Ceramics International 48 (2022) 21552–21560

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Spectroscopic properties and conduction mechanism of KAl(SO4)2:xSm: A

multifunctional materials for optical and electrochemical applications
Ahmed Souemti *, Islem Labidi, Adel Megriche
Laboratoire de Chimie Minérale Appliquée LCMA (LR19ES02), Faculté des Sciences de Tunis, Université de Tunis El Manar, Campus Universitaire Farhat Hached El
Manar 1, 2092, Tunis, Tunisia

A R T I C L E I N F O A B S T R A C T

Keywords: Anhydrous α-alum materials doped with the trivalent samarium oxide Sm2O3 and denoted as KAl(SO4)2:xSm (x
Samarium oxide = 0; 0.5; 1; 1.5; 2; 2.5% mol.) are prepared by the solid-state reaction method at 350 ◦ C. The resulting phases are
Solid-state reaction crystallized in a simple hexagonal structure with space group P321. Powder X-ray diffraction (XRD), Infrared
Activation energy
(IR), and Raman spectroscopies confirmed a high purity of phases with variation in lattice parameters according
Arrhenius law
Energy storage
to the amount of doping.
Optical measurements through absorption and fluorescence spectroscopies in the ultra-violet and visible re­
gions prove the different electronic transitions between excited levels and 6H5/2 ground state of Sm3+, the
incorporation of samarium in the crystal structure, and suggest the quenching phenomenon.
The materials presented in the study showed an ionic semiconductor behavior with an increase in their
conductivity as a function of the doping level. A 1D conduction is made according to the Correlated Barrier
Hopping CBH model by cations mobility in crystalline sites under the effect of thermal agitation in the
[170–250 ◦ C] region. KAl(SO4)2: xSm (x = 1.5% mol.) with its lower activation energy value, is suggested as a
suitable cathode material for aluminum-based batteries.

1. Introduction sulfate materials. As an example: langbeinite type materials K2Mg

(SO4)3:Ln (Yb3+ [12]; Dy3+ [13]; Gd3+ [24]), picromerite type materials
The research on double sulfated materials is increased exponentially K2Mg(SO4)2⋅6H2O:Ln(Nd3+ [14]; Pr3+ [17]), and vanthoffite type ma­
day after day, because of their interesting structure, low coast synthesis terials Na6Mg(SO4)4:Eu3+ [23].
procedure, physical properties, and their applications in a wide range of First of all, these materials are temperature stable. No phase transi­
fields such as energy storage, dosimetry, and medical domain [1–10]. tions or decomposition have been reported from the room temperature
By and large, the double sulfated materials have the following up to 1000 ◦ C [11,15,21]. Furthermore, they have a regular and
chemical formula M1IM2II(SO4)x.nH2O (MI = K, Na, Li, NH4,... MII = Mg, well-defined structure. Indeed, by their cubical or hexagonal structures,
Co, Zn, Ni, …., n = 0,1,2, …). In the case of n = 0 these materials are these materials can accept lanthanum or metal transition doping
called anhydrous and obtained by a dry chemical process, i.e. prepara­ without any deformation of the crystalline lattice. Usually, the rare earth
tion by solid-state reaction at moderate temperatures (generally not over element substitutes the divalent cation in the crystal structure [12,24].
1000 ◦ C) [11–15]. The variation of M1, M2, and x in the framework gives From a physical point of view, the double sulfate materials doped
rise to an unlimited number of materials that can be prepared. The in­ with rare-earth ions are excellent ionic semiconductors [24]. The studies
vestigations made have revealed that these materials have a rigid and of their electrical properties reveal that they have a thermally activated
well stable structure from room to high temperatures [16–19]. The ionic conduction in the area of temperatures [300–600 ◦ C] [15,18–24].
crystal phase is, in most cases, a primitive cubic one with coordination Their conductivities are improved with the amount and type of doping.
polyhedral such as MIO6 or MIO5 and MIIO6 with common oxygen atoms, It has been found that Gd3+ and Yb3+ exhibit low activation energy
the sulfate ions being in a regular tetrahedral environment such as SO42− values. Such properties make them suitable candidates for electrodes for
[20–24]. sodium and lithium batteries [12,24].
Several studies have been undertaken on rare earth ion doped double The electrical conductivity is 1D, is achieved by grains or grain

