectrometer (magnetic field of
9.4 T, Lille, France). For this, the spectrometer was operated at
a Larmor frequency of 105.2 MHz using a 2.2 mm rotor
spinning at 30 kHz with a 10° flip angle and a 2 s delay
relaxation time (these values were also first optimized before
measurements). For 29Si, 27Al, and 51V nuclear magnetic
resonance (NMR) spectroscopy measurements, Si(CH3)4,
Al(NO3)3, (saturated aqueous solution), and VOCl3 were
used as chemical shift (δiso) references, respectively. NMR
spectra were analyzed using DMfit software.32
The glass surface composition and the chemical state of the
elemental components were assessed by X-ray photoelectron
spectroscopy (XPS) with a Specs GmbH equipment. Glass
slides of ∼3 mm thickness were fractured and introduced
immediately (to prevent high C contamination) into the
analysis chamber (which was subsequently vacuumed up
rapidly) and analyzed. The measurements were performed at a
pressure of ∼10−7 Pa using an XR 50 M monochromatic X-ray
source set at 300 W with Al Kα (1486.7 eV) radiation and a
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Table 2. Properties of the Glassesa
ρ (g cm−3) Vm (cm3 mol−1)
V0.027 2.354 ± 0.003 23.43 ± 0.03
V0.2 2.3654 ± 0.0005 23.41 ± 0.01
V0.5 2.3655 ± 0.0008 23.57 ± 0.01
V1.0 2.3700 ± 0.0008 23.80 ± 0.01
V2.0 2.3759 ± 0.0008 24.28 ± 0.01
a
ρ, density; Vm, molar volume; Tg, glass transition temperature; Tc, onset crystallization temperature; and Tp, peak crystallization temperature
(typical error for Tg, Tc, and Tp is ±2 °C).
spot size of ∼0.5 mm × 3 mm. A Phoibos 150 electron
analyzer with a radius of 150 mm was employed with an
ultimate resolution of 0.44 eV (given as full width at half
maximum (FWHM) of the Ag3d5/2 spectral line, measured
under best conditions), equipped with a nine channeltron
detector. The analyzer was operated at a pass energy of 50 eV
for the survey spectra and 20 eV for the high-resolution scans
of relevant core electron levels. The sample neutralization
during the measurements was achieved using a Specs FG15/40
flood gun with an acceleration energy of 1 eV and an emission
current of 1 mA. The fitting of the spectra was performed using
the spectral data processor program, Voigt functions, and
tabulated Scofield sensitivity factors.
For conductivity measurements, the annealed samples were
cut into rectangular shapes and polished. The conductivities
were measured in ambient air with a complex electrochemical
impedance spectrometer (EIS) using a HP 4284A LCR meter.
The samples were first coated with silver paint (purchased
from G302 Agar Scientific Ltd., Stansted, UK) on both sides of
the sample by manual brush painting, which acted as an
electrode. The cell assembly containing the glass sample and
the silver electrodes was sandwiched between the gold foils
before introducing into the furnace. The ionic conductivity
measurements were carried out over a temperature range of 50
to 400 °C at intervals of 50 °C. The samples were stimulated
over a range of frequencies varying from 20 Hz to 1 MHz at a
constant signal amplitude of 500 mV. The obtained data were
analyzed using ZView software.
X-ray diffraction (XRD) analysis on the samples was
conducted using a Rigaku Geiger Flex D/Mac C Series
instrument with Cu Kα radiation. The patterns were recorded
in the Bragg−Brentano geometry at a step size of 0.026 in a 2θ
angular range of 10−60°. The microstructures of these samples
were examined by stereomicroscopy using a microscope with
an LED and a HD Camera LEICA EZ4HD.
■
MD SIMULATIONS
The glass samples were prepared with the use of classical MD
simulations in the large-scale atomic/molecular massively
parallel simulator software package.33 Two-body pair potentials
developed by Pedone et al.34 were used to compute the
interactions between Si−O, Al−O, Li−O, K−O, and O−O
atom pairs. The parameters for V−O atom pairs were obtained
from the study of Ori et al.35 The pair potential consists of
three terms: (1) long-range Coulomb interactions, (2) short-
range Morse function, and (3) repulsive contribution C/r12,
see eq 1. The parameters of the potential are presented in the
Supporting Information (Supporting Information). The
Coulombic interactions were computed using the Ewald
summation technique with a precision of 10−5 in force.36
The velocity Verlet algorithm was used with a time step of 1 fs
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NBO/BO
Tg (°C) Tc (°C) Tp (°C)
480 707 824 0.351
459 608 705 0.353
449 603 704 0.355
439 594 689 0.358
435 575 617 0.365
to integrate Newton’s equation of motion. Periodic boundary
conditions were imposed along the three axes. The temper-
ature and pressure were controlled using a Nosé−Hoover
thermostat and a barostat whenever required.37,38
ZiZje 2 Cij
U (r ) = + Dij{[1 − e−aij(r − r0)]2 − 1} +
r r12 (1)
Initially, “N” number of positions was generated randomly
within a cubic box and assigned a unique number to identify
each particle, and the box length was calculated based on the
experimental density. The particles were selected randomly
and assigned the atom type, and this procedure was continued
until the desired composition was reached. The obtained
configuration was then equilibrated at 300 K using the NVE
ensemble for 10 ps. The sample was then heated from 300 to
5000 K at a heating rate of 100 K/ps by keeping the volume
constant. The sample was thermalized for 100 ps at 5000 K to
get a well-equilibrated melt. The melt was then cooled to room
temperature at a rate of 1 K/ps using the NVT ensemble. At
300 K, the sample was thermalized for 100 ps with NVT and
an additional 100 ps with the NPT ensemble to obtain a
completely relaxed sample. These samples were then used for
computing the physical and structural properties. For statistical
relevance, three samples were prepared for each composition.
■ RESULTS
The XRD patterns of bulk glasses showed no crystalline phases
(Figure S1 of Supporting Information), confirming the good
glass forming ability of the system. During melting, the V-
containing compositions showed small amounts of bubbling,
which increased slightly with increasing V2O5 contents.
Bubbling results from the reduction of vanadium from the
5+ oxidation state to lower oxidation states. This process is
discussed in more detail in the Discussion Section. Because of
the low viscosity of the melts at 1550 °C, the bubbles easily
surfaced, resulting in final clear glasses. The scanning electron
microscopy (SEM) observation of glass samples revealed a
significant reduction of the LLPS trend upon adding V (Figure
S2 of Supporting Information). The characteristic temper-
atures obtained from the DTA curves (Figure S3 of Supporting
Information), namely, glass transition (Tg), onset crystalliza-
tion (Tc), and peak crystallization (Tp) temperatures are listed
in Table 2. The densities (ρ) are also listed in Table 2. Using
the ρ values, the molar volume (Vm) of the glasses could be
calculated using the following formula
Vm =
X Li2OM Li2O + X K2OM K2O + X Al2O3M Al2O3 + XSiO2MSiO2 + X V2O5M V2O5
ρ
(2)
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Figure 1. NMR spectra of the nuclei (a) 29Si, (c) 27Al, and (d) 51V. Panel (b) shows an example of the deconvolution of the 29Si NMR spectra.
Asterisks represent the spinning side bands.

