materials

Article
Towards the High Phase Purity of Nanostructured
Alluaudite-Type Glass-Ceramics Cathode Materials for Sodium
Ion Batteries
Maciej Nowagiel , Mateusz J. Samsel and Tomasz K. Pietrzak *

Faculty of Physics, Warsaw University of Technology, Koszykowa 75, PL-00-662 Warsaw, Poland;
[email protected] (M.N.); [email protected] (M.J.S.)
* Correspondence: [email protected]

Abstract: Alluaudite-type materials are systematically attracting more attention as prospective

cathode materials for sodium ion batteries. In this paper, we strove to optimize various synthe-
sis parameters of three alluaudite compositions (Na2 Fe3 (PO4 )3 —FFF, Na2 VFe2 (PO4 )3 —VFF, and
Na2 VFeMn(PO4 )3 —VFM) to obtain nanostructured alluaudite-type glass-ceramics with high phase
purity. We systematically investigated the role of the chemical reactions, temperature and time of
melting, cooling rate, and reducing factors on the quality of the final products. A detailed synthesis
protocol along with X-ray diffractometry, thermal analysis, scanning electron microscopy imaging,
and electrical conductivity measurements (with impedance spectroscopy) are reported. As a result, a
significant increase of the conductivity was observed in the nanomaterials. The highest value was





 reached for the VFF composition and was equal to 6 × 10−4 S/cm at room temperature.

Citation: Nowagiel, M.; Samsel, M.J.;

Keywords: glass-ceramics; nanomaterials; cathode materials; nanocrystallization; alluaudite
Pietrzak, T.K. Towards the High
Phase Purity of Nanostructured
Alluaudite-Type Glass-Ceramics
Cathode Materials for Sodium Ion
Batteries. Materials 2021, 14, 4997.
1. Introduction
https://doi.org/10.3390/ The rapidly increasing development of and global demand for portable electronics,
ma14174997 electric vehicles, and stationary storage for renewable energy sources encourage looking
beyond well-established lithium ion battery technologies. Therefore, it comes as no surprise
Academic Editors: Matteo Tonezzer that the interest in Na+ ion conductors has recently revived, driven by a vision of sodium
and Davide Barreca ion batteries (NIBs). Due to the common abundance of sodium, NIBs (despite their slightly
lower OCV and capacity) could be a solution to shrinking resources of lithium. Therefore,
Received: 16 July 2021 many candidates for NIB chemistry have been studied. Among them, NASICON-type
Accepted: 26 August 2021 materials have drawn much interest, with the possibility to be used as solid electrolytes
Published: 1 September 2021
(predominant ionic conductors) and electrode materials (mixed electronic ionic conductors).
On the contrary, alluaudite-type materials (e.g., NaMnFe2 (PO4 )3 ) are much less known in
Publisher’s Note: MDPI stays neutral
this field, even though their ability to reversibly intercalate sodium ions was demonstrated
with regard to jurisdictional claims in
almost 20 years ago.
published maps and institutional affil-
Alluaudites were firstly discovered in natural minerals. In 1848, Damour studied
iations.
iron, manganese, and sodium phosphate derived from the pegmatite of Chanteloube near
Limoges in central France. He postulated classifying this mineral into separate species.
He also proposed naming it after a French mineralogist François Alluaud [1]. It was not
until 1955 that Fisher described the structure of alluaudite. It belongs to the monoclinic
Copyright: © 2021 by the authors. system and the C2/c space group. The unit cell parameters of a material containing iron
Licensee MDPI, Basel, Switzerland. Fe
and manganese in a proportion of Mn = 1.76 were determined as follows: a = 12.004 Å,
This article is an open access article
b = 12.533 Å, c = 6.404 Å, β= 114 220 [2].
◦
distributed under the terms and
Sixteen years later, Moore made a detailed structural analysis. The ideal crystalline
conditions of the Creative Commons
compounds with an alluaudite structure can be described by a number of chemical formu-
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
las, limited, on the one hand, by the composition, in which there are lower (2+) oxidation
4.0/).
states of manganese and iron—NaCaMn2+ Fe22+ (PO4 )3 —and on the other hand, in which

Materials 2021, 14, 4997. https://doi.org/10.3390/ma14174997 https://www.mdpi.com/journal/materials