* Corresponding author.
E-mail address: ahmed.souemti@fst.utm.tn (A. Souemti).

https://doi.org/10.1016/j.ceramint.2022.04.125
Received 2 March 2022; Received in revised form 11 April 2022; Accepted 12 April 2022
Available online 15 April 2022
0272-8842/© 2022 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
A. Souemti et al. Ceramics International 48 (2022) 21552–21560

boundaries and manifested by cation mobility in the network of the 2.2. Experimental techniques
crystal by thermal agitation. The amount of these migrating cations has
a significant effect on the conduction because, for high concentrations of X-ray Powder Diffraction (XRPD) analysis was carried out using a
rare earth, the electrical conductivity is decreased [12]. BRUKER D8-advance diffractometer with CuKα radiation (λ = 1.5406
Investigations on rare-earth ion-doped langbeinite-type materials Å). X-ray diffraction data were collected with a step size of 0.026, a
have been carried out. The obtained results showed that the materials LynxEye detector, a counting time of 12s, and a variation of 2θ between
K2Mg(SO4)3: Ln (Ln = Dy3+, Yb3+, Gd3+) display broad emission spectra 3.5 and 60◦ . The XRD pattern was first identified to its analog of the
ranging from ultraviolet to infrared, with cooperative emissions in the International Centre for Diffraction Data (ICDD) databases and then the
visible range, and a relatively low relaxation time [12,13,24]. These cell parameters were found after refinement of the structure using the
properties qualify them as suitable thermoluminescent materials, as LPL Celref program.
(Long Persistent Luminescent) minerals, and for uses in fluorescent The Fourier Transform Infrared FTIR spectrum was recorded using a
lamps, scintillation for X-ray tomography. On the other side, research on PerkinElmer UATR Two FT-IR spectrometer in the 1500–450 cm-1 fre­
the material features of picromerite type K2Mg(SO4)2⋅6H2O: Ln (Ln = quency range.
Nd3+, Pr3+) has proved that such materials can be used for laser pointers Raman spectroscopy at room temperature was recorded using the
in the diode commerce as well as in the field of telecommunications as Horriba-Jobin Yvon T64000 instrument. Raman measurements were
optical amplifiers [14,17]. performed in a backscattering cofocal configuration using the 488 nm
The vanthoffite materials doped with trivalent europium Na4Mg excitation line of Ar + laser with a spectral resolution less than 0.5 cm− 1.
(SO4)4: Eu3+ have rather a short relation time (τ = 4.3 ms) that allows to The fluorescence spectrum was recorded by a PerkinElmer LS 55
categorize them as potential agents for the cathode ray tube production Fluorescence Spectrometer with an excitation wavelength equal to 270
[23]. nm.
On the other side, one of the current fields of application of such Electrical impedance spectra (EIS) measurements are carried out
materials is in the energy storage domain, which relies on the elabora­ over a temperature range from room temperature (RT = 25 ◦ C) up to
tion of rechargeable batteries. For this reason, several electrochemical 300 ◦ C and over a large frequency range (5Hz-13 MHz) using a tem­
investigations have been performed on sulfated materials as electrodes perature regulator (Linkam TMS94) and an impedance analyzer
in sodium or lithium-based batteries [25–30]. In particular, the (Solartron 1260 coupled to a dielectric interface 1296). Ec-Lab software
Alluaudite type materials NaM(SO4)3 (M = Fe, Co, Ni, …) present high was used to assess the impedance data in equivalent circuits.
voltage capacities. As an illustration the material Na2+2xCo2-x(SO4)3 can
achieve a voltage of 5 V [26], and Li2Fe(SO4)2 of 3.83 V [25]. 3. Results and discussion
From early 2021, aluminum-based batteries have been subject to
several publications for many reasons [31–40]: Firstly, because of their 3.1. XRD analysis
natural abundance, lightweight, and low cost [33]. Secondly, for its very
high charging capacity and the sufficiently low redox potential of The room temperature XRD patterns of the synthesized materials
Al3+/Al [31–33]. Finally, aluminum was used as an electrode with the collected in the region of 2θ from 5 to 60◦ are illustrated in Fig. 1. The
highest volumetric capacity of 8.04 Ah.cm-3 (four times higher than intensities and peak positions reveal well-crystallized phases. They are
lithium), which is an order of significance greater than the graphite compared to the database file with the ICDD file number 00-003-0337
electrodes used in the traditional batteries (0.84 Ah cm-3) [31]. corresponding to the KAl(SO4)2 undoped material. The hkl values of
The present work context is mainly based on the electrical, optical, the various peaks are assigned to the hexagonal simple system with
and electrochemical properties of double sulfated materials previously space group P321.
mentioned. For this reason, we aim to synthesize a family of α-alum Known that the particle size in powder form can be estimated from
materials doped with Sm3+ ions, which are considered multifunctional XRD patterns using the Scherer relation given by Ref. [44]:
materials. These phosphors have interesting optical properties origi­
Kλ
nated samarium elements in their structure on one hand [41–43], and D= (1)
β.cosθ
significant electrical properties due to their ionic semiconductor
behavior at low temperatures on the other hand. The electrochemical Where: D (nm) is the crystalline size, K = 0.9 is the shape factor; λ =
properties of these materials are not discussed here. They will be the 0.15405 nm is the wavelength of X-ray source; β is the full-width a half
subject of future research. maximum of corresponding peak (FWHM); and θ is peak positions
(radians).
2. Experimental procedure The particle sizes that were obtained are presented in Table 1. A
linear increase in the doping rate is noticed due to the difference in
2.1. Synthesis procedure atomic radius. The Sm3+ doping level may increase the tendency for the
agglomeration of crystallite size to get bigger ones. In addition, with
KAl(SO4)2:xSm solid powder phases are prepared by a simple solid- these important particle sizes, all signals are well observed with lower
state method, in which an equimolar mixture of K2SO4 (99.99% background intensities and they are easily refined with precision.
Aldrich), Al2(SO4)3⋅18H2O (99.99% Aldrich), and x molar of Sm2O3 The lattice parameters refinements done by the Celref program are
(99.99% Aldrich) relative to K2SO4 are finely ground for 1 h and then given in Table 1 and represented in Fig. 2. It is seen that the lattice values
undergoes a thermal treatment in a programmed furnace for 5 h at do not follow a linear increase with the samarium doping ratio. In fact,
350 ◦ C under air with a heating rate of 5 ◦ C.min-1, then slowly cooled for a doping rate of 1%, the crystal has the highest volume, no privileged
down to room temperature. The obtained phases are then annealed direction is observed for the inclusion of doping into the crystal lattice. It
twice successively at 320 ◦ C and 280 ◦ C to homogenize the phases. is well known that in a solid-state solution, and at a constant tempera­
The reaction scheme is as follows: ture, there is a linear relationship between lattice parameters of the
K2SO4 (s) + Al2(SO4)3⋅18H2O (s) + xSm2O3 (x) → 2 KAl(SO4)2:xSm (s) + crystalline structure and the proportions of its elements, this relation­
18H2O (g) ship is known as Vegard’s law, which can be written as Ealloy = x.EA + (1
- x).EB, where EA, EB, and Ealloy are the respective properties of pure A,
pure B, and the alloy AxB1-x, and x is the fraction of one ingredient in a
material point [45]. As a consequence, Vegard’s law is not verified in the

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Fig. 1. Powder XRD patterns of synthesized KAl(SO4)2:xSm (x = 0; 0.5; 1; 1.5; 2; 2.5% mol.) compared to the ICDD database file.

materials is a powerful technique for identifying the bond vibrations

Table 1 modes for a given material. IR spectra of KAl(SO4)2:xSm materials
Lattice parameters; cell volume (V); and crystallite sizes of KAl(SO4)2:xSm
registered in the 1600-400 cm-1 wavenumber range are given in Fig. 3.
materials.
From literature references, the anhydrous double sulfate materials
Material a (Å) c (Å) V (Å3) D (nm) exhibit only SO42− sulfate group and Metal-O bond vibrational modes in
x¼ 0% mol. 4.6869 148.52 7.8082 35 the above range. In particular, sulfate groups in tetrahedral symmetry
x¼ 0.5% mol. 4.6912 148.64 7.799 42 have four vibrational modes noted as υ1-4 [21–23].
x¼ 1% mol. 4.696 149.67 7.8369 47
The attribution of the observed bands on IR spectra, by using Origin
x¼ 1.5% mol. 4.6928 149.23 7.8245 55
x¼ 2% mol. 4.6941 149.58 7.8387 57 2021 software, is given in Table 2. The observed band in lower wave­
x¼ 2.5% mol. 4.6923 149.23 7.8261 62 number region 435-440 cm-1 is assigned to the doubly degenerated
mode (ν2). ν4 is a triply degenerated mode but appeared as two suc­
cessive bands in the region [595-684 cm-1].
In addition, a non-degenerate mode (υ1) is shown as a weak band at
about 1060 cm-1. The broadband located at 1100 and 1260 cm-1 are
associated with the triply degenerated mode υ3.
The results of this analysis suggest that delta nu is a weak de­
pendency on the samarium doping rate. Indeed, the sulfate ions are in a
regular tetrahedral environment in that structure and its slight distor­
tion is caused by a slight difference in atomic positions of oxygen atoms

Fig. 2. Refined cell parameters as a function of samarium doping level in the

host lattice of KAl(SO4)2:xSm materials using the Celref program.

present case. A nonlinear variation of lattice parameters is shown in

Fig. 2.
This deviation from Vegard’s law is also seen in several other ma­
terials such as Ce1-xMxO2 [46] and semiconductors types Ge1-ySny and
Ge1-xSix [47].

3.2. FTIR spectroscopy analysis

Fourier Transformed Infrared spectroscopy FTIR for solid-state Fig. 3. FTIR spectra of synthesized KAl(SO4)2:xSm materials.

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Table 2
IR and Raman band assignments for KAl(SO4)2:xSm materials.
SO42− IR vibrational position Raman vibrational position
modes
xSm (% mol.) xSm (% mol.)

0 0.5 1 1.5 2 2.5 0 0.5 1.5 2 2.5

υ1 1067 1058 1063 1060 1067 1063 1071 1073 1075 1075 1077
υ2 441 435 437 437 436 437 486 482 485 486 488
υ3 1104; 1102; 1103; 1104; 1105; 1105; 1140; 1298; 1154; 1298; 1158; 1302; 1154; 1302; 1155; 1298;
1260 1261 1258 1259 1261 1262 1420 1423 1423 1442 1420
υ4 602; 683 598, 583 602; 685 598; 601 597; 600 596; 601 607; 733; 607; 717; 607; 721; 612; 611;
896 900 903 717; 900 733;
903

of the SO42− tetrahedral as a relation to the concentration of the doping the intensity of the band corresponding to ν1 situated around 1070 cm-1,
agent and does not indicate any further deformation of the polyhedral. undergoes a slight shift towards the high values wavenumber values
Moreover, in the case of the sulfated material, a band appeared at when the samarium content increases in the crystal structure. These
around 550 cm-1 indicating the Metal-O connection (M = Sm; Al, K in observations indicate that samarium trivalent has been inserted into the
this case) which is not visible in this situation. crystalline matrix as a dopant. This behavior is also seen for the band at
Thus, these investigations indicate the good crystalline structure of about 480 cm-1. It is also worth noting, according to these results and the
the synthesized samples; confirming the XRD results; and suggesting the Raman and IR spectra profiles, that the crystalline matrix does not un­
incorporation of the samarium into the structure with no distortion of dergo a distortion of the tetrahedral of sulfate ions as a function of the
the lattice. dopants in one hand and the absence of any impurities or second phases
in the synthesized materials in another hand [48].
3.3. Raman spectroscopy analysis
3.4. Optical properties of Sm3+ in KAl(SO4)2 matrix
Fig. 4 shows the Raman spectra of KAl(SO4)2:xSm materials in the
450-1500 cm-1 wavenumber region. On these spectra the bands char­ The UV absorption spectra of the Sm3+ ion in the sulfate matrix
acteristic of the sulfates SO42− group vibrational modes are schown. The registered in the 200–400 nm region are given in Fig. 5-a. The spectra
band assignments are given in Table 2. By comparison with IR spec­ present the bands corresponding to the transitions from the ground state
troscopy, the Raman spectra display all the active modes with their main 6
H5/2 to the different excited states [49,50]. The plots show absorptions
multiplicity. Indeed, the bands situated around 1420 and 900 cm-1 are peaks with maximum intensity easily assigned according to the ener­
observed on the Raman spectra and are not present in IR. Furthermore, getic diagram of the free Sm3+ ion given in Fig. 5-c. It is seen that in the
studied region the maximum intensities located at 210; 230; 252; 282;
320; 365; 379; 445; and 465 nm are attributed to (6H5/2 →6D5/2); (6H5/2
→(4H, 4G)9/2)); (6H5/2 →2H11/2); (6H5/2 →4H7/2); (6H5/2 →4F11/2);
(6H5/2 →4F9/2); (6H5/2 →6D5/2); (6H5/2 →4I15/2) transitions respectively
[49].
Maximum absorption of samarium ion is situated at 252 nm. A slight
shift of that value compared to other matrixes is justified by the ligand
effect in the sulfated matrix. These bands resulting from the 4f-4f tran­
sitions between the energy levels for the trivalent ion are attenuated by
the effect of the field force of the ligands presented in the crystalline
lattice.
Moreover, the broadband behavior observed on the absorption
spectra is due to several interactions in the crystalline matrix. In fact, for
rare earth ions, the 4f-4f transitions disruption due to the crystal field is
weak because the 4f electrons are shielded by the 5s 5p electrons,
therefore the mixing of 4f with 5d orbitals (opposite parity) is low and
the symmetry orbital 4f is only slightly altered. Thus, the spin- orbit
coupling outweighs the effect of the crystal field [12,13,17]. It is also
known that the position and intensity of certain transitions of rare-earth
ions are found to be very sensitive to the environment around the ion.
Absorption peaks result from ground state to various excited levels are
due to magnetic dipole (MD) and electric dipole (ED) transitions. In our
case, the permitted Sm3+ transitions observed in the absorption spectra
intensity are strongly affected by the crystal field strength around the
Sm3+ ion. In this way, the intensity of an absorption transition depends
strongly on the site symmetry of Sm3+. For example, the high symmetry
exhibits the low absorption intensity. Basically, the intensity of ED and
MD transitions has been used to determine the symmetry of the local
environment of the trivalent 4f ions [13]. It is also important to note that
the difference in K+, Al3+, and Sm3+ radius reduces the symmetry of
Sm3+ in the matrix. Reduced symmetry of the coordination environment
around the Sm3+ ions will enhance a broadband absorption transitions.
Fig. 4. Raman spectra of synthesized KAl(SO4)2:xSm materials. This behavior confirms that the Sm3+ ions are mainly located in sites of

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446, and 529 nm, corresponding to electron transitions from the 5P5/2,
4
G9/2, and 4F3/2 excited levels to the ground level 6H5/2 [49].
It is noticed that the intensity of the band situated at 422 nm in­
creases with the doping rate and reaches a maximum value of x = 1.5%
mol. This behavior is a quenching fluorescence. In this way, fluorescence
quenching refers to any process that decreases the fluorescence intensity
of a sample. A variety of molecular interactions can result in quenching.
These include excited-state reactions, molecular rearrangements, energy
transfer, ground-state complex formation, and collisional quenching
[51–53]. It is well known that the fluorescence intensity can be
decreased by a variety of mechanisms. Such decreases in intensity are
known as quenching. Luminescence quenching may occur by different
mechanisms such as collisional extinction occurring when an excited
state of a fluorophore is deactivated upon contacting another atom in the
main material like oxygen, which is referred to as the quencher. This
self-quenching phenomenon involves a loss of energy by a collision
between excited atoms and ground state atoms. This leads to a reduction
of atoms in the excited state which relax by fluorescence emissions. The
self-quenching rises in direct proportion to the rate at which the colli­
sions take place. Therefore, an increase in the concentration leads to a
decrease in fluorescence emissions. In our case, the emission spectrum
reveals that the obtained collisions are of Sm3+ type at different dis­
tances and different numbers [51–53]. These interactions are different
by their transition forces and electric dipole-dipole type interaction. For
these reasons, the high number of Sm3+ ions in the excited state for
doping levels higher than 1.5 mol% enhances the collisions by creating
clusters of Sm3+ ions, which makes their desexcitation time to the
ground state become relatively slow and subsequently their emissions
decrease.