29
Table 3. Parameters for Simulation of the Si NMR Spectra
δiso (ppm) FWHM (ppm) amount (%)
peak A peak B peak C peak A peak B peak C peak A peak B peak C
V0.0 −77.7 −92.2 −104.8 5.0 15.6 12.8 0.4 73.0 26.6
V0.2 −77.7 −92.0 −104.4 5.0 15.9 13.2 0.9 72.0 27.1
V0.5 −77.7 −91.9 −104.3 5.0 16.5 13.5 0.3 73.5 26.2
V1.0 −77.7 −92.2 −104.7 5.0 16.3 14.3 0.3 66.1 33.6
V2.0 −93.4 −105.9 17.6 13.5 0.0 66.8 33.2

where Xα and Mα are the mole fraction and the molecular effect on the 29Si nuclei, progressively shifting the peak toward
weight, respectively, of the αth component. Here, Vm is the the right side.
volume occupied by one mole of the glass components. Figure 1c shows the 27Al NMR spectra of glasses. The 27Al
To know the overall polymerization of the glasses, the nuclei have a spin of 5/2 and experience second-order
NBO/BO ratios were calculated for each composition, again quadrupolar effects. To obtain the isotropic chemical shift
assuming the network-forming role of V, using the following (δiso) and quadrupolar coupling constant (CQ) values, the
equation spectra were fitted with a single line shape of the Czjzek
distribution.39,40 The obtained values are listed in Table 4. It
NBO 2(X Li 2O + X K 2O − X Al 2O3 + X V2O5)
= can be noticed that with the increasing V content, there is a
BO 2XSiO2 + 5X Al 2O3 + 3X V2O5 − X Li 2O − X K 2O slight increase in the shielding effect on the 27Al nuclei, which
(3) is similar to 29Si but much less pronounced.
The 51V nucleus has a natural abundance of 99.75%;
These theoretical results suggest that the addition of V however, because of its spin being 7/2, the 51V spectra show
increases the NBO/BO ratio (Table 2). first- and second-order quadrupolar effects.41 Furthermore, the
MAS-NMR and FTIR-ATR Spectroscopies. Figure 1a
shows the 29Si NMR spectra of the glasses. These spectra were
Table 4. Parameters for Simulation of the 51V and 27Al NMR
decomposed into three peaks corresponding to Peak A, Peak B,
Spectra
and Peak C, and the results are presented in Table 3 and in
Figure S4 and Figure 1b. The assignment of these peaks to the
δiso (ppm) CQ (MHz)
QnSi units is complicated due to the ambiguities brought by the 27
presence of Al2O3 in the glasses.30 Al2O3 creates Q4Si(mAl) Al NMR parameters
-type Si units, m ∈ {3, 4}, which would have chemical shifts at V0.0 59.6 4.8
about −90 ppm, similar to pure Q3Si units, causing a mixing of V0.5 59.5 5.0
the peaks. Therefore, Peak B could be a mixture of Q3Si, V1.0 59.1 5.0
51
Q4Si(3Al), and Q4Si(4Al) units. Furthermore, the addition of V V NMR parameters
would make the peak assignment even more complicated. This V0.2 −564.9 5.71
intricate peak assignment is discussed in the Discussion V0.5 −565.0 5.36
Section. However, it could be qualitatively noticed from Figure V1.0 −563.5 5.16
1a that the addition of V resulted in an increasing shielding V2.0 −562.5 5.17

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localized unpaired electrons present in V3+ and V4+ would
cause paramagnetic broadening of the 51V NMR spectra.42
Thus, these species could not be detected by the 51V NMR
spectra. On the other hand, V5+ having no unpaired electrons
([Ar] 4s0, 3d0) would not exhibit paramagnetic broadening.
According to Lapina et al.,43 the second-order quadrupolar
effects could be minimized using a high magnetic strength
greater than 7 T; in the current study, the magnetic field used
was 9.4 T. Figure 1d shows the 51V NMR spectra of vanadium-
containing glasses. The NMR parameters of the spectra were
obtained by performing simulations similar to those of the 27Al
NMR spectra. The results of the simulations, δiso and CQ
values, are summarized in Table 4.
The comparative FTIR-ATR spectra of the glasses are
shown in Figure 2. The IR spectra were broad, typical for
Figure 2. FTIR-ATR spectra of the glasses.
silica-based glasses,44,45 eliciting two absorption maxima,
located in the 850−690 and 1270−850 cm−1 wave number
regions, and associated to the symmetric (νs) and asymmetric
(νas) stretching vibrations of bonds in various silicate units,
respectively.45−48 The prominent νas vibration band had three
shoulders peaking at ∼940 to 946 cm−1, 1015−1023 cm−1, and
∼1145 to 1152 cm−1, yielded by the Si−O− (NBO) in Q2Si and
Q3Si units, Si−O−Si (BO) TO3 (transverse-optical), and Si−
O−Si LO3 (longitudinal-optical) type bonds, respectively.47,49
A slight shift to higher wave numbers of the BO absorption
bands was noticed with the increased V concentration in the
glasses (Figure 2 (inset)), suggesting some degree of
polymerization of the silicate network.48
UV−Vis and XPS Spectroscopies. Figure 3a shows the
UV−vis spectra of the glasses. The spectra were deconvoluted
(Figure 3b−e) to identify the fractions of several oxidation
states of vanadium (V3+, V4+, and V5+) according to the
procedure described elsewhere.50,51
The XPS survey spectra of the glasses are presented
comparatively in Figure 4a. All the glass components (Si, O,
Li, V, Al, and K) were clearly evidenced. The binding energy
positions of the Li 1s (∼55.2 to 55.4 eV), Al 2p (∼74.1 to 74.3
eV), and K 2p1/2/K 2p3/2 (∼296.1/293.2 to 296.4/293.6 eV)
lines indicated their complete oxidation.52 The V 2p3/2 peak
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present in the vanadium glasses was situated at ∼517.6 to
517.8 eV (Figure 4b) and could be fitted by a single
component corresponding to the 5+ oxidation state.53,54 No
traces of V4+ (∼516.5 eV), V3+ (∼515.5 eV), V2+ (513.5 eV),
or metallic V (∼512 eV) were evidenced52−54 at the sensitivity
limit of the XPS equipment.
Two major components were observed in the O 1s region in
the glasses (Figure 4c). The higher energy peak (at ∼532.2 to
532.4 eV) represents the Si−O−Si bond contribution, while
the lower binding energy component (at ∼530.6 to 530.8 eV),
further denoted as “M−O,” stands for chemical assemblies in
which oxygen interacts with metal (M) species in the glass (i.e.,
Si−O−M, thus with NBOs; M−O and MO, in the case of
metal−oxygen standalone structural units).48,55,56 However,
the Si−O−Si bond component also incorporates a (minor)
contribution of various oxygen−carbon bonds, which could
not be safely separated. An additional third minor O 1s
component was evidenced, positioned at the highest binding
energies (at ∼533.9 to 534.2 eV), ascribed to the adsorbed
water,56 and attributed to the hygroscopic character of the
glasses. The M−O/Si−O−Si ratio of the two prominent
components of O 1s generally showed a discrete monotonous
increase with the V content in glasses, which was expected
since the overall metal ion content was incrementally enlarged.
The surface oxide compositions of the glasses (as estimated
by XPS) are presented in Supporting Information (Figure S5)
with respect to the bulk glass oxide concentration. One can
observe a good surface/bulk compositional equivalence for all
elements (in the typical experimental errors of XPS
quantification),57 with the V2O5 content within the projected
concentration ranges.
Impedance Spectroscopy. Figure 5a shows the Nyquist
plots of impedance of the glasses collected at 200 °C. It can be
noticed that with increasing V, the impedance initially
increases and then starts to decrease. The temperature
dependence of the conductivity in ion-conducting systems is
given by
σo ijj EA yzz
expjj− z
j kBT zz
k {
σ=
T (4)
where σ is the conductivity, σo is the pre-exponential factor, EA
is the activation energy for conduction, kB is the Boltzmann
constant, and T is the temperature. The plot of ln(σT) versus
1/T is shown in Figure 5b. The activation energies of the
glasses are obtained from the slope of these lines. Figure 5c
shows the variation of the activation energy with the amount of
V2O5 content.
Crystallization of Glasses. The microscopic examination
of the samples (not shown) revealed that adding V drastically
reduced the bulk crystal nucleation extent. A small amount of
V (0.2 mol %) almost eliminated this phenomenon, in clear
contrast to the parent glass composition as documented
elsewhere.30,58 Therefore, V-containing samples presented
predominant surface crystallization. The thickness of the
crystallized surface layer was measured for each sample at
each crystallization temperature by optical microscopy. The
surface crystal growth rates (U) could then be calculated by
dividing the thickness of the surface layer by the duration of
the heat treatment (1 h), and the results are plotted in Figure
6a. These growth rates were fitted using the Arrhenius
equation59 as described below
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Figure 3. (a) UV−vis spectra of the glasses and (b−e) their deconvolution.
i E y
U = Uoexpjjj− U zzz
k RT { (5)
where Uo is the pre-exponential factor, EU is the activation
energy for crystallization, and R is the gas constant. For fitting
the data with this curve, only lengths that are less than 1.30
mm were considered. The results are presented in Figure 6b.
The XRD patterns showing the phase compositions of the
crystallized layers are presented in Figure S6 in Supporting
Information. The samples showed three different crystal
phases: (1) lithium disilicate (Li2Si2O5, LS2), (2) lithium
metasilicate (Li2SiO3, LS), and (3) quartz (SiO2, Q).
MD Simulations. According to MD simulations, the
coordination numbers of cations Si4+, Al3+, V5+, Li+, and K+
are around 4.0, 4.0, 4.5, 3.8, and 7.0, respectively. The radius of
Li+ ions (0.59 Å) being smaller compared to that of O− ions
(1.42 Å) results in a lower coordination number of ∼4.0.60,61
In comparison, the larger radius of K+ (1.38 Å) results in a
coordination number of ∼7.0. However, both Li+ and K+ ions
act as network modifiers resulting in the creation of NBOs,
which occurs by converting a BO into two NBOs, with the
additional NBO provided by Li2O or K2O, and these ions then
charge balance the newly formed NBOs. The ions Si4+ and Al3+
are in fourfold coordination and act as network formers. A
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majority of V5+ ions exist in fourfold coordination with minor
fractions in five- and sixfold coordination. The distribution of
V5+ ions in different coordination environments is 60, 25, and
15% in four-, five-, and sixfold coordination, respectively. MD
simulations provide complete information about the structure
of the glasses both at short- and intermediate-range orders.
The environment of oxygen is one of the important parameters
for assessing the nature of the network. Figure 7 presents the
information about the oxygen environment. It can be noticed
that with the increasing addition of V into the base glass
composition, the amounts of Si−O−Si and Si−O−Al linkages
decrease, and consequently, the amounts of Si−O−V, Al−O−
V, and V−O−V linkages increase. However, the amounts of
Al−O−V and V−O−V linkages are exceedingly small (Figure
7 inset). Furthermore, the distribution of silicate units into
various QnSi (αAl, βV) structural forms was also quantified and
is summarized in Table 5. Here, α and β represent the
numbers of Al and V units attached to the central Si unit
through the BOs and n represents the total number of BOs
attached to the central Si unit. A majority of fourfold-
coordinated Al units are mostly fully polymerized, that is, they
exist mainly as Q4Al units. The distribution of the fourfold-
coordinated vanadium units into different QnV units is also
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Figure 4. (a) XPS survey scans of the glasses. (b,c) High-resolution XPS spectra of (b) V 2p3/2 and (c) O 1s core photoelectron levels and their
deconvolution. Symbols: experimental spectrum, solid line: fit sum, and filled area curves: spectral components.

Figure 5. (a) Nyquist plots for the impedance at 200 °C, (b) temperature dependence of conductivity, and (c) variation of activation energy with
the composition.

summarized in Table 5. The vanadium units mainly exist as Q2V depends largely on the structure of these channels and how
units. well they are connected to each other. Therefore, quantifying

■ CONNECTIVITY OF CONDUCTING IONIC SITES

As mentioned in the Introduction, the conduction of ions in
glasses is explained by the MRN model, which proposes the
microsegregation of the network-modifying ions (such as Li+
and K+) to form channel-like regions. Under an applied electric
field (E), these ions flow through these channels contributing
to ionic conductivity. Therefore, the ionic conductivity
16849
the connectivity of these channels is important. Qualitatively,
one could say that two channels are weakly connected/
disconnected if they are far apart from each other. However,
under a sufficient thermal energy, they get connected to form a
single channel.
If s is the distance an ion needs to jump to an adjacent site,
then whenever this jump takes place, the two sites would be
considered as connected to form a channel (of size 2, in this
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Figure 6. (a) Surface growth rates of the crystals (the error bars are too small for some data points to be visible) and (b) variation of Arrhenius
parameters with composition.

the channels grow and merge into each other. For s = 5.4, all
the channels merge by forming a single channel or a connected
region. Figure 9 shows the same idea in 3D applied to the
sample V0.0 that is obtained from MD simulations. Here, the
connectivity is considered only based on the Li+ ions.
The number of connected ions thus is a function of the jump
distance s, which we call here as the connectivity distribution
function, given by h(s), which is a cumulative distribution
function that depends on the jump distance for given atomic
positions (xp, yp, and zp). This connectivity distribution
function h(s) quantitatively defines the connectivity of the
conducting ions in the glass. We could also define the
connectivity density function, given by n(s), which is a measure
of the number of connected ions per unit length. The functions
h(s) and n(s) are related to each other as
s
h(s) = ∫0 n(s′)ds′
(6)

Eq.
Figure 7. Oxygen environment in the simulated glasses. The n(s) distribution was computed using the MD
simulation data (three samples for each composition). Figure
case, for example). As more ions get connected in this way, the 10 shows an example of the n(s) distribution functions
channel grows or new channels form (which will be computed for Li+ ions. The n(s) distributions for both Li+ and
subsequently explained in detail using an example). If the K+ ions together were also calculated. However, it was not
ion does not have enough energy to jump a distance greater different from just Li+, considering the small amount of K+ ions
than s, then the two sites would be considered as disconnected in the glass composition. The data were fitted to the skew
Ä É
(s − so)2 Å
ÅÅ (s − so)σ Ñ
ÑÑ
ÅÅ1 + erf Ñ. As seen in Figure
from each other. Thus, the connectivity of the ionic sites to normal distribution function,

form conduction channels can be measured as a function of the
jump distance s, which is related to the available thermal
energy. For a very small value of s, all the sites will remain
disconnected; contrariwise, for a sufficiently large value of s, all
the sites will be connected forming a single universal channel.
In Figure 8, a two-dimensional schematic of eight randomly
arranged ions inside a box without periodic boundary
conditions is presented explaining the dependence of s on
their connectivity. The points represent ions, and each colored
region represents an isolated channel or a connected region. In
this figure, r is the radius of the circles such that s = 2r. If d is
the distance between any two ions, then the two ions would be
considered as connected if d ≤ s. Therefore, as s increases, ions
ÅÇ 2 Δs Ñ ÑÖ
n(s) = exp −( 2Δs 2 ) ( )
10, the peak maximum, smax, goes through a maximum at 0.2
mol % vanadium. The trend is similar to that of the activation
energies obtained from the conductivity measurements (Figure
5c).
As mentioned before, the average jump distance depends on
the available thermal energy, which could be obtained using
statistical mechanics. If ϵ is the energy required by a given ion
to jump a distance s such that ϵ = αs, where α is a
proportionality constant that depends on the amount of
resistance experienced by the ion, then the partition function Q
for this system would be

ji αs zyz
get connected first to form smaller channels and then they

expjjj− zds = B
j kBT zz
∞
merge to form large channels. Here, for s = 0.8, all the sites are
disconnected from each other. When s increases to 1.2, four
ions get connected forming two independent channels. When s
Q= ∫ 0 k {
kT
α (7)
further increases to 2.2, one channel grows and a new channel
starts to develop, resulting in a total number of three The ensemble averages for energy ⟨ε⟩ and jump distance ⟨s⟩
independent channels. For s = 3.6 and 4.2, we can see that are given by
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Table 5. Distribution of Si and V Species in the Glasses according to MD Simulations

