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Influence of Cobalt Introduction on the Phase Equilibrium and

Sintering Behavior of Lithium-Ion Conductor Li1.3Al0.3Ti1.7(PO4)3
Shogo Miyoshi,* Yoshihiko Nishihara, and Kazunori Takada

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ABSTRACT: After the reported high sinterability of a NASICON-type lithium-ion

conducting electrolyte Li1.3Al0.3Ti1.7(PO4)3 (LATP) in contact with LiCoPO4, which
was found in the studies on a co-firing process for an all-solid-state battery, the present
Downloaded via 190.43.228.173 on September 27, 2022 at 07:48:50 (UTC).

authors have investigated the influence of cobalt introduction on the sintering behavior
of LATP as well as the phase equilibrium. It was indicated that 1−2 mol % cobalt is
allowed to be a substitute for the constituent cation in the NASICON structure. The
slightly Co-doped LATP phase shows a clearly high sinterability compared with a
normal LATP, with the relative density approaching 80% after firing at 800 °C. A
further increase in the cobalt content results in the separation of the excess cobalt as
LiCoPO4 together with the other second phases. In the case of the nominal
composition such that titanium in LATP is partly replaced by cobalt
(Li1.3+2xAl0.3CoxTi1.7‑x(PO4)3), a remarkable densification behavior was observed; e.g.,
a relative density approximating 100% was attained after firing at 800 °C for x = 0.1.
The significantly high sinterability is ascribed to a low melting point compound LiPO3, which forms as the second phase together
with LiCoPO4 and LiTiO(PO4).
KEYWORDS: Li1.3Al0.3Ti1.7(PO4)3, NASICON, all-solid-state battery, electrolyte, cobalt, low-temperature sintering