3.5. Electric and dielectric properties

3.5.1. Nyquist plots

Complex Impedance Spectroscopy (CIS) is a technique that evaluates
the electrical conduction as a function of both temperature and fre­
quency in a given material to determine the nature of charge carriers. Its
concept is to apply a sinusoidal voltage of low amplitude and to measure
the current through the material. The determination of the electric
current and the voltage gives the value of the electrical resistance R. The
conductivity σ can be determined according to the relation [18,23]:
e
σ= (2)
R.S
Fig. 6 a-b shows the Nyquist diagrams of the KAl(SO4)2: xSm mate­
rials as a function of doping rate and temperature. Firstly, the materials
showed the same behavior in the frequency region, a semi-circle for high
frequency and a straight line for the lower frequencies. Secondly, the
total resistance is a sum of the above two regions. Thirdly, in this tem­
perature range, the materials are electrical conductors and that equiv­
alent circuit is shown in situ of Fig. 6-a. It is noticed that conductivity
does not follow a linearity increase with Sm3+ doping rate, in particular
with x = 1.5% mol. material has the lowest resistance value and
therefore the highest conductivity value according to eq. (2). This result
is in good accordance with the fluorescence quenching phenomenon
described in section 3.3. In this case, by analogy, a “conduction
Fig. 5. (a) UV–visible absorption spectra of KAl(SO4)2:xSm synthesized mate­ quenching” phenomenon is to be mentioned.
rials; (b) Visible fluorescence emission spectra for Sm3+ ion in KAl(SO4)2 matrix In the following, we will focus on studying the properties of the
under excitation wavelength λex = 270 nm; (c) Energy levels diagram of free material x = 1.5 mol%.
Sm3+ ion. In addition, conductivity is proportional to the number of mobile
cations of Sm3+ because at a particular doping value it is at saturation.
the crystal lattice without inversion symmetry or they can be found in This behavior is also observed in materials type langbeinite K2M2(SO4)3
different coordination polyhedral [12–14,17]. doped with Yb3+ and Gd3+ [12,24].
The fluorescence spectrum in the 350–700 nm region of KAl(SO4)2: According to Fig. 6-b, the conductivity for KAl(SO4)2: xSm (x = 1.5%
xSm materials is shown in Fig. 5-b. The spectra present broad low- mol.) is thermally activated since, beyond this temperature region, the
intensity bands, of which the most prominent are observed at 422, material behaves like an insulator, and its conductivity increases as the
temperature increases.

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Fig. 7. Arrhenius plots of KAl(SO4)2:xSm synthesized materials.

supposition Fig. 8-b compares the present work with other double
sulfated materials doped with lanthanides element and because doping
these materials with rare earth elements increases the electrical con­
ductivity even more than with transition or alkali metals [18,23,24],
several conclusions can be derived:
Conduction properties in sulfate materials M1M2(SO4)z: xLn is a
complicated function of several parameters, in fact, in that structure ‘z’
does not affect the activation energy which means that the effect of
sulfate ions in their tetragonal symmetry on the conductivity is practi­
cally negligible. Additionally, the presence of the rare earth element
balances the activation energy in a significant manner. Hence, the
trivalent element with well-defined content enhances the conduction
much better than the non-doped material. Moreover, the alkali metal
radius is an important parameter in this process as in most cases po­
tassium is more mobile than sodium. In summary, according to Fig. 8,
two materials will be considered to be the positive electrode in sodium
K2Mg2(SO4)3:xGd (x = 0.5% mol.) or aluminum KAl(SO4)2:xSm (x =
Fig. 6. (a) Nyquist plots of imaginary part Z′′ vs. real part Z′ of the impedance
for KAl(SO4)2:xSm materials; (b) Nyquist plots of KAl(SO4)2:xSm (x = 1.5% 1.5% mol.) batteries on the one hand, and to be suitable as phosphors for
mol.) as a function of temperature. optical applications on the other hand.