Materials 2021, 14, 4997 2 of 15

these metals are at higher (3+) valence state, which at the same time results in the absence
of sodium and calcium in the composition—Mn3+ Fe32+ (PO4 )3 . Alluaudites tend to crys-
tallize in a partially oxidized form with a chemical composition somewhere in between.
Alluaudites are characterized by the simultaneous presence of iron at different degrees of
oxidation (2+, 3+), which can be expressed by a formula: Na2 Mn2+ (Fe2+ Fe3+ )(PO4 )3 . In
general, compounds with an alluaudite structure can be described by a structural formula
4X(1)X(2)M(1)M(2)2 (TO4 )3 , where X is a large cation with a polyhedral environment of
oxygen ions (e.g., Na+ , Ca2+ , K+ ), M is an element whose surroundings have the shape
of a distorted octahedron (e.g., Mn, Fe, Li, Mg), and T is an element with a tetrahedral
environment (e.g., P, As). The numbers in parentheses refer to different atomic positions [3].
The alluaudite structure consists of chains of M(2) octahedron pairs connected to each
other by means of distorted M(1) octahedrons. The chains are connected through tetra-
hedra TO4 (e.g., PO4 ). As a result, they create surfaces extending in the plane (a,c). The
three-dimensional structure of the alluaudite is the result of connecting these surfaces by
tetrahedra PO4 . This results in the formation of two types of channels in the direction
c [3,4]. The channels may be filled with atoms X. There is more than one possible atom
position in each channel. According to the nomenclature used in Hatert’s work, these
will be A(1), A(1)’, and A(1)” in Channel 1 and A(2) and A(2)’ in Channel 2, respectively.
Unlike the M positions, the channel positions may be partially or completely empty. In
most alluaudites, the atoms are at positions A(1) and A(2)’, and there are gaps at positions
A(1)’, A(1)”, and A(2) [5].
Crystalline compounds with the alluaudite structure can be also synthesized. Hatert
in his work [5] described the synthesis of a compound NaMnFe2 (PO4 )3 —with a similar
chemical composition to the natural alluaudite originating from Buranga in Rwanda, stud-
ied earlier by Fisher. Synthesis by the solid-state reaction method resulted in obtaining a
material with unit cell parameters compatible with the natural mineral [5]. The presence of
channels in which unoccupied ion sites may additionally exist has attracted interest in these
materials for use in reversible batteries. In 2003, Richardson presented preliminary elec-
trochemical results, using NaFe3 (PO4 )3 as a cathode material in lithium ion batteries [6].
Usage of NaMnFe2 (PO4 )3 as a cathode in sodium batteries was demonstrated by Trad in
2010 [4].
A growing number of alluaudites with other stoichiometries and different transition
metals have been reported, including iron, manganese, vanadium, and cobalt. Many
of them were investigated as cathodes in sodium batteries, and their electrochemical
capacity was determined. The values varied from 50 to 140 mAh/g, while most of the
papers reported values about 100 mAh/g. A review of such parameters can be found,
e.g., in [7]. Among the compositions containing iron, vanadium, and manganese, e.g.,
Na2 Fe2 V(PO4 )3 [8] and Na2 Mn2 V(PO4 )3 [9] have been synthesized and studied.
Redox reactions at the cathode side are limited by low Na+ ion diffusivity [10]. Low
electrical conductivity is another obstacle for alluaudites studied to date for use in sodium
batteries. The attempts to improve these drawbacks include coating the grains of the
material with carbon, nanostructuring, filling the M position with various cations, or a
combination of the above. Often, these treatments are insufficient, and it is necessary to add
conductive carbon also at the stage of cathode preparation (e.g., [8,11–13]). However, this
increases its volume and decreases the volumetric capacity. Therefore, it is worth trying to
reduce its amount in electrochemical devices.
In recent years, J.E. Garbarczyk, T.K. Pietrzak, and coworkers investigated the phe-
nomenon of the thermal nanocrystallization of amorphous analogues of cathode materials
for lithium batteries (e.g., [14,15]). This method consists of two stages: (i) rapid cooling
of the molten mixture of substrates and (ii) proper heat treatment of the glass in order
to obtain nanocrystalline glass-ceramics. The advantage of this approach is the lack of
carbon additives during the process. Nonetheless, as a result, nanomaterials often exhib-
ited a giant increase of electrical conductivity, when containing crystalline grains of sizes
up to several nanometers. The success of the method was attributed to the creation of
Materials 2021, 14, 4997 3 of 15

favorable conditions for the electron (polaron) hopping conductivity on the surfaces of
the nanograins.
A similar approach was applied recently to NASICON [16] and alluaudite-type [17]
materials. It was shown that it is possible to obtain glassy analogues of these materials
and subject them to thermal nanocrystallization. However, the observed increase of the
conductivity was not very high. Furthermore, our in-depth studies revealed that the
reproducibility of phase purity was low. Therefore, in this work, we decided to focus on
optimizing the synthesis conditions to strive for the better phase purity and reproducibility,
as well as higher conductivity of alluaudite-type nanostructured glass-ceramics. We
selected the compositions reported previously in our paper [17], namely: Na2 Fe3 (PO4 )3 ,
Na2 VFe2 (PO4 )3 , and Na2 VFeMn(PO4 )3 . According to our best knowledge, the latter
composition has not been reported elsewhere.

2. Materials and Methods

For the syntheses, the following reagents were used: Na2 CO3 (99.8%, Polish Chem-
icals), FePO4 · 2H2 O (pure, Roth) or FeC2 O4 · 2H2 O (99%, Aldrich), V2 O5 (99.6%, Roth),
Mn(CH3 COO)2 · 4 H2 O (99%, Aldrich), NH4 H2 PO4 (99%, Polish Chemicals). Stoichiomet-
ric amounts of the reagents were homogenized in a mortar and put into porcelain crucibles.
The crucibles were put in an inductive furnace (Argenta AFI–02) preheated to 700 °C and
heated up to 1300–1350 °C, depending on the sample. The heating was carried out at
the full power of the furnace (4 kW). This resulted in the heating rate reaching up to 100
°C/min. To ensure a nonoxidizing atmosphere, a double-crucible technique was used. In
other words, the main crucibles were put into a larger crucible filled with activated charcoal
and covered with a lid. The visualization of this concept can be seen in Figure 1 in [18].
The batches were kept at the maximum temperature for 15 min and eventually quenched
between two metal plates (stainless steel or copper) in air.
The amorphousness of the as-synthesized samples and the structure of glass-ceramics
were investigated with X-ray diffractometry. A Malvern Panalytical Empyrean diffrac-
tometer was used, equipped with a copper lamp. The measurements were carried out
in the 5–110° 2θ range at room temperature. The temperatures of glass transition and
crystallization were determined by differential thermal analysis. The measurements were
carried out with a TA SDT Q600 device with a constant heating rate of 1 °C/min and
10 °C/min in a flow of argon. The temperature dependencies of the electrical conductivity
were investigated with impedance spectroscopy using either Solartron 1260 or Novocontrol
Alpha-A analyzers, in a tube furnace (manufacturer: Czylok). The measurements were
carried out in an argon atmosphere. High temperature stabilization was ensured by a
Eurotherm 2404 controller and self-developed software, as described in [19]. Due to the
modest conductivity of the pristine glasses, a signal of 1 V amplitude was used in these
experiments. The temperature was stabilized for at least 30 min prior to each measure-
ment. The temperature drift during each impedance measurement was lower than 0.5 °C.
The microstructure of the samples was observed using field emission scanning electron
microscopy (FE-SEM) on a Zeiss Ultra Plus instrument at the Institute of High Pressure
Physics, PAS. The cross-sections of the samples were sputtered with a thin (several nm)
conducting layer of carbon. EDS elemental analyses of the glasses were performed during
the SEM experiments.

3. Optimization of the Synthesis Route

The phase purity of alluaudite-type glass-ceramics synthesized previously by us [17]
was still unsatisfactory and appeared to be partially irreproducible. Therefore, the most
important part of this study was to adjust different parameters of the syntheses to obtain
alluaudite-type nanostructured glass-ceramics with high phase purity. The following
parameters were altered during subsequent syntheses of alluaudite-like glasses:
1. The time of melting;
2. The temperature of melting;
Materials 2021, 14, 4997 4 of 15

3. The source of iron (iron phosphate or iron oxalate);

4. Additional presynthesis before high-temperature melting;
5. Plates being used for quenching;
6. The use of an additional lid, providing a better reduction of the reagents;
7. The time between the homogenization of the reagents and the synthesis;
8. The amount of the reagents in the crucibles.
Due to numerous synthesis parameters (the key factors are presented in Figure 1), let
us introduce the following system of sample identification: MMM-Fe-pp-ld-mq, where
the meaning of the symbols are as follows: MMM—the presence of transition metals in
the nominal composition, Fe—the iron source, pp—presynthesis, ld—covering lid, mq—
cooling plates used for melt-quenching. The possible values of each parameter are—for
clarity—listed in Table 1.

Figure 1. Scheme of the key factors taken into account during the optimization of the syntheses.

Table 1. Key to the symbols used in the sample identification system MMM-Fe-pp-ld-mq.

Category Value Meaning

MMM FFF Na2 Fe3 (PO4 )3
(nominal composition) VFF Na2 VFe2 (PO4 )3
VFM Na2 VFeMn(PO4 )3
Fe IO iron oxalate
(iron source) IP iron phosphate
pp WP with presynthesis
(presynthesis) NP no presynthesis
ld L crucible covered with a lid
(cover) X crucible not covered with a lid
mq S stainless steel plates
(cooling plates) C copper plates

Previous investigations (both reported in [17] and other studies of ours, unpublished)
indicated that the optimal time and temperature of the syntheses were 15 min at 1300 °C.
Therefore, all further syntheses were carried out with these fixed conditions. Precisely, the
batches were put into the outer crucible preheated to 700 °C, rapidly heated to 1300 °C, and
kept at that temperature for 15 min, before quenching.
The optimization started from samples FFF (i.e., with the nominal composition of
Na2 Fe3 (PO4 )3 ). In Figure 2, the XRD patterns of several synthesized samples after heat
treatment at 650 °C are shown. Due to numerous syntheses with a wide variety of parame-
ters, we reduced the data to show the most important factors affecting the final phase purity.
We started from the synthesis using iron (III) phosphate as a precursor, no presynthesis,
no additional cover, and quenching with stainless steel plates (FFF-IP-NP-X-S). These
parameters resulted in a sample with the alluaudite phase with considerable Na3 Fe2 (PO4 )3
secondary phase impurities (ICDD Card No. 00-045-0319). In Na3 Fe2 (PO4 )3 , iron exists at
Materials 2021, 14, 4997 5 of 15

the 3+ oxidation level, whereas in alluaudite, the average oxidation level is 7+/3. Therefore,
we decided to cover the outer crucible with an additional lid (FFF-IP-NP-L-S), providing
a better reducing atmosphere, which resulted in a much lower content of the secondary
phase. However, traces of orthorhombic NaFePO4 (ICDD Card No. 01-083-9002) were de-
tected. We also tried to substitute iron (III) phosphate with iron (II) oxalate (FFF-IO-NP-L-S).
At first, the results were disappointing. The batch would not easily glassify, and further
heat treatment resulted in significant amounts of NaFePO4 and other, unidentified phase
impurities. The use of presynthesis was previously experienced as a factor improving
phase purity. To further facilitate the glassification process, we changed the stainless steel
plates to copper ones, which would provide a faster cooling. The batch synthesized in such
conditions (FFF-IO-WP-L-C) resulted in superior phase purity after nanocrystallization.
One might expect that similar conditions would be also optimal for the syntheses of
the samples VFF (i.e., with the nominal composition of Na2 VFe2 (PO4 )3 ). Unfortunately,
this was not the case, and therefore, various parameters were checked once again. We
started from syntheses using iron (III) phosphate, no presynthesis, and no additional lid
(VFF-IP-NP-X-S). This resulted in samples with NaVOPO4 impurities (ICDD Card No. 04-
009-5707). In NaVOPO4 , vanadium exists at the 4+ oxidation level, whereas in alluaudite,
its oxidation state should be 3+. Therefore, a more reducing atmosphere was provided
with the use of an additional lid (VFF-IP-NP-L-S). This resulted in reduced amounts of the
NaVOPO4 secondary phase. Substitution of the iron source (with iron oxalate) resulted in
a material with high phase purity (VFF-IO-NP-L-S). The influence of the presynthesis was
additionally checked (VFF-IO-WP-L-S). Surprisingly, in this case, the procedure reduced
the phase purity by introducing the NaVOPO4 secondary phase.
The beginnings of VFM optimization (i.e., Na2 VFeMn(PO4 )3 ) started from the syn-
thesis using iron phosphate without the presynthesis (VFM-IP-NP-X-S). This procedure
resulted (after further heat treatment at 650 °C) in materials with the alluaudite structure
containing NaVOPO4 impurities. In this case, however, the use of an additional lid (VFM-
IP-NP-L-S) was enough to obtain the sample with the pure alluaudite structure. It was
also checked whether the use of the presynthesis affected the final phase purity. In such
a procedure (VFM-IP-WP-L-S, not shown in the figure), minor impurities of NaVOPO4
were detected. Substitution of iron phosphate with iron oxalate (VFM-IO-NP-L-S and
VFM-IO-WP-L-S) also resulted in materials with poor phase purity. Additionally, the
procedure without the presynthesis caused much lower glass-forming properties of the
batch. It is worth mentioning that, sometimes, the procedure VFM-IP-NP-L-S was not
fully reproducible, i.e., it resulted in minor phase impurities. This issue was carefully
investigated. The period between the homogenization of the reagents and the synthesis
appeared to play a noticeable role. The satisfactory phase purity was obtained when the
reagents were kept for several days in an ambient atmosphere and standard humidity.
There is no quantitative explanation of this phenomenon. However, in our opinion, it was
the low humidity (e.g., caused by air conditioning) that had a negative influence on the
final phase stability.
The purpose of these efforts was to obtain alluaudite nanocrystalline materials with
high phase purity. Additionally, we observed the influence of the quenching rate on the
glassification of the as-received materials. In particular, it was possible to obtain glassy FFF
only by quenching between copper plates. Cooling with stainless steel plates (lower rate)
usually resulted in partially crystallized materials. However, the primary phase was in
agreement with alluaudite reference patterns. The phase persisted also after their thermal
treatment. The compositions VFF and VFM did not require quenching with copper plates
to obtain satisfactorily amorphous samples.
Materials 2021, 14, 4997 6 of 15

(a)

(b)

(c)
Figure 2. XRD patterns of glasses at various conditions, after their heat treatment at 650 °C:
(a) Na2 Fe3 (PO4 )3 , (b) Na2 VFe2 (PO4 )3 , (c) Na2 VFeMn(PO4 )3 . Gray vertical lines show the positions of
the diffraction lines of the reference Na2 Fe2 Mn(PO4 )3 alluaudite (ICDD Card No. 04-012-0978) pattern.
Major peaks ascribed to impurity phases are marked as follows: hexagons—Na3 Fe2 (PO4 )3 (ICDD
Card No. 00-045-0319); squares—NaFePO4 (ICDD Card No. 01-083-9002); diamonds—NaVOPO4
(ICDD Card No. 04-009-5707).
Materials 2021, 14, 4997 7 of 15

4. Results
The samples with the highest phase purity from the previous section were selected for
further in-depth investigation, namely: FFF-IO-WP-L-C, VFF-IO-NP-L-S, and VFM-IP-NP-L-S.
In the following text and figures, they are referred to simply as FFF, VFF, and VFM, respectively.

4.1. Differential Thermal Analysis

Differential Thermal Analysis (DTA) traces of the as-synthesized glasses are shown
in Figure 3. Their shape is typical for glassy materials. An endothermic step-like glass
transition was followed by a distinct exothermic crystallization process. The temperatures
of the observed thermal events (namely glass transition Tg and main crystallization Tc ) are
shown in Table 2. In the sample VFM, an additional crystallization process was observed
at a higher temperature (peak maximum at Tc2 = 623 °C).

Figure 3. DTA traces of as-synthesized glasses. The measurements were carried out with a 10 °C/min
heating rate in argon flow. The glass transition and crystallization processes are marked with arrows
and vertical lines, respectively.

Table 2. Glass transition (Tg ) and crystallization (Tc ) temperatures in the studied glassy samples,
determined from DTA measurements carried out with a 10 °C/min heating rate in argon flow.

Sample ID Tg /°C Tc /°C

FFF 519.3 570.5
VFF 514.9 593.7
VFM 507.3 576.1

4.2. X-ray Diffractometry

The XRD patterns of the as-synthesized glasses are shown in Figure 4a. All samples
exhibited an amorphous halo and lacked significant Bragg reflexes, which confirmed their
amorphousness. Only in the pattern of the samples of VFM, several minor peaks were
observed. They were ascribed to the V2 O3 karelianite phase (ICSD Card No. 98-000-1871).
This proved that the V2 O5 used as a reagent in the synthesis was reduced to vanadium (III)
oxide, but was not incorporated entirely into the glass network.
The patterns of glassy samples that were subject to heat treatment at 650 °C are shown
in Figure 4b. A pattern of Na2 Fe2 Mn(PO4 )3 alluaudite [20] (ICDD Card No. 04-012-0978) is
Materials 2021, 14, 4997 8 of 15

given as a reference. Two conclusions can be drawn from this plot: (i) all nanocrystallized
samples (containing different transition metals) preserved the monoclinic structure of
alluaudite; (ii) no impurity phases were detected besides the primary alluaudite phase.
Furthermore, the precipitates of V2 O3 that were observed in the glassy VFM samples were
no longer detected by XRD. This is probably because the V3+ ions were incorporated into
the alluaudite structure.

(a)

(b)
Figure 4. XRD patterns of the as-synthesized glasses (a) and samples after heat treatment at 650 °C
(b). The impurities of the V2 O3 karelianite phase (ICSD Card No. 98-000-1871) are marked with
the asterisks. A pattern of Na2 Fe2 Mn(PO4 )3 alluaudite (ICDD Card No. 04-012-0978) is given as a
reference for the nanocrystalline samples.

4.3. Impedance Spectroscopy

In general, the values of the electrical conductivity of the as-synthesized glasses were,
as expected, modest and slightly varied among the samples from the same batch. Therefore,
several measurements were carried out for different fragments, and average values were
calculated. This procedure yielded conductivity (σg ) as follows: 1.5(2) × 10−8 S/cm,
2(1) × 10−10 S/cm, and 3.5(9) × 10−11 S/cm for batches FFF, VFF, and VFM, respectively.
Subsequently, the glassy samples were heat-treated in argon flow up to different
maximum temperatures (with a heating rate of 2 °C/min) and cooled down to room
temperature. The electrical conductivity of each nanocrystallized sample was measured.
Materials 2021, 14, 4997 9 of 15

The summary results are presented in Figure 5a–c. It was shown that the proper heat
treatment led to a significant increase in the conductivity. The increase was significantly
different depending on the composition. The conductivity of nanocrystallized FFF samples
was only ca. 100-times higher than the starting glass. On the contrary, the conductivity
of nanocrystallized VFF and VFM samples was approximately five orders of magnitude
higher.

(a) (b)

(c)
Figure 5. Electrical conductivity at room temperature of samples after their nanocrystallization at
different maximum temperatures: (a) FFF, (b) VFF, (c) FVM. The conductivity of the starting glass
(σg ) is marked with a horizontal line. DTA traces taken at 1 °C/min are given for comparison.

Impedance spectroscopy carried out in situ during the heating and subsequent cooling
ramps gave a better insight into the influence of the nanocrystallization on the electrical
conductivity in the samples. When planning these experiments, the maximum temperature
was selected accordingly to the highest conductivity reached previously in ex situ measure-
ments.
From these measurements, the values of activation energy (Ea ) of conductivity were
determined: 0.57 eV, 0.71 eV, and 0.88 eV for the FFF, VFF, and VFM glasses, respectively.
After nanocrystallization, Ea slightly dropped in the case of FFF to 0.46 eV. For other
compositions, the decrease was more pronounced, i.e., 0.21 eV and 0.11 eV for the VFF and
VFM nanomaterials, respectively.
Analyses of the shape of the impedance figures revealed that both glasses and highly
conductive nanomaterials exhibited predominant electronic conductivity. The Nyquist
plots showed well-defined single semicircles. Only in the case of the VFM samples, high-
Materials 2021, 14, 4997 10 of 15

temperature impedance spectra showed low-frequency spurs originating from ionic con-
ductivity. This is the reason why the VFM samples exhibited different (higher) activation
energies (Figure 6c) in a high-temperature range.

(a) (b)

(c)
Figure 6. Temperature dependencies of electrical conductivity upon heating and subsequent cooling
of initially glassy samples: (a) FFF, (b) VFF, (c) VFM The values of the activation energy upon
heating and cooling are given, along with the value of the room temperature conductivity of the
nanomaterials. Corresponding DTA traces taken at 1 °C/min are provided for comparison. The
estimated uncertainties of the values are smaller than the least significant digit in the notation.

4.4. Scanning Electron Microscopy with EDS Microanalysis

During SEM imaging, the average elemental composition of the as-synthesized glasses
was studied by EDS. The main purpose was to identify impurities (i.e., the elements not
present in the nominal compositions) and their content. It came as no surprise that minute
amounts of aluminum and silicon were detected. The ceramic crucibles used in the synthe-
ses were said to be the origin of these elements. Their content was, however, negligible and
varied between 0.2–0.4 at.% and 0.4–0.7 at.% for aluminum and silicon, respectively.
SEM images of the as-synthesized glasses (Figure 7a,c,e) taken at low magnifications
showed, in general, a uniform amorphous structure without noticeable polycrystalline
grains. However, high magnifications revealed the microstructure of the samples consisting
of fine grains. In the sample FFF, the dimensions of the grains were ca. 10 nm. The sample
VFF exhibited indistinct structures aligned in one direction. This alignment was more
clearly visible at higher magnification (Figure 7d). This was probably the result of the
melt-quenching method, where the orientation was determined by the cooling plates. The
Materials 2021, 14, 4997 11 of 15

microstructure of the VFM sample exhibited some other inhomogeneities, e.g., pores and
infrequent grains. An image taken at high magnification (Figure 7f) revealed ca. 100 nm
grains precipitated in the surrounding matrix. The origin of these grains was unclear.
These might have been SiO2 gains, but SEM images in the backscattered mode showed
no distinct contrast between the matrix and the grains. This suggested that there was
no significant difference in composition (precisely: the average atomic number of the
elements) between these features. Furthermore, the XRD measurements of all samples
visible in Figure 7a–f showed no Braggs’ reflexes. Hence, we came to the conclusion
that the nanograins were either amorphous or were the nuclei of crystalline grains that
would grow after thermal treatment. This would be in agreement with the facts that it
was not easy to synthesize entirely amorphous samples and we were on the very edge of
glassification-crystallization region.
The SEM images of the samples after thermal treatment are shown in Figure 8a–f. At
first, at low magnifications, their microstructure resembled polycrystalline materials, as
large (micrometric) structures were visible. However, at higher magnifications, a more
complex microstructure was revealed. The large grains were composed of smaller nano-
metric grains, which were mostly pronounced in the sample VFM (Figure 8f). As was
demonstrated earlier (e.g., [14,15]), the presence of nanocrystallites with disordered shells
provides favorable conditions for electronic transport due to polaron hopping between
aliovalent transition metal ions.

(a) (b)

(c) (d)
Figure 7. Cont.
Materials 2021, 14, 4997 12 of 15

(e) (f)
Figure 7. SEM images of the as-synthesized glassy samples taken at low magnifications (1–5 kX, left
images) and high magnifications (100 kX, right images): FFF (a,b), VFF (c,d), VFM (e,f).

(a) (b)

(c) (d)

(e) (f)
Figure 8. SEM images of the nanocrystallized samples with significantly improved electrical conduc-
tivity, taken at low magnifications (1 kX, left images) and high magnifications (100 kX, right images):
FFF (a,b), VFF (c,d), VFM (e,f).
Materials 2021, 14, 4997 13 of 15

5. Discussion
The studies of the alluaudite-type glassy and nanostructured materials presented in
this paper were in agreement with other reports on this phenomenon in various glass
systems. At the same time, some differences between this study and our previous work
about alluaudites [17] need to be underlined.
DTA traces in this work (Figure 3) and in the previous work (Figure 1 in [17]) slightly
differed. The glass transition and crystallization peaks were now more distinct. Previously,
DTA traces contained additional minor peaks, probably resulting from the crystallization
of secondary phases. Now, only VFM glass exhibited two crystallization peaks. This
was, however, not reflected in the XRD patterns, where only the primary alluaudite
phase was observed. One can conclude that the secondary peak may originate from
the recrystallization processes of the primary phase.
The temperatures of the thermal events varied between compositions. Such an effect
was observed earlier many times in different glass systems, e.g., LiF–M2 O3 –P2 O5 [21] or
NaF–M2 O3 –P2 O5 [16]. Different transition metals create bonds of various strengths and
therefore affect the temperatures of the glass transition and crystallization. In addition to
this, the synthesis conditions may have an influence on the temperatures of thermal events
occurring in samples with the same compositions. Such an effect was observed, e.g., in
vanadate–phosphate glasses [22].
The alluaudite-type cathode materials studied in this work belong to a class of mixed
electronic ionic conductors. The ionic part is due to mobile Na+ ions. Electronic conduction
occurs due to polaron hopping between transition metals at various oxidation levels, e.g.,
Fe2+ /Fe3+ or V3+ /V4+ [15]. In this work, higher values of electrical conductivity than
previously found were observed. The conductivity of the initial glasses ranged roughly
between 10−10 and 10−8 S/cm. This was probably because more favorable conditions for
electron hopping appeared. In the previous work [17], the conductivity of nanocrystalline
alluaudites was still modest (mostly between 10−12 and 10−11 ). In this work, as a result
of systematic studies, nanostructured materials with significantly improved conductivity
were obtained. Previously, the nanocrystallized samples exhibited predominant ionic
conductivity. Now, the electronic part was significantly improved. Thus, the samples
exhibited predominant electronic conductivity. The decrease of the activation energy after
nanocrystallization is a typical phenomenon. Values as low as 0.1–0.2 eV were observed,
e.g., in highly conducting olivine-like nanomaterials [14]. In Figure 5, one can observe
the changes of the conductivity of the nanomaterials at room temperature depending on
the nanocrystallization (i.e., heat treatment) maximum temperature. The increase began
around a crystallization peak observed in the DTA trace and was the highest soon after the
peak. Further heating resulted in a conductivity drop. A similar behavior was observed
previously in vanadate–phosphate glasses (Figure 14 in [23]).
One can see that the highest values of the conductivity presented in Figure 5 slightly
differed from the values obtained during in situ measurements (Figure 6). This was proba-
bly because the final value of conductivity was very sensitive to the nanocrystallization
temperature. For both heat treatments, furnaces of the same model were used. However,
in the case of in situ measurements, the sample was held in a holder in the middle of the
tube. In the other case, the samples were put in alumina combustion boats lying at the
bottom of the tube. Thus, even though the set temperature of the furnace was the same,
the different geometry could make a noticeable difference in the exact temperature of the
heat-treated samples.
The values of the conductivity of the nanocrystallized samples were in qualitative
agreement with their microstructure. A lower conductivity was observed in the FFF sample.
In this material, the amount of small nanocrystallites (Figure 8b) was lower than in other
materials. VFF and VFM exhibited higher conductivity, and their microstructure was
dominated by nanocrystallites (Figure 8d,f). Such a correlation was previously observed,
e.g., in the case of olivine-like nanomaterials [14].
Materials 2021, 14, 4997 14 of 15

6. Conclusions
In this work, a systematic optimization of the synthesis conditions of three alluaudite-
like glasses was conducted: Na2 Fe3 (PO4 )3 (FFF), Na2 VFe2 (PO4 )3 (VFF), and Na2 VFeMn(PO4 )3
(VFM). Numerous factors that had an influence on glassification and the final phase purity
of the nanomaterials were identified. They were, however, not the same in all cases. The
optimal synthesis conditions for the samples FFF were as follows: use of iron oxalate,
presynthesis, melt-quenching with copper plates. In the case of VFF, the conditions were:
use of iron oxalate, no presynthesis, melt-quenching with steel plates. In the latter case
(VFM), iron phosphate was used, no presynthesis, and melt-quenching with steel plates. In
all cases, the additional covering with a lid was beneficial for the phase purity.
The selected samples were subsequently subject to a systematic optimization of the
nanocrystallization conditions. This resulted in samples with a microstructure consisting of
small nanocrystallites and much improved conductivity. The highest value was observed
for the VFF composition and was equal to 6 × 10−4 S/cm. The electrical conductivity of the
other nanocrystalline samples reached 5.6 × 10−7 S/cm (FFF) and 6.7 × 10−5 S/cm (VFM).
In all cases, the conductivity exhibited a predominant electronic nature. In these mixed
conductors, the ionic conduction must have been lower by at least an order of magnitude
and therefore not observed in the impedance spectroscopy measurements. This is, however,
also important for electrochemical performance in NIBs. Therefore, the electrochemical
properties of these materials will be studied in the near future.

Author Contributions: Conceptualization, funding acquisition, supervision, and methodology,

T.K.P.; investigation, M.N. and M.J.S., visualization, M.N. and T.K.P., writing—original draft prepara-
tion, M.N. and T.K.P. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by POB Energy of Warsaw University of Technology within the
Excellence Initiative: Research University (IDUB) program.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data sharing not applicable.
Acknowledgments: We are grateful to Jan Mizeracki from the Institute of High Pressure Physics,
Polish Academy of Sciences, for providing us with the SEM images.
Conflicts of Interest: The authors declare no conflict of interest.

Abbreviations
The following abbreviations are used in this manuscript:
XRD X-ray Diffractometry
DTA Differential Thermal Analysis
IS Impedance Spectroscopy
SEM Scanning Electron Microscopy
EDS Energy Dispersive Spectroscopy

References
1. Damour, M.A. Sur un nouveau phosphate de fer, de manganèse et de soude, l’Alluaudite, trouvé dans le département de la
Haute-Vienne. Ann. Des Mines 1848, 13, 341–350.
2. Fisher, D.J. Alluaudite. Am. Mineral. 1955, 40, 1100–1109.
3. Moore, P.B. Crystal chemistry of the alluaudite structure type: Contribution to the paragenesis of pegmatite phosphate giant
crystals. Am. Mineral. 1971, 56, 1955–1975.
4. Trad, K.; Carlier, D.; Croguennec, L.; Wattiaux, A.; Amara, M.B.; Delmas, C. Structural Study of the Li0.5 Na0.5 MnFe2 ( PO4 )3 and
Li0.75 Na0.25 MnFe2 ( PO4 )3 Alluaudite Phases and Their Electrochemical Properties As Positive Electrodes in Lithium Batteries.
Inorg. Chem. 2010, 49, 10378–10389. [CrossRef]
5. Hatert, F.; Keller, P.; Lissner, F.; Antenucci, D.; Fransolet, A.-M. First experimental evidence of alluaudite-like phosphates with
high Li-content: The ( Na1− x Li x ) MnFe2 ( PO4 )3 series (x = 0 to 1). Eur. J. Mineral. 2000, 12, 847–857. [CrossRef]
6. Richardson, T.J. Phosphate-stabilized lithium intercalation compounds. J. Power Sources 2003, 119–121, 262–265. [CrossRef]
Materials 2021, 14, 4997 15 of 15

7. Dwibedi, D.; Barpanda, P.; Yamada, A. Alluaudite Battery Cathodes. Small Methods 2020, 4, 2000051.
8. Wen, M.; Liu, X.; Zhao, Y.; Liu, S.; Liu, H.; Dong, Y.; Kuang, Q.; Fan, Q. Synthesis of alluaudite-type Na2 VFe2 ( PO4 )3 /C and its
electrochemical performance as cathode material for sodium ion battery. J. Solid State Electrochem. 2018, 22, 891–898.
9. Zhang, P.; Yang, K.; Song, L.; Feng, H.-J.; Gao, J. An alluaudite-type sodium ion battery cathode candidate Na2 Mn2 V ( PO4 )3 :
Crystal growth, preparation, structure and electrochemical properties. J. Alloys Compd. 2019, 783, 409–415. [CrossRef]
10. Walczak, K.; Kulka, A.; Molenda, J. Alluaudite-Na1.47 Fe3 ( PO4 )3 : Structural and electrochemical properties of potential cathode
material for Na ion Batteries. Solid State Sci. 2019, 87, 21–26. [CrossRef]
11. Huang, W.; Zhou, J.; Li, B.; An, L.; Cui, P.; Xia, W.; Song, L.; Xia, D.; Chu, W.; Wu, Z. A New Route Toward Improved Sodium Ion
Batteries: A Multifunctional Fluffy Na0.67 FePO4 /CNT Nanocactus. Small 2015, 11, 2170–2176. [CrossRef] [PubMed]
12. Kim, J.; Kim, H.; Lee, S.; Myung, S.-T. Development of a new alluaudite-based cathode material with high power and long
cyclability for application in Na ion batteries in real-life. J. Mater. Chem. 2017, 5, 22334. [CrossRef]
13. Liu, S.; Chen, L.; Zhao, Y.; Wen, M.; Lian, X. Structural and electrochemical properties of Na2 V Mn2 ( PO4 )3 /C as cathode materials
for sodium ion batteries. J. Electroanal. Chem. 2019, 832, 121–128. [CrossRef]
14. Pietrzak, T.K.; Wasiucionek, M.; Michalski, P.P.; Kaleta, A.; Garbarczyk, J.E. Highly conductive cathode materials for Li ion
batteries prepared by thermal nanocrystallization of selected oxide glasses. Mater. Sci. Eng. 2016, 213, 140–147. [CrossRef]
15. Pietrzak, T.K.; Wasiucionek, M.; Garbarczyk, J.E. Towards Higher Electric Conductivity and Wider Phase Stability Range via
Nanostructured Glass-Ceramics Processing. Nanomaterials 2021, 11, 1321. [CrossRef]
16. Pietrzak, T.K.; Kruk-Fura, P.E.; Mikołajczuk, P.J.; Garbarczyk, J.E. Syntheses and nanocrystallization of NaF—M2 O3 —P2 O5
NASICON-like phosphate glasses (M = V, Ti, Fe). Int. J. Appl. Glass Sci. 2020, 11, 87–96. [CrossRef]
17. Chamryga, A.E.; Nowagiel, M.; Pietrzak, T.K. Syntheses and nanocrystallization of Na2 O-M2 O3 -P2 O5 alluaudite-like phosphate
glasses (M = V, Fe, Mn). J. -Non-Cryst. Solids 2019, 526, 119721. [CrossRef]
18. Pietrzak, T.K.; Goł˛ebiewska, A.; Płachta, J.; Jarczewski, M.; Ryl, J.; Wasiucionek, M.; Garbarczyk, J.E. Photoluminescence of
partially reduced Eu2+ /Eu3+ active centers in a NaF-Al2 O3 -P2 O5 glassy matrix with tunable smooth spectra. J. Lumin. 2019, 208,
322–326. [CrossRef]
19. Pietrzak, T.K. Multi-device software for impedance spectroscopy measurements with stabilization in low and high temperature
ranges working under Linux environment. Ionics 2019, 25, 2445–2452. [CrossRef]
20. Hatert, F.; Rebbouh, L.; Hermann, R.P.; Fransolet, A.M.; Long, G.J.; Grandjean, F. Crystal chemistry of the hydrothermally
synthesized Na2(Mn1− x Fe2x+ )2 Fe3+ (PO4 )3 alluaudite-type solid solution. Am. Mineral. 2005, 90, 653–662. [CrossRef]
21. Pietrzak, T.K.; Michalski, P.P.; Wasiucionek, M.; Garbarczyk, J.E. Synthesis of nanostructured Li3 Me2 (PO4 )2 F3 glass-ceramics
(Me = V, Fe, Ti). Solid State Ionics 2016, 288, 193–198. [CrossRef]
22. Pietrzak, T.K.; Zajkowska, W.K.; Wasiucionek, M.; Garbarczyk, J.E. Observation of the metal-insulator transition of VO2 in glasses
and nanomaterials of MV2 O5 -P2 O5 system (M = Li, Na, Mg). Solid State Ionics 2018, 322, 11–17. [CrossRef]
23. Pietrzak, T.K.; Garbarczyk, J.E.; Gorzkowska, I.; Wasiucionek, M.; Nowiński, J.L.; Gierlotka, S.; Jóźwiak, P. Electrical properties vs.
microstructure of nanocrystallized V2 O5 -P2 O5 glasses. J. Power Sources 2009, 194, 73–80. [CrossRef]