Solid State Ionics 378 (2022) 115888

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Solid State Ionics

journal homepage: www.elsevier.com/locate/ssi

Electrochemical stability of a NASICON solid electrolyte from the lithium

aluminum germanium phosphate (LAGP) series
Vinicius Martins Zallocco a, c, *, Jhonys Machado Freitas b, Nerilso Bocchi b,
Ana Candida Martins Rodrigues c
a
Graduate Program in Materials Science and Engineering, Federal University of São Carlos, 13565-905 São Carlos, SP, Brazil
b
Department of Chemistry, Federal University of São Carlos, C.P. 676, 13565-905 São Carlos, SP, Brazil
c
Center for Research, Technology and Education in Vitreous Materials, Department of Materials Engineering, Federal University of São Carlos, 13565-905 São Carlos,
SP, Brazil

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

Keywords: Li1.5Al0.5Ge1.5(PO4)3 glass-ceramics from NASICON series was synthesized using two different methods: single
LAGP heat treatment and glass sintering with concurrent crystallization of a pressed pellet, which exhibit ionic con­
NASICON, glass-ceramic ductivity of 4.15 × 10− 4 S cm− 1. The electrochemical stability window was investigated by cyclic voltammetry,
Electrochemical window
utilizing a mixture of powder solid electrolyte, carbon, and binder as the working electrode, resulting in the Li/
Solid electrolyte
LAGP/LAGP+C/Au configuration. As a comparison, conventional set-up for cyclic voltammetry was also used,
resulting in the Li/LAGP/Au setup. An electrochemical stability window around 3.5 V was found.

1. Introduction
In order to achieve the transformations needed for a more sustain­
able way of living, the United Nations created “The 2030 Agenda for
Sustainable Development” which includes 17 sustainable development
goals (SDGs) [1]. Renewable energy sources, electric cars, portable
electronic devices, and reducing our reliance on fossil fuel play an
important role in future development. In this scenario, energy storage
devices are a key technology to make this future reality.
Lithium batteries are desired because lithium is the lightest and most
electropositive metal available, making it a good candidate for anode
material yielding high-density batteries. However, the combination of Li
metal and liquid electrolyte cause dendrite growth, which leads to short-
circuiting of the cell and poses a serious risk of explosion due to the
flammability of liquid electrolytes [2]. The dendrite growth was cir­
cumvented by using carbonaceous anode intercalation compounds
because, in this case, lithium is used in its ionic state. This change led to
the most successful battery technology available nowadays: lithium-ion
battery [2]. Nevertheless, these batteries still utilize liquid flammable
electrolytes. Thus, the use of solid electrolytes has been proposed, and
all-solid-state batteries (ASSB) are now the subject of intense research
[3–6].
To fulfill all-solid-state battery requirements, much effort has been
made to study and develop new inorganic solid electrolytes and over­
come challenges that hinder the development of these batteries, for
instance high internal resistance [7,8]. Because the solid-solid contact
between electrodes and electrolytes exhibits high resistance, which is
detrimental to the battery capacity, several studies have focused on
reducing the resistance at the interface through different strategies
[9–14]. Although the interfacial contact resistance plays an important
role, the spontaneous chemical reaction between electrodes and elec­
trolyte may suggest chemical incompatibility [15–18], i.e., the electrode
potentials may be outside of the electrolyte's stability window, revealing
another variable other than solid-solid contact to add up on the total
interfacial resistance.
Solid-state electrolytes are considered an alternative to replace liquid
electrolytes in both lithium and lithium-ion batteries because their non-
flammable nature protects against explosion if the cell is eventually
short-circuited, thus being inherently safer than organic flammable
liquid electrolytes. Besides the advantage of not being flammable,
another advantage would be the wide electrochemical stability window,
which has been proven by some experimental results [19–22].
However, those experimental results contradict theoretical studies
based on a computational thermodynamic assessment of the phase's
stability as a function of the applied potential [23,24]. As stated by Zhu
et al. [23], the origin of the outstanding electrochemical stability

* Corresponding author.
E-mail address: vini.zallocco@gmail.com (V.M. Zallocco).

https://doi.org/10.1016/j.ssi.2022.115888
Received 23 October 2021; Received in revised form 16 February 2022; Accepted 22 February 2022
Available online 16 March 2022
0167-2738/© 2022 Elsevier B.V. All rights reserved.
V.M. Zallocco et al. Solid State Ionics 378 (2022) 115888

window observed in many experiments is originated by a kinetic po­ in batches of 15 g. After weighing, the reagents were previously mixed
larization, which requires an overpotential to detect the currents related for 3 h in a rotary mill jar with alumina balls. The homogenized material
to the sluggish rate of solid-state decomposition reactions, and the was transferred to an alumina crucible and calcinated at 700 ◦ C for 1 h to
passivation mechanism that forms a SEI (Solid Electrolyte Interface) release volatiles such as ammonia, water, and carbon dioxide from the
[23]. Thus, to investigate a more realistic electrochemical stability starting materials. The mixture was then melted at 1250 ◦ C for 30 min.
window of solid electrolytes, an improved contact area between the The melt was splat-cooled between two stainless steel plates to increase
solid electrolyte and electronic conductive material is ideal for ampli­ the glass cooling rate. The use of alumina crucible was already reported
fying the redox currents from the electrolyte decomposition [25,26], by other authors [19,37], and no extra Al was detected by ICP-OES and
since the sluggish kinetics of solid-state reaction yields tiny currents. ICP-AES in the LAGP stoichiometry. Glass transition (Tg) and crystalli­
Having said that, Han et al. [25] proposed a modified set-up for cyclic zation (Tx) temperatures were determined by Differential Scanning
voltammetry, in which the solid electrolyte is mixed with carbon pow­ Calorimetry using a DSC-Netzsch 404, at 10 ◦ C min− 1, in a platinum
der, leading to the configuration: Li/Solid Electrolyte/powder mixture crucible with a lid.
of Solid Electrolyte and Carbon/Inert Metal (e.g., Au or Pt). Using this After glass preparation, glass crystallization was achieved through
configuration, they analyzed two well-known solid electrolytes as two different procedures. Li1.5Al0.5Ge1.5(PO4)3 glass-ceramic was first
models: Li10GeP2S12 (LGPS) and Li7La3Zr2O12 (LLZO). prepared by single heat treatment for crystallization of the bulk glass. In
Several solid-state electrolytes are proposed due to their high ionic the second procedure, to improve sample homogeneity, glass-ceramics
conductivity [27–30]. Among them, NASICON (Na Superionic were obtained by sintering and concurrent crystallization of the glass
Conductor) for example, lithium‑aluminum‑titanium-phosphates powder. For the single heat treatment, the bulk glass was crystallized at
(LATP) and lithium‑aluminum‑germanium-phosphates (LAGP) have 800 ◦ C for 3 h in a vertical electric furnace having a precision of ±1 ◦ C.
been widely studied given not only their relatively high ionic conduc­ After the heating treatment, the sample was removed from the furnace
tivity but also their stability in air and water [31–33]. Thus, the and left to cool down at ambient temperature (~25 ◦ C). For the sintering
NASICON-structured Li1.5Al0.5Ge1.5(PO4)3 is seen as a promising solid- and crystallization method, the glass was grounded in agate mortar in
state electrolyte. Moreover, some studies have investigated the elec­ particles between 45 and 65 μm. Then, two different processing condi­
trochemical stability window of LAGP. Table 1 summarizes the value for tions were used. In the first case, the glass powder was isostatically cold
the cathodic and anodic limits of LAGP published in the literature by pressed at 267 MPa and was heated from room temperature to 571 ◦ C at
different authors. 5 K min− 1 for 30 min to allow sintering to occur. After that, the sample
As seen in Table 1, there is a notorious discrepancy between exper­ was heated until 800 ◦ C at 40 K min− 1 for 3 h to allow crystallization.
imental and theoretical results concerning the anodic and cathodic Then the furnace was turned down for cooling. In a second procedure,
limits for the decomposition of LAGP, as well as a disagreement between 10 wt% of dextrin was added to the glass powder, the pellet was then
the experimental results. Given that, this work aims to determine the isostatically cold pressed at 267 MPa and then heated up to 200 ◦ C (5 K
electrochemical stability window for the LAGP using a composite min− 1), held for 2 h to release volatiles from dextrin, then heated to
working electrode, where carbon and solid electrolyte powders are 571 ◦ C (5 K min− 1) for sintering and finally to 800 ◦ C (40 K min− 1) for 3
mixed to increase the contact area between the solid electrolyte and the h to allow crystallization to occur. The furnace was turned down for
electronic conductive material. The conventional cyclic voltammetry, cooling. The sintering temperature of 571 ◦ C was determined by optical
Li/LAGP/Au, was also utilized as a comparison. To optimize the ionic dilatometer (Misura HSM-ODHT 1600–8002, TA instruments), using a
conductivity of the solid electrolyte, we obtained LAGP glass-ceramic in green body of 3.2 mm in diameter and 4.5 mm height pressed at 25 MPa
different ways, by direct crystallization of the glass and by sintering the at a heating rate of 10 ◦ C min− 1.
glassy LAGP powder with and without a binder (dextrin) to obtain The obtained crystalline phase was determined by X-ray diffraction
pellets. (Rigaku Ultima IV X-ray diffractometer) between 10◦ to 80◦ 2θ angle, at
40 kV and 20 mA, using the step scan procedure with an integration time
2. Experimental of 3 s and a step size of 0.015◦ .
The ionic conductivity of the pellet was determined by complex
Li1.5Al0.5Ge1.5(PO4)3 solid electrolyte was prepared through the impedance spectroscopy, (Novocontrol Alpha-A High Performance
glass-ceramic route [37]. The precursor glass was obtained by melting Frequency Analyzer) in a two- point cell in air, at a frequency range of
stoichiometric amounts of Li2CO3 (Dinâmica, 99.00%), GeO2 (Alfa 107–101 Hz at 308 K with voltage amplitude of 300 mV. The pellets were
Aesar, 99.99%), Al2O3 (Aldrich, 99.00%) and NH4H2PO4 (Aldrich, 98%) polished to ensure two parallel surfaces. Before measurements, gold
electrodes were sputtered on both parallel sides using Quorum Q150R
ES equipment.
Table 1
The electrochemical analyses were performed using two different
Values for reduction and oxidation potentials for NASICON solid electrolyte
LAGP.
cells. The first one was similar to that proposed by Han et al. [25], in
which its components are set up as Li/LAGP/LAGP+C/Au. The com­
Cathodic Anodic Analysis type Experimental set-up Reference
posite electrode of LAGP+C/Au was prepared by mixing LAGP powder
Limit (V vs Limit (V vs or theoretical
Li/Li+) Li/Li+) approach and acetylene black (Vulcan XC 72-6P 2800, Cabot) in the mass pro­
portion of 50:50 besides 10 wt% of polyvinylidene fluoride (PVDF,
0 6* Experimental CV – Li/LAGP/SS** [19]
0.8 7* Experimental CV – Li/LAGP/Ag [20]
Aldrich) and a sufficient volume of N-methyl-2-pyrrolidone (NMP, Acros
0.9 4* Experimental CV – Li/LAGP/Au [34] Organic) to form a viscous paste. This latter was then deposited on one
1.5 6* Experimental CV – Li/LAGP/Au [35] side of the LAGP pellets and dried overnight at 120 ◦ C. Afterwards, gold
0.2 5.3 Experimental CV – three [36] was sputtered on the top of the paste to improve electrical contact. Then,
electrodes setup
a Teflon® swagelok-type cell was assembled inside a glove box
1.85 4.9 Experimental CV – composite [26]
working electrode (MBraun, model LabMaster) under an argon atmosphere, with humidity
2.70 4.27 Theoretical FPC*** [23] control and at room temperature (~25 ◦ C). Finally, metallic lithium, the
* LAGP pellet and the composite electrode were placed inside this
Represents the maximum potential applied to the experiment and no
oxidation current was detected, indicating anodic stability at least up to the swagelok-type cell to result in the Li/LAGP/LAGP+C/Au setup. The
indicated potential. CV = Cyclic Voltammetry. second cell was assembled similarly to the first one but using a semi-
**
SS – Stainless Steel. blocking electrode thus resulting in Li/LAGP/Au configuration.
***
FPC = First Principle Calculations. All cyclic voltammetries (CV) were performed using an Autolab

2
V.M. Zallocco et al. Solid State Ionics 378 (2022) 115888

PGSTAT-204 potentiostat/galvanostat (Metrohm Autolab) controlled by

the NOVA 2.1 software. Metallic lithium was used as counter and
reference electrodes. All potential values were always referred to as the
Li/Li+ reference electrode. The working electrodes were varied ac­
cording to the assemblies as described previously. A scan rate of 0.1 mV
s− 1 in various potential ranges was used in the CV measurements.

3. Results and discussion

3.1. Characterization of precursor glass and glass-ceramic

The melted glass is transparent and colorless. The DSC (Differential

Scanning Calorimetry) curve of bulk glass obtained at a heating rate of
10 K min− 1 is shown in Fig 1. As can be seen, the glass transition and
crystallization temperatures are comparable to results previously re­
Fig. 2. Retraction of LAGP glass as a function of the temperature.
ported in the literature [19,37–39], which indicates that the target glass
was successfully synthesized.
One of the methods adopted to obtain the glass-ceramic pellet
involved the sintering of glass powder and concurrent crystallization. In
this case, the sintering temperature was defined using an optical dila­
tometer test. Fig 2 exhibits the sample's retraction as a function of the
temperature. In this figure, the sintering temperature is defined by the
equipment software at the beginning of the retraction curve, i.e., at
around 5% retraction. The beginning of the retraction curve indicates
the beginning of viscous flow. For this reason, it is important to sinter
the pellet at this temperature, to minimize the crystallization effect
while sintering. The inset of Fig 2 shows a picture of the body before and
after sintering.
The next step in the glass-ceramic route is the controlled crystalli­
zation of the precursor glass, to yield a glass-ceramic with a micro­
structure aimed to optimize ionic conductivity, that is, favor grain
growth over nucleation. In fact, increased grain size reduces the inter­
facial area between grain boundaries, thus reducing the intergranular
resistance [37]. As described in the Experimental section, two different
procedures were adopted to obtain the glass-ceramic. The first one
consisted of the direct crystallization of a bulk glass sample (geometric
factor of 0.394 cm− 1) through single heat treatment (SHT). The second
procedure consisted of the sintering and crystallization of a pressed glass
powder pellet. A pellet was prepared with a sintering additive (dextrin)
aiming to improve the mechanical strength of the green body; and
another tablet was prepared without the dextrin for the sake of com­ Fig. 3. Complex impedance of LAGP bulk glass-ceramics, sintered pellet
without dextrin and with dextrin as indicated in the legend. Inset a) shows
parison. The sintered pellet without dextrin exhibited microcracks and
imperfections on the LAGP pellet sintered and crystallized without dextrin and
deformation as shown in inset a) of Fig 3.
b) shows the pellet with optimized processing conditions using dextrin.

The sintered pellet with dextrin (1.020 cm diameter and 0.079 cm

thick), without dextrin (diameter of 1.070 cm and 0.089 cm thick) and
bulk glass crystallized through SHT were then characterized by complex
impedance spectroscopy as shown in Fig 3. It is worth noting that the
maximum order of magnitude (10− 4 S cm− 1) for conductivity was ach­
ieved for this system. This value is also comparable with data published
in the literature [19,38]. As demonstrated, the sintered sample without
sintering additive, which exhibited cracks, has the lowest ionic con­
ductivity of the three samples, leading to ionic conduction equal to 1.76
× 10− 4 S cm-1. This relativity low value is expected as defects such as
pores and cracks are known to decrease the ionic conductivity of ma­
terials. On the other hand, it is worth mentioning that the sample sin­
tered with dextrin showed a higher ionic conductivity at room
temperature (4.15 × 10− 4 S cm-1), as compared to that obtained via SHT
(2.77 × 10− 4 S cm-1).
A sintered pellet was grounded to verify the obtained crystalline
phases. X-ray diffraction spectra of the glass-ceramic is shown in Fig 4.
The peaks match the NASICON LiGe2(PO4)3 - PDF: 80–1924. According
to the Rietveld refinement (Software GSAS-II), a percentage of 3.4% of
the AlPO4 (space group C 2 2 21) phase was formed in the LAGP pellet.
Fig. 1. DSC curve for Li1.5Al0.5Ge1.5(PO4)3 bulk glass at heating rate of 10
Furthermore, a CIF file of x = 0.48 was used for the refinement of
K min− 1.

3
V.M. Zallocco et al.
Fig. 4. XRD pattern of grounded pellet of LAGP and Rietveld refinement.
Li1+xAlxGe2-x(PO4)3), yielding a theoretical density of 3.42 g cm− 3. The
Archimedes principle was used to calculate the experimental density of
four different samples, resulting in an average relative density of 80%.
Since the porosity of the sample is relatively high, it could be argued
that dendrites may grow though the pores [40]. However, dendrites are
likely to grow under high current densities, i.e., tens of mA cm-2 [41,42].
In contrast, low current densities around tens of μA cm-2 were measured
in our experiments. In addition, LAGP porosity should not interfere in
the cathodic and anodic limit as electrochemical window depends
markedly on the nature of electrolyte and electrodes [43].
3.2. Electrochemical measurements
Fig 5 shows cyclic voltammetry profiles obtained for the LAGP+C/
Au electrode in the cell assembled with the Li/LAGP/LAGP+C/Au setup.
While the first cycle was performed in the potential range of 0–6 V, the
second and third cycles were carried out increasing the upper limit
potential to 7 V. Analyzing the potential scan of the first cycle from OCP
Fig. 5. Cyclic voltammetries obtained at a scan rate of 0.1 mV s− 1 for the first
cell: Li/LAGP/LAGP+C/Au. The inset is a picture of the process step by step,
where the composite electrode was deposited on an LAGP pellet and gold was
sputtered on the top of the composite electrode after drying overnight. (For
interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)
4
Solid State Ionics 378 (2022) 115888
toward 0 V, the onset of a reduction process at 1.70 V is clearly observed.
This can possibly be associated with the reduction of Ge4+ to Gex+ (0 ≤
x ≤ 3) on the surface of the LAGP+C/Au electrode in contact with the
LAGP solid electrolyte. This reduction process is in agreement with the
works of Hartmann et al. [44] and Chung and Kang [45] who pointed
out that germanium undergoes a reduction when in contact with
lithium, as well as a distribution of oxidation states of germanium across
the interphase depth formed upon contact. Although the present work is
slightly different from those authors, as we are investigating a composite
material (LAGP+C) in contact with LAGP, it is expected that the LAGP of
the electrode becomes unstable as the potential values are decreased.
Therefore, Ge4+ on the surface of the LAGP+C/Au electrode possibly
starts to reduce to Ge3+ at 1.70 V initially forming an LAGP with a
modified stoichiometry [45] before decomposing in other phases. As the
potential decreases beyond 1.70 V, Ge3+ can reduce to even lower
oxidation states leading to the formation of other different germanium
compounds, as well as distinct phases containing the other LAGP com­
ponents such as Li, Al and P. According to the literature [23,45,46],
possible LAGP decomposition products can be formed in the potential
range of 1.70–0 V are Li4P2O7, GeO2, AlPO4, LiPO3, Li9Al4, Ge, Li–Ge
alloys, Li3P, Li2O2 and Li2O. Applying experimental techniques to detect
these possible phases as a function of the applied potential is a challenge
and should be the subject of a future study. From 0 V to higher poten­
tials, the cathodic currents of the reverse scan intersect and cross over
the cathodic currents of the forward scan only for the second and third
cycles. This behavior is associated to a nucleation process [47], which
occurs only after the reduction processes at ~4.26 V and ~ 2.80 V are
revealed.
Regarding the anodic potential scans in Fig 5, oxidation processes are
observed at a potential range of 0.82–1.50 V in all three cycles, which
can be related to phase oxidation such as Ge and Li–Ge alloys. The onset
of another oxidation process is clearly observed at 5.25 V for all cycles.
This process can be attributed to the oxidation of LAGP reduction
products formed at lower potential values in the previous cathodic scan,
such as oxides and phosphates as previously mentioned. At these higher
potential values, the spectrum of phases that can be formed are O2, Ge5O
(PO4)6, AlPO4, GeP2O7 and GeO2 [23,24]. Once again, the application of
experimental techniques to detect these possible phases as a function of