3.5.3. Jonscher’s power-law analysis

3.5.2. Arrhenius law analysis
The dependency of the AC conductivity σ ac with the frequency was
The evolution of the conductivity as a function of temperature obeys
measured at varying temperatures and the resultant curves are pre­
the Arrhenius law which can be written as [21]:
sented in Fig. 9-a.
Ln (σ .T) = Ln A −
Ea
(3) The values increased with increasing temperature and displayed a
K.T significant change in slope at certain frequency values (around 14.5 Hz).
The frequency at which the conductivity slope changes is called the
Where σ, T, A, KB, and Ea are the conductivity (S⋅cm− 1), absolute tem­
‘‘hopping frequency’‘, ωp . the plot of the conductivity as a function of the
perature (K), a pre-exponential factor, the Boltzmann constant, and
frequency follows Jonsher’s power law which can be written in the form
activation energy (eV), respectively.
[18]:
Activation energy Ea value is calculated from the slope of eq. (3)
plots for different materials as illustrated in Fig. 7. σ (ω) = σ dc + A.ωn (4)
It is generally believed that a suitable electrode material for battery
technology applications must have the lower activation energy value or in its neperian logarithmic form:
possible. Fig. 8-a exhibits the variation of activation energy as a function Lnσ (ω) = Lnσdc + LnA + n.Ln(ω) (5)
of samarium doping rate. First of all, up to x = 1.5% mol. a decrease in
activation energy values with increased doping rate is noticed. Secondly, σ dc is the value of the conductivity independent of the frequency and
a saturation of mobile cations is noticed for x = 1.5% mol. (Ea = 0.84 is given by the intersect of the plots on the Ln σ axis at a frequency of 0
eV), and then it continues to increase slowly with increasing of Hz, A is a pre-factor that depends on the temperature and the compo­
samarium doping rate in the structure. sition of the sample, and n is the frequency exponent.
In conclusion, the conductivity in these kinds of materials is related It is well known that n generally varies as a function of temperature
to the concentration of mobile cations in the structure when thermally and adopts 0 ≤ n ≤ 1 values. The determination of its value indicates the
agitated. In this process, cations will displace in the network in high conduction model in a solid material. Indeed, for a 3D conductor, n
numbers and the ionic conduction will occur, however, a high yield is values were located between 0.64 and 0.70. In 2D ionic conductors, the
linked to a well-defined trivalent dopant concentration. To enhance this ‘n’ values were in the 0.51–0.60 range. For the 1D ionic conductor, ‘n’
takes a value in the 0.2–0.4 region [18].

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Fig. 8. Variation of activation energies of KAl(SO4)2:xSm materials as function of samarium doping level with comparing to some double sulfated materials.
*Note: the cases where KAl(SO4)2:xSm (x = 2; 2.5% mol) are not plotted on the histogram in order to make the comparison homogenous for all materials.

With M = ωC0 Z′′ and M′′ = ωC0 Z (Co geometrical capacitance).

′ ′

The frequency-dependent variation of M′ and M′′ at different tem­

peratures for the compound x = 1.5% mol. is given in Fig. 10 a-b. The M′
and M′′ values increase with temperature and frequency indicating a
continuous dispersion of short-range mobility of ions/carriers. This
variation suggests that bulk (intra-grain) is responsible for the electrical
properties of the materials. The values of M′ and M′′ become maximum
at high frequency, while at the low frequency they tend towards zero,
indicating the presence of an electrode polarization phenomenon in the
samples. Peaks with maximum values at a higher frequency are assigned
to the confinement of ion/mobile carriers within short-range in their
potentials.
The variation of M′′ as a function of M′ at different temperatures is
shown in Fig. 10-c.

Fig. 9. Variation of the conductivity of KAl(SO4)2:xSm (x = 1.5% mol.) ma­

terial as frequency and temperature.

As shown in Fig. 9-b, the n values are calculated for the higher fre­
quencies from the straight-line slopes. The variations of n against tem­
perature are illustrated in Fig. 9-c. From the above observations, the
studied material has a 1D conduction mechanism and follows the
correlated barrier hopping (CBH) model.
Thus, in this way, the conductivity occurs by the jump of mobile ions
into the sites of the network due to thermal agitation. Such behavior is
also observed in other materials like ytterbium-doped langbeinite
K2Mg2(SO4)3:Yb3+.

3.5.4. Modulus analysis

The complex modulus is a powerful method for the analysis and the
interpretation of several dynamic aspects of the electrical properties,
such as the average relaxation times, the jump rate of the conductors.
The high resistance contributions are mainly dominated in the imped­
ance spectra analysis, while the contribution of the capacitance can be
determined from the complex modulus spectroscopy. The electrical
modulus is given as follows [54,55]:

(5a)
′
M ′′ (ω) = M + jM ′′
Fig. 10. Modulus frequency dependency at different temperature values for
KAl(SO4)2:xSm (x = 1.5% mol.) material.

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A. Souemti et al. Ceramics International 48 (2022) 21552–21560

The observed semi-circular arcs indicate the contribution of both

grain and grain boundary in the conductivity. The center of each semi-
circle being under the M′ axis suggests the non-Debye type relaxation in
the samples. However, the intercepts of the arc tend to move to higher
values as the temperature increases. This may be related to the capacity
increase with rising temperature.

3.5.5. Permittivity and loss studies

The dielectric properties of a material are obtained from the deter­
mination of the dielectric permittivity constants ε’; ε’’ and the dielectric
loss tang δ. These factors are related to the impedance of the material by
the relations [22]:
Z ′′
(6)
′
ε (ω) = − ( )
ωC0 Z ′ 2 + JZ ′′ 2
′
Z
ε′′ (ω) = ( ) (7)
ω C0 Z ′′2 + JZ ′′2
Fig. 11. Frequency dependency of dielectric parameters at different tempera­
ε′′ ture values for KAl(SO4)2:xSm (x = 1.5% mol.) material.
Tang δ = (8)
ε′
Declaration of competing interest
Where:Z′ is the real part of impedance; Z′′ is its imaginary part; C0= ε0eA:
ε0 is the permittivity of the vacuum equal to 8.854*10− 12 Fm− 1; A is the
The authors declare that they have no known competing financial
cross-sectional area of the flat surface of the pellet (62.2*10− 6 m2); e is
interests or personal relationships that could have appeared to influence
its thickness (1.5 mm).
the work reported in this paper.
Fig. 11 a-c shows the variation of the dielectric parameters of the
material x = 1.5% mol. at various temperatures and as a frequency
Acknowledgments
dependence.
It can be observed in the figure that the dielectric parameters present
The authors are thankful to Mr. Lazher LINOUBLI technician of the
high values at low frequencies (105–106 Hz) and then rapidly decrease at
condensed matter physics laboratory for his assistance during the
high frequencies where they become constant (at about Ln F = 5 Hz).
spectrometer and fluorescence measurements. We are also grateful to Pr.
The pattern form of the dielectric values is the result of the inhomoge­
Abdelaziz MEFTAH (Director of ‘Unité de nanomatériaux et photo­
neous nature of the dielectric structure. In this way, the large dielectric
nique’, Department of Physics, Faculty of Sciences of Tunis, Tunis El
constant values at lower frequencies are principally due to the existence
Manar University) for accepting the use of Raman spectroscopy.
of different types of polarization, including the contributions of electron,
dipole and space charge. Effectively, this phenomenon is due to the
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