species V0.0 V0.2 V0.5 V1.0 V2.0
distribution of Si species
Q4(0Al, 0V) 33.73 ± 0.36 33.02 ± 0.25 33.22 ± 0.45 31.70 ± 0.36 29.47 ± 0.58
Q3(0Al, 0V) 33.03 ± 0.34 32.60 ± 0.60 31.79 ± 0.40 31.50 ± 0.26 31.69 ± 0.40
Q4(1Al, 0V) 11.89 ± 0.41 11.98 ± 0.76 11.77 ± 0.12 11.40 ± 0.20 10.58 ± 0.28
Q2(0Al, 0V) 8.76 ± 0.34 8.81 ± 0.35 9.26 ± 0.30 9.89 ± 0.34 9.49 ± 0.25
Q3(1Al, 0V) 7.87 ± 0.40 8.36 ± 0.46 7.51 ± 0.15 7.65 ± 0.54 8.25 ± 0.19
Q4(2Al, 0V) 1.50 ± 0.17 1.44 ± 0.16 1.57 ± 0.11 1.52 ± 0.18 1.39 ± 0.06
Q2(1Al, 0V) 1.43 ± 0.20 1.43 ± 0.13 1.11 ± 0.53 1.29 ± 0.16 1.57 ± 0.10
Q1(0Al, 0V) 0.90 ± 0.11 0.92 ± 0.25 1.06 ± 0.09 1.22 ± 0.03 1.35 ± 0.24
Q4(0Al, 1V) 0.26 ± 0.10 0.58 ± 0.09 1.19 ± 0.18 2.31 ± 0.38
Q3(0Al, 1V) 0.17 ± 0.03 0.36 ± 0.11 1.13 ± 0.05 1.79 ± 0.18
Q3(2Al, 0V) 0.76 ± 0.14 0.67 ± 0.18 0.69 ± 0.04 0.63 ± 0.06 0.51 ± 0.04
Q2(0Al, 1V) 0.05 ± 0.03 0.70 ± 0.61 0.19 ± 0.05 0.44 ± 0.08
Q4(1Al, 1V) 0.09 ± 0.00 0.17 ± 0.08 0.30 ± 0.07 0.62 ± 0.07
Q3(1Al, 1V) --- 0.03 ± 0.02 0.08 ± 0.02 0.19 ± 0.05 0.33 ± 0.03
Q1(1Al, 0V) 0.06 ± 0.03 0.05 ± 0.03 0.08 ± 0.02 0.11 ± 0.03 0.11 ± 0.02
Q4(3Al, 0V) 0.08 ± 0.02 0.09 ± 0.05 0.03 ± 0.02 0.05 ± 0.00 0.06 ± 0.03
Q4(2Al, 1V) 0.03 ± 0.02 0.03 ± 0.02 0.05 ± 0.03 0.03 ± 0.02
distribution of 4-coordinated V species
Q4 9.09 ± 4.55 6.52 ± 0.00 6.67 ± 1.90 5.34 ± 1.28
Q3 13.64 ± 13.64 23.91 ± 5.75 23.81 ± 2.52 24.27 ± 4.85
Q2 63.64 ± 16.39 45.65 ± 7.53 55.24 ± 7.80 46.12 ± 4.23
Q1 13.64 ± 7.87 23.91 ± 9.48 10.48 ± 0.95 20.87 ± 4.31
Q0 0.00 ± 0.00 0.00 ± 0.00 3.81 ± 1.90 3.40 ± 0.97

Figure 8. Two-dimensional schematic showing that the increase of s

(where s = 2r, r being the radius of the circle) leads to the increase of
connectivity of the conducting ions to form different channels,
represented by different colors. The eight points represent eight
randomly chosen ions inside a two-dimensional box without periodic
boundary conditions.

∂ln Q
⟨ε⟩ = −kBT 2 = kBT
∂T
kT
⟨ε⟩ = ⟨αs⟩ ⇒ ⟨s⟩ = B
α (8)

At lower temperatures, the average jump distance ⟨s⟩ would

be small. Consequently, the conduction channels would be less
connected. At sufficiently high temperatures, all the ions will be
connected forming a large single channel. Figure 9. Variation of ionic connectivity with cutoff distance s in

■
sample V0.0. Left-hand side shows a large, continuous connected main
channel. Right-hand side shows isolated individual ions/channels.
DISCUSSION
Oxidation State of Vanadium. The V 2p3/2 XPS spectra
(Figure 4b) show that at the sensitivity limit of the XPS V5+ units, having no electrons in the outer shell ([Ar] 4s0, 3d0),
equipment, V exists solely in the 5+ oxidation state.53,54 The result in charge transfer (CT) bands in the UV−vis spectrum.
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Figure 10. The n(s) distributions for samples calculated based on the MD simulation data. The solid black lines for V0.0−V2.0 show the fitting curve.
The CT bands are caused by the transfer of the charge density
from ligand (O−2) to the metal ions (V5+) and generally these
bands are very intense. The large intensity of the CT bands
causes an absorption edge in the UV region of the spectrum
(Figure 3a). The UV−vis spectra also reveal the presence of
V3+ and V4+ states (Figure 3). In the case of V3+ and V4+
species, the absorption is caused by the d → d transitions. For
V3+, the band at ∼12,000 cm−1 is generated by the 3T1g → 3T2g
transitions. For V4+, the bands at ∼9000, ∼15,000, and
∼22,000 cm−1 are engendered by the 2T1 → 2T2, 2T1 → 2E,
and 2T1 → 2A1 transitions, respectively.50 Nevertheless, the
deconvolution of the UV−vis absorption spectra reveals that
the major fraction of V exists in the 5+ oxidation state in all the
glasses, in good agreement with the XPS results.
The presence of a small fraction of V3+ and V4+ indicates the
reduction of V5+ cations and this could be described by the
following equilibrium reactions
1 compound exists in sixfold coordination environments and
V2O5 ⇔ 2VO2 + O2 ↑
2 (9)
1 1
VO2 ⇔ V2O3 + O2 ↑
2 2 (10)
Equations 9 and 10 describe the reduction of V and the 5+
associated release of oxygen. The possibilities for the
occurrence of these reactions were validated by the bubbling
phenomena noticed during melting of the glasses. The
amounts of V3+ and V4+ units are shown in Figure 3.
Considering ideal gas conditions, the amount of O2 released
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from 100 g of glass melts based on eqs 9 and 10 would be 3, 4,
and 5 mL for compositions V0.5, V1.0, and V2.0, respectively.
Thus, though the fraction of V reducing to 3+ and 4+
oxidation states is extremely small and insignificant, that is,
<0.4%, there would still be considerable bubbling of the melt.
Short-Range Structure. According to Lapina et al.,43 the
51
V NMR δiso values for alkali orthovanadates (VO43−, Q0V)
range from −540 to −560 ppm. In the case of alkali
pyrovanadates (V2O74−, Q1V), the 51V NMR δiso values range
from −560 to −580 ppm. Both Q0V and Q1V units are analogous
to orthophosphate and pyrophosphates, respectively, which
exist in silicate glasses when a small amount of P2O5 is added
to the glass.62 According to Skibsted et al.63 and Hayashi et
al.,64 alkali metavanadates (VO3−, Q2V) with alkali ions Li+ and
K+ have δiso values in the range of −573 to −577 ppm and
−553 to −558 ppm, respectively. The metavanadates also have
a distorted tetrahedral structure. A pure V2O5 crystalline
does not exist as tetrahedral units (Q3V).65 Furthermore, the δiso
value of these octahedral vanadium units is ∼ −610 ppm.66
Nevertheless, pure QV3 units do not form in crystalline
materials. In glasses, however, the formation of these units
might be possible, but detection by NMR spectroscopy is too
difficult owing to the quadrupolar effects. Due to the broad
peak observed for all the 51V NMR spectra, the presence of
higher coordinated V cannot be excluded for the glass systems
studied here. According to MD simulations, about 40% of V
exists in five- or sixfold coordination in the current glasses. The
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δiso values of 51V NMR spectra have peak maxima at ∼ −562.7
ppm with a broad resonance (Figure 1d and Table 4). This
would indicate that QnV units in the current glasses exist for n
ranging from 0 to 3. However, decomposition of these broad
resonance peaks into individual components would be
unreliable. Nevertheless, this distribution could be obtained
from MD simulations as shown in Table 5, according to which
most of the vanadium species exist as Q2V units. Moreover,
these QnV units are mainly connected to QnSi units forming Si−
O−V linkages (Figure 7). From Table 5, we see that QnV units
are mainly connected to Q3Si and Q4Si units forming Q3Si(0Al,1V)
and Q4Si(0Al,1V) units. Thus, vanadium units mostly go into
the silicate network regions.
With the addition of vanadium, the 29Si MAS-NMR spectra
progressively shift toward the shielding side. This effect could
happen due to two scenarios:
i. The vanadium units would form lower polymerized
states such as Q0V and Q1V units. Consequently, extracting
the Li+ or K+ cations from the silicate network region
increases the silicate network connectivity, leading to a
shielding effect on the 29 Si nuclei. These less
polymerized QnV units, having few to no BOs, would
stay separated/disconnected from the silicate network,
thus not having any chemical shielding on the 29Si
nuclei. In this scenario, the amount of Q4Si units increases
from 36 to 50% when V2O5 is added from 0.0 to 2.0 mol
%. After accounting for the formation of Q4Si(3Al) and
Q4Si(4Al) units, these amounts would correspond to Peak
C (Table 3). Therefore, in this scenario, Peak A
corresponds to Q2Si units; Peak B corresponds to Q3Si,
Q4Si(3Al), and Q4Si(4Al) units; and Peak C corresponds to
Q4Si units. Furthermore, in this scenario, the slight
chemical shielding effect on the 27Al spectra (Figure 1c
and Table 4) could be due to the increased Si
connectivity since Al tetrahedra are connected to highly
polymerized QnSi units in the next nearest neighborhood.
ii. The vanadium units would form higher polymerized Q2V
and Q3V units. These units, having BOs, might be
connected to other V, Si, and Al tetrahedra forming V−
O−V, Si−O−V, and Al−O−V linkages. In this scenario,
V atoms having a larger atomic number and thus a larger
electron density result in chemical shielding on the 51V,
29
Si, and 27Al nuclei. Therefore, the 29Si and 27Al NMR
peaks would shift to lower δiso values. However, the
relative intensity of the peaks would not change much.
Furthermore, the silicate species would form mixed units
such as QnSi(αAl, βV). Therefore, the Peaks B and C
contain a much more complex mixture of the said units.
According to the MD simulations, both the abovementioned
scenarios are at play simultaneously. It can be seen that the
vanadium units are distributed within a range from Q0V to Q3V
(Table 5).
Intermediate-Range Structure. Though many properties
of glasses depend on the short-range order, properties such as
ionic conductivity and crystallization behavior depend on the
intermediate-range order. As both ionic conduction and
crystallization behavior depend on the ionic diffusion at
intermediate-range distances, therefore, understanding the
intermediate-range structure by MD simulations is of great
interest. The conducting ionic sites’ connectivity density
function, n(s), introduced in this study serves as a tool to
quantify the ion-conducting channels in the glasses. The n(s)
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distribution functions calculated from MD simulations (Figure
10) show right skewness. This right skewness would be due to
the short-range order of the glass/liquid structure. This short-
range order dictates many properties of the glasses. Therefore,
techniques like NMR spectroscopy that probe the short-range
structure have been of much interest to glass science and
technology. According to eq 8, the energy for an ion to jump
from its position to an adjacent site depends on the distance
between two adjacent sites. This implies that the activation
energies for ionic conduction would be directly proportional to
the average jump distance, which in turn is related to the n(s)
distribution. The value of smax initially increased with the
addition of V2O5 (up to 0.2 mol %). However, upon further
addition, the smax value decreased (Figure 10). This together
shows a nonmonotonic trend. Thus, activation energies for
both conduction (Figure 5c) and crystallization (Figure 6b)
also follow a similar trend.
This nonmonotonic trend of smax can be explained by
assuming two different structural roles for V in the
intermediate-range order, as shown in Figure 11. The first
Figure 11. Schematic representation of the intermediate-range glass
structure showing two different roles of V: (a) network-V with narrow
channels and (b) channel-V with broad channels.
type of V enters the glass network without being associated to
the channel regions. These V species are named as “network-
V” as represented in the schematic in Figure 11a. Since V exists
as lower polymerized QnV units, they would have Li+ ions
associated with them and these ions are locked away from the
channel regions. The second type of V species is associated
with the channel regions and named as “channel-V” as
represented in the schematic in Figure 11b and the Li+ ions
associated with them are also part of the channel regions. The
network-V sites depend on the concentration of other
network-forming units, such as Si and Al, because they go
into the interstitial spaces in the network. The larger the
concentration of the other network-forming units, the larger
the interstitial spaces and thus the larger the network-V sites.
Contrariwise, the channel-V sites do not depend on the
concentration of the other network-forming units but on the
size of the channel regions, which is not constrained and could
be expanded and contracted as required by various means,
namely, broadening, meandering, and branching out.
If the aforementioned hypothesis is true, then the
distribution of V into network-V and channel-V species
might depend on the availability of the network-V sites in
each composition and the Boltzmann statistics. It might be
energetically more favorable (from MD standpoint) to form
network-V units, but the available sites are constrained as
discussed above. Therefore, at lower concentrations, the glass
mainly contains network-V units because there are more
network-V sites available. At higher concentrations, network-V
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sites become exhausted, and the rest of the V units go to the
channels. Thus, the glass mainly contains channel-V units that
enhance the connectivity of the ion-conducting channels. This
enhanced connectivity therefore increased the overall ionic
conductivity even when the concentration of charge carriers
decreased. This hypothesis is further supported by the
nonmonotonic trends observed in Ea (Figure 5), EU (Figure
6b), smax (Figure 10), and Vm (Table 2) values.
Structure−Property Relationship. The ionic radii of the
elements present in the glass compositions are as follows: Li+
+ 3+ 4+ 5+
(IV) = 0.59; K (VI) = 1.38; Al (IV) = 0.39; Si (IV) = 0.26; V
2− 60
(IV) = 0.35; and O (II) = 1.35 Å. Considering that the ionic
radius of V5+ is smaller than most of the other ions that it
replaces, the overall Vm must decrease. However, the
experimental values of the glasses show that apart from a
slight initial decrease, there is an overall increase of the molar
volume with vanadium addition. This suggests that vanadium
creates a more open structure in the intermediate-range order,
even when its ionic radius is smaller. The decrease in Tg values
(Table 2) also supports the formation of the open structure
with increasing V additions. Also, the theoretical NBO/BO
ratio increases with increasing additions of V (Table 2). The
modifications in the network structure could be further
understood from the crystallization behavior of the glasses.
Since crystallization involves intermediate-range reordering of
the network structure, studying the crystallization behavior
could be used as a probe to investigate the intermediate-range
structure. The crystalline phase assemblage (Supporting
Information) showed an interesting trend. At lower and higher
concentrations of V, the main phase is LS2. At intermediate
concentrations, the main phases are LS and Q. In a previous
study,31 we have explained the reason behind the formation of
the metastable LS phase in the present glass systems. In the
crystallization sequence, regions that are rich in Li+ ions
(microsegregation owing to the MRN model) with depoly-
merized Si units have large probability (kinetically speaking) to
form the LS phase, whereas the formation of the LS2 phase
requires the presence of Li+ ions in the polymerized network
region (Figure 11a,b) of the glass. Also, V-containing samples
showed predominant surface crystallization. This indicates that
V acts as a nucleation inhibitor in these glass compositions,
diminishing the crystal nucleation rate. However, its addition
resulted in an increase in the crystal growth rates as shown in
Figure 6a. Therefore, it can be assumed that at lower
concentrations of V2O5, the vanadate tetrahedral units occupy
the interstitial sites of the silicate network regions that are
highly polymerized. The as-formed isolated vanadate tetrahe-
dral units connect with each other through modifier cations
and reduce the size of the polymerized network regions (2Q3V
↔ Q2V + Q4V) into polymerized and depolymerized silicate
structural units with the increase of V2O5 concentration up to 1
mol %. The depolymerized silicate structural units along with
Li+ cations convert into the LS phase during the heat
treatment. However, at the highest V2O5 concentrations (2
mol %), the glass network consists of highly polymerized
silicate units as confirmed by NMR (Figure 1a).
■
CONCLUSIONS
Small additions (0.2−2.0 mol %) of vanadium oxide to the
parent glass (23Li2O−2.64K2O−2.64Al2O3−71.72SiO2) in-
duce remarkable variation trends in the ionic conductivity.
Therefore, these glasses are promising candidates for further
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exploration through different compositional modifications to
tailor ionic conductivity toward potential uses as electrolytes
for Li-ion batteries for high-temperature applications. In
addition to doping with vanadium, other components with
similar structural roles could be employed to design
compositions with improved conduction channels. Moreover,
the application temperature could be modified by tailoring
Li2O concentrations that will change the number of Li ions in
the channels.
The small additions of vanadium also have other important
technological implications: (i) enhanced glass forming ability
by substantially reducing the bulk crystal nucleation rates
without affecting much the transparency in the visible region
(Figure 3a) and (ii) drops in Tg (at 1012 Pa s), indicating
decreases in the viscosity, allowing to reduce the processing
temperatures.
In the studied glasses, vanadium exists mostly in the V5+
oxidation state forming ortho- or pyrovanadate units. These
units exist as network-V units at lower concentrations and as
channel-V units at higher concentrations. The network-V units
lock away the network modifier ions thus hindering the ion
transport (Figure 11a). The channel-V units on the other hand
promote ion transport through the channels (Figure 11b). This
dual structural role of vanadium brings nonmonotonic changes
in molar volume, network volume, ionic conduction, and
crystallization behavior with variations in the glass composi-
tion.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jpcc.1c05059.
XRD patterns of the glasses and glass ceramics, SEM
images, DTA curves, decomposition of NMR spectra,
XPS surface composition analysis, and MD simulation
potential parameters (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Anuraag Gaddam − CICECOAveiro Institute of Materials,
Department of Materials and Ceramic Engineering,
University of Aveiro, Santiago University Campus, 3810-193
Aveiro, Portugal; orcid.org/0000-0002-4266-6092;
Phone: +351 234 370 242; Email: anuraagg@ua.pt;
Fax: (+351) 234 370 204
José M. F. Ferreira − CICECOAveiro Institute of Materials,
Department of Materials and Ceramic Engineering,
University of Aveiro, Santiago University Campus, 3810-193
Aveiro, Portugal; orcid.org/0000-0002-7520-2809;
Phone: (+351) 234 370 242; Email: jmf@ua.pt;
Fax: (+351) 234 370 204
Authors
Amarnath R. Allu − Energy Materials and Devices Division,
CSIRCentral Glass and Ceramic Research Institute,
Kolkata 700 032, India; orcid.org/0000-0003-0450-
0929
Sudheer Ganisetti − CICECOAveiro Institute of Materials,
Department of Materials and Ceramic Engineering,
University of Aveiro, Santiago University Campus, 3810-193
Aveiro, Portugal; Energy Materials and Devices Division,
CSIRCentral Glass and Ceramic Research Institute,
https://doi.org/10.1021/acs.jpcc.1c05059
J. Phys. Chem. C 2021, 125, 16843−16857
The Journal of Physical Chemistry C
Kolkata 700 032, India; National Institute of Materials
Physics, RO-077125 Magurele, Romania; Univ. Lille, CNRS,
Centrale Lille, Univ. Artois, UMR 8181UCCSUnité de
Catalyse et Chimie du Solide, F-59000 Lille, France; Present
Address: Schubert Str. 1, 91052 Erlangen, Germany;
orcid.org/0000-0003-1030-7156
Hugo R. Fernandes − CICECOAveiro Institute of
Materials, Department of Materials and Ceramic
Engineering, University of Aveiro, Santiago University
Campus, 3810-193 Aveiro, Portugal; orcid.org/0000-
0002-9689-3127
George E. Stan − National Institute of Materials Physics, RO-
077125 Magurele, Romania; orcid.org/0000-0003-0289-
8988
Catalin C. Negrila − National Institute of Materials Physics,
RO-077125 Magurele, Romania; orcid.org/0000-0002-
5756-2851
Atul P. Jamale − CICECOAveiro Institute of Materials,
Department of Materials and Ceramic Engineering,
University of Aveiro, Santiago University Campus, 3810-193
Aveiro, Portugal; orcid.org/0000-0003-3786-0816
François Mear − Univ. Lille, CNRS, Centrale Lille, Univ.
Artois, UMR 8181UCCSUnité de Catalyse et Chimie
du Solide, F-59000 Lille, France
Lionel Montagne − Univ. Lille, CNRS, Centrale Lille, Univ.
Artois, UMR 8181UCCSUnité de Catalyse et Chimie
du Solide, F-59000 Lille, France; orcid.org/0000-0001-
7607-8558
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jpcc.1c05059
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was developed within the scope of the project
CICECO-Aveiro Institute of Materials, UIDB/50011/2020
and UIDP/50011/2020, financed by national funds through
the FCT/MEC and when appropriate cofinanced by FEDER
under the PT2020 Partnership Agreement. A.G. is grateful for
the financial support from CICECO. A.P.J. is thankful for the
support provided by national funds (OE), through FCT, IP, in
the scope of the framework contract foreseen in the numbers 4,
5, and 6 of the article 23 of the Decree-Law 57/2016, of
August 29, changed by Law 57/2017, of July 19. The NMR
spectrometers from CICECO are part of the National NMR
Network (PTNMR) and are partially supported by Infra-
structure Project No 022161 (cofinanced by FEDER through
COMPETE 2020, and POCI, PORL, and FCT through
PIDDAC). A.G. is thankful to Chevreul Institute (FR 2638)
for providing access to the NMR measurements. Chevreul
Institute (FR 2638), Ministère de l’Enseignement Supérieur,
de la Recherche et de l’Innovation, Hauts-de-France Region,
and FEDER are acknowledged for supporting and partially
funding this work. G.E.S. and C.C.N. acknowledge the support
of PN-III-P1-1.1-TE-2019-0463 and PED-PN-III-P2-2.1-PED-
2019-4519 grants and Institutional Core Program 21 N. H.R.F.
is grateful for the project CICECO-Aveiro Institute of
Materials, UIDB/50011/2020 and UIDP/50011/2020, fi-
nanced by national funds through the FCT/MEC and when
appropriate cofinanced by FEDER under the PT2020
Partnership Agreement. Part of the work was developed
16855
pubs.acs.org/JPCC Article
under the frame of the project funded by DST-SERB (ECR/2
018/000292). A.R.A. acknowledges the financial support by
DST-SERB (ECR/2 018/000292). S.G. would like to thank
Dr. Julien Guénolé and Dr. Yedukondalu Neelam for their
support and encouragement.
■
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