the applied potential is a challenge and should be the subject of a future
study. Oxidation of LAGP was also detected and will be discussed below
Fig. 6. Cyclic voltammetries obtained at a scan rate of 0.1 mV s− 1 for the first
cell: Li/LAGP/LAGP+C/Au. The inset represents the first two cycles scanned in
a potential range of 0–7 V.
V.M. Zallocco et al.
based on the results shown in Fig. 6.
From the second and third cycles, it is interesting to note that the
cathodic potential scans in Fig 5 reveal two other reduction processes at
~4.26 V and ~ 2.80 V, as well as the disappearance of that reduction
process observed in the first cycle after 1.70 V. The absence of the
reduction process at 1.70 V in the second and third cycles, added to the
fact that there is no oxidation peak related to this reduction process,
indicates the irreversibility of the LAGP phase decomposition. As the
other two reduction processes seem to be associated with the oxidation's
products formed at higher potential values in the previous anodic po­
tential scan, a new set of cyclic voltammetries for the LAGP+C/Au
electrode was performed starting from OCP toward 2 V, and then
sweeping back toward 7 V, as shown in Fig. 6 and its inset for the first
two cycles. In this figure, the third and fourth cycles were carried out
from OCP toward 0 V, and then swept back toward 7 V. In the first two
cycles, only an oxidation process starting at ~5.25 V is observed in the
anodic potential scan, which can be undoubtedly attributed to the LAGP
oxidation process as this scan was performed before decomposing the
electrode material at lower potential values, i.e.: 1.70 V, as previously
described. No reduction processes are evident in the subsequent
cathodic potential scans of the first two cycles. These observations
indicate the irreversibility of the LAGP oxidation process and, therefore,
can be attributed to the oxidation of oxygen anion in the LAGP crystal
lattice as mentioned before. On the other hand, the absence of reduction
processes in the first two cycles together with the appearance of two
reduction processes in the third and fourth cycles, as well as the higher
oxidation current observed at ~5.50 V confirm that the reduction pro­
cesses at ~4.26 V and ~ 2.80 V are related to the oxidation products
formed at high potential values. However, these reduction processes are
revealed only after the previous cathodic scan reached the potential
value of 0 V.
As a way of comparison, Fig 7 shows cyclic voltammetric profiles
obtained for the setup Li/LAGP/Au, in which Au acts as working elec­
trode in the setup assembled as Li/LAGP/Au. The cycles were carried out
in a potential range of 0–7 V, starting from OCP toward 0 V and then
sweeping back to 7 V. At first glance, the onset of a reduction process at
~0.80 V is clearly observed which was attributed to the LAGP reduction
by Feng et al. [20]. However, the inset shows a reduction current arising
at ~1.95 V which is hidden in the main voltammograms. It is worth
noting that the Li/LAGP/Au cell exhibits, at a potential range of 0–1 V,
values of a reduction current about twelve times higher than those
registered for the Li/LAGP/LAGP+C/Au cell. However, a magnification
Fig. 7. Cyclic voltammetries obtained at a scan rate of 0.1 mV s− 1 for the cell:
Li/LAGP/Au. The inset is a zoom of the voltammograms between − 6 and 6 μA.
5
Solid State Ionics 378 (2022) 115888
in the region of interest, as illustrated by the inset in Fig. 7, reveals the
currents related to the LAGP reduction process starting at ~1.95 V vs Li/
Li+. Regarding the anodic potential scans, oxidation processes are also
observed at a potential range of 0.45–1.50 V in all three cycles, which
can also be related to the oxidation of Ge-containing phases, and the
formation of Li–Ge alloys. In the same way as for the Li/LAGP/
LAGP+C/Au cell, an onset of oxidation processes is clearly observed at
~5.25 V for all cycles (see inset in Fig 7). These processes are attributed
to the oxidation of the products formed at lower potential values, during
the reduction of LAGP in the previous cathodic scan, such as oxides and
phosphates described before.
In order to detect LAGP oxidation with the cell configuration Li/
LAGP/Au, another set of cyclic voltammetries was performed starting
from OCP toward higher potential values, as shown in Fig 8. In the first
cycle, an oxidation process is clearly observed at ~5.42 V vs Li/Li+,
which is attributed to the oxidation of oxygen anions (O2− ) present in
the crystal lattice of LAGP, as predicted by other authors [23,24].
Regarding the cathodic scan, the onset of a reduction process at ~1.67 V
vs Li/Li+ is observed in the first cycle, which can be attributed to the
LAGP decomposition, although its potential is shifted when compared
with that in Fig 7. This shift occurred because the previous anodic scan
reached the anodic potential limit of 7 V, thus changing the surface of
the electrode material and, consequently, its potential in the subsequent
cathodic scan. In the second cycle, the oxidation process detected at
~5.25 V vs Li/Li+ corroborates previous results, where these currents
are attributed to the oxidation of oxygen anions present in oxides and
phosphates formed at lower potential values in the previous cathodic
scan. Furthermore, for the second cycle, reduction processes at ~3.00 V
vs Li/Li+ can be observed, which have already previously been observed
and discussed, having been attributed to reductions of oxidation prod­
ucts formed at high potential values, which are revealed only after the
previous cathodic scan reached the potential value of 0 V.
In both cell configurations, i.e., Li/LAGP/Au and Li/LAGP/LAGP+C/
Au, the reduction and oxidation currents of the LAGP detected are very
small (~1 μA) due to sluggish solid-state reaction kinetics. There was no
significant difference between the results of the two configurations. The
Li/LAGP/Au and Li/LAGP/LAGP+C/Au cell configurations reveal a
LAGP reduction process starting at ~1.95 V vs Li/Li+ and ~ 1.70 V vs Li/
Li+, respectively. On the other hand, these configurations revealed a
LAGP oxidation process starting at ~5.42 V vs Li/Li+ and ~ 5.25 V vs Li/
Li+, respectively. It is interesting to note that the potential values for
anodic and cathodic limits are shifted about 0.16 V toward higher po­
tentials for the Li/LAGP/Au when compared to the Li/LAGP/LAGP+C/
Au cell. However, an equal electrochemical window of ~3.5 V was
Fig. 8. Cyclic voltammetries obtained at a scan rate of 0.1 mV s− 1
for the
second cell: Li/LAGP/Au.
V.M. Zallocco et al.
detected for both cell configurations. In contrast, oxidation processes in
the potential range of 0.45–1.50 V vs Li/Li+ related to Li and Li–Ge
alloys are better observed for the Li/LAGP/Au cell configuration.
Based on the voltammetric observations described hereinbefore, a
schematic illustration (Fig 9) was made to clarify the processes occur­
ring at the interface of LAGP/composite electrode – (LAGP+C/Au) and
to bring together critical information related to the LAGP solid elec­
trolyte and its application on solid-state batteries. First, the image in­
dicates the electrochemical stability window of the solid electrolyte
LAGP, which is in the potential range of 1.70–5.25 V. Since this solid
electrolyte has high ionic conductivity (~10− 4 S cm− 1) and low elec­
tronic conductivity (~10− 9 S cm− 1) [20] and the composite electrode
LAGP+C/Au has low ionic conductivity, but high electronic conduc­
tivity due to the high amount of carbon added to it, charge carriers (Li+
and e− ) should be redistributed and concentrated at the interface under
a certain cathodic/anodic polarization. This interface is represented in
the zoom image at 1.70 V where germanium ions (Ge4+) start to be
reduced. Only germanium ions at this interface can combine with
electrons due to the low electronic conductivity of the LAGP phase,
which explains the low current values detected in the cathodic scans of
the voltammetric profiles; germanium ions away from the interface
LAGP/LAGP+C, and therefore in the LAGP bulk maintain their oxida­
tion state (Ge4+).
As the potential decreases beyond 1.70 V, the LAGP continues
decomposing, yielding an interphase properly called MCI (mix con­
ducting interphase) [44,49], as it has a substantial electronic conduc­
tivity [44,45] and is unable to passivate the interface. As a result, the
MCI grows continually into the LAGP bulk, thus altering its properties.
Composition and relative quantities of the formed MCI interphase
should vary as a potential function. For instance, the Li–Ge alloy could
only be formed at potential values lower than 0.4 V [46], therefore it is
expected that this phase will not be detected in a potential interval be­
tween 0.40 and 1.70 V, although LAGP has already been decomposed at
this range.
On the other hand, regarding the potential values higher than the
OCP, the LAGP becomes unstable at 5.25 V. Oxygen anions (O2− )
Fig. 9. Schematic illustration of the possible processes occurring at the LAGP/composite electrode interface in the Li/LAGP/LAGP+C/Au setup as a function of the
applied potential. MCI formation indicates that the interface is not stable.
6
Solid State Ionics 378 (2022) 115888
present in the crystal lattice of the LAGP phase oxidize yielding gas
oxygen [26], and consequently, lithium ions migrate toward the lithium
electrode (LAGP delithiation) to maintain electrical neutrality. As a
result, lithium-free phases are formed at higher potential values as
already pointed out previously. Finally, the experimental identification
of phases formed at both low and high potentials could bring insights to
the MIC formation mechanism, which is not fully understood, and
should be the focus of future studies.
A theoretical study based on a thermodynamic assessment of phases
pointed out an electrochemical stability window of LAGP between 2.70
and 4.27 V [23]. The difference between the experimental and theo­
retical analysis is most likely originated by kinetic polarization, and thus
an overpotential is required in the experimental analysis to detect
decomposition currents due to a sluggish rate of solid-state reactions.
Even though the experimental results indicate an electrochemical sta­
bility window in the range of 1.70–5.25 V (or 1.95–5.42 V), it is
important to highlight that the LAGP decomposition is still thermody­
namically feasible at this potential range, leading to slow deterioration
over an extended period of time [23]. Therefore, solid-state batteries
operating in that experimental potential range are highly likely to in­
crease their internal resistance over time.
4. Conclusion
In summary, LAGP glass-ceramic pellets were successfully synthe­
sized throughout sintering and crystallization methods with a better
ionic conductivity compared to single heat treatment of the bulk glass.
Sinter-crystallized LAGP exhibited an ionic conductivity of 4.15 × 10− 4
S cm− 1, with a relative porosity of 80% and 3.4% of AlPO4 as a sec­
ondary phase. The electrochemical measurements resulted in cathodic
and anodic potential limits of 1.70 V and 5.25 V vs. Li/Li+, respectively,
revealing an electrochemical stability window around 3.5 V, which is far
from that predicted theoretically (1.57 V). This difference can be
attributed to the kinetic polarization caused by the sluggish kinetics of
solid-state reaction that requires an overpotential to be detected.
V.M. Zallocco et al.
CRediT authorship contribution statement
MVZ: Conceptualization, Data Acquisition, Formal Analysis, Inves­
tigation, Data Curation, Original Draft.JMF: Methodology, Data Acqui­
sition, Formal Analysis, Software.NB: Methodology, Formal analysis,
Resources, Writing - Review & Editing, Supervision.ACMR: Conceptu­
alization, Formal Analysis, Resources, Writing - Review & Editing,
Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The authors acknowledge the São Paulo Research Foundation
(FAPESP) for its financial support, under CEPID Process no.2013/
07793-6. VNZ and NB acknowledges Brazil's National Council for Sci­
entific and Technological Development (CNPq) for scholarships granted
under project processes nos. 138854/2019-0 and 309900/2019-0,
respectively. Prof. Francisco Carlos Serbena, from State University Ponta
Grossa - Brazil, is deeply acknowledged for helpful discussion on the
Rietveld analysis. This study was financed in part by the Coordenação de
Aperfeiçoamento de Pessoal de Nível Superior - Brasil (CAPES) - Finance
Code 001.
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