1. INTRODUCTION titanium-based ones are capable of superior conductivity.3−5

In response to the demand for energy storage technology with
higher reliability and energy density, research and development
of all-solid-state lithium-ion batteries are increasing in activity.
The forthcoming implementation of the solid-state batteries
based on sulfide electrolytes is followed by serious effort
toward realization of the oxide-based solid batteries, which are
expected to offer further reliability. Ensuring sufficient ionic
conductivity of the solid electrolyte, which is essential to
materialize the solid-state batteries, requires high spatial
density of the material as well as ion-conductive connection
between the grains. For oxide-based electrolyte materials, such
properties are typically attained via a sintering phenomenon
through a high-temperature firing process. Considering an
industrial co-firing process of an electrolyte and electrode
active material, lowering the process temperature is beneficial
for suppressing the formation of undesired products from the
reaction between them. Low-temperature sintering is also
desirable for the reduction of processing costs. Thus, lowering
the sintering temperature is the key technology for the
realization of oxide-based solid state batteries.
A series of NASICON-type lithium-ion conductors,
LiM2(PO4)3, is characterized by a three-dimensional frame-
work structure composed of corner-shared PO4 tetrahedra and
MO6 octahedra,1 which offers excellent chemical stability as
well as high lithium-ion conductivity.2 In particular, the
© 2022 The Authors. Published by
American Chemical Society
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Compared with undoped LiTi2(PO4)3, the lithium-ion
conductivity is significantly increased by partial substitution
of trivalent cations for Ti4+, and the highest conductivity is
att aine d with an alu minum-doped composit ion,
Li1.3Al0.3Ti1.7(PO4)3 (LATP); the bulk (grain-interior) con-
ductivity reaches 3 × 10−3 S·cm−1 as reported by Aono et al.6
The total lithium-ion conductivity of the ceramics, which is
affected by both the grain-interior and grain-boundary
resistance, is also as high as 7 × 10−4 S·cm−1.6 On the other
hand, the values of the total conductivity in the other reports,
most of which were evaluated for materials with a bulk
conductivity comparable to their value, are somewhat
dispersed in the order of 10−6−10−4 S·cm−1.5,7−10 The total
conductivity is thus limited by the resistance originating from
the grain boundary, and its extent significantly depends on the
preparation route, processing parameters, and probably
knowledge and skillfulness. This situation tells us the
Received: April 1, 2022
Accepted: May 13, 2022
Published: May 25, 2022
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ACS Applied Energy Materials
Figure 1. Densification behavior of series (A) (Li1.3+2xAl0.3CoxTi1.7‑x(PO4)3) specimens. (a) Relative density of the sintered specimens as a function
of firing temperature. (b) Linear dimensional change of the as-pressed LATP and x = 0.1 specimen during the simulated firing process. The heating
and isothermal step are separately displayed as a function of temperature and time, respectively.
importance of the science and technology of processes for
fabricating lithium-ion conducting ceramics.
There have been studies on solid batteries which employ
LATP-based electrolytes in combination with olivine-type
LiCoPO4 (LCP) as the active material of the positive
electrode.11−14 In those studies, the electrolyte and positive
electrode layers were fabricated via a co-firing process, showing
the electrochemical activity of the resulting cells. In addition,
there have been reports showing that, after the co-firing or
postannealing process of the electrolyte−electrode mixture or
layered structure, both phases remain.11,14−17 On the other
hand, significant diffusion of cobalt from LCP into the LATP
layer was acknowledged after co-firing11 and postannealing of a
LCP thin film deposited on a LATP substrate.18 Probably
related to the cobalt diffusion, the LATP layer was found to be
remarkably densified in the vicinity of the interface with the
LCP layer, while the other side of the LATP layer remained
porous.11 In addition, during the course of the study on the
chemical compatibility between LATP and LCP,15 it was
observed that the LATP region in the LATP-LCP mixed
ceramics is fully densified at a firing temperature where the
ceramics from the identical LATP powder alone show
negligible densification. For establishing the science of ceramic
processes for lithium-ion conducting oxides, it would be
valuable to understand the enhanced sinterability of LATP
with the introduction of cobalt and/or coexistence of a cobalt-
including phase.
In the present study, the influence of cobalt on the sintering
property of LATP has been systematically examined with the
phase relation clarified. Since a certain extent of cobalt
dissolved into the LATP structure is anticipated, the examined
compositions have been set so as to satisfy the stoichiometry of
the NASICON structure. On the other hand, it is difficult to
predict which crystallographic site the substituted cobalt atoms
occupy, the lithium site or titanium site. Therefore, the authors
examined two series of compositions on the suppositions of
the cobalt atoms occupying either the lithium site or titanium
site, which in turn provides an examination of both lithium-
rich and titanium-rich composition series with totally different
phase equilibria. The variation of the densification behavior
depending on the series of compositions as well as the content
of introduced cobalt will be discussed on the basis of phase
analyses.
2. EXPERIMENTAL SECTION
The nominal compositions of the examined starting materials are
Li1.3+2xAl0.3CoxTi1.7‑x(PO4)3 (series (A)) and
Li1.3−2yCoyAl0.3Ti1.7(PO4)3 (series (B)). Series (A) is the composition
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such that titanium in Li1.3Al0.3Ti1.7(PO4)3 (LATP) is partly replaced
by cobalt, and the resultant decrease in positive valence charge is
compensated by increasing lithium under the supposition of divalence
of the Co ion. In series (B), on the other hand, part of lithium in
LATP is replaced by cobalt in a manner assuming the divalence of
cobalt and lithium is doubly decreased upon an increase of cobalt.
Thus, both composition series satisfy the stoichiometry of the
NASICON-type structure on the respective assumptions of Co ion
occupation of the Ti site and Li site. It is noted that the
crystallographic site relevant to cobalt atoms is considered as identical
in the NASICON structure regardless of the nominal composition,
series (A) or (B). It is also noted that as will be shown later, the
solubility range of cobalt in the LATP phase is quite limited, and the
secondary phase(s) are totally different between the former and latter
compositions, which is closely related to the difference in the sintering
behavior.
The powders of nominal composition of Li1.3Al0.3Ti1.7(PO4)3,
Li1.3+2xAl0.3CoxTi1.7‑x(PO4)3 (x = 0.01, 0.02, 0.05, 0.1, 0.2, 0.3), and
Li1.3−2yCoyAl0.3Ti1.7(PO4)3 (y = 0.01, 0.02, 0.05, 0.1, 0.2, 0.3), which
were prepared via a solid-state reaction route, were purchased from
TOSHIMA Manufacturing Co., Ltd. The composition of each powder
was controlled to be exactly same as the nominal composition, that is,
no addition of extra lithium sources was applied. According to the
ICP analyses, the deviation in the molar coefficient of each element
from the nominal one is below 2%. The powders were similarly
ground by ball-milling with a dispersion medium of 2-propanol,
showing a median particle diameter of around 1 μm. The powders
were uniaxially pressed into disks and then isostatically pressed at 300
MPa, followed by firing in ambient air at given temperatures for 10 h.
The surface of the as-sintered disks was removed by grinding with
abrasive papers. The apparent density was evaluated as the weight
divided by the apparent volume defined by the diameter and thickness
of the disk. The uncertainty in the density evaluation is below 1%,
which mainly originates from the uniformity in thickness after surface
grinding. In addition to the above firing experiments for specimen
preparation, in situ observation of shrinkage behavior during the firing
process was carried out with a dilatometer (DIL402 Expedis Classic,
NETZSCH-Gerätebau GmbH) for selected compositions. The green
disk as pressed in the above procedure was set to the dilatometer and
heated under a flow of synthetic air for measurement of temperature-
programmed linear dimensional changes.
For X-ray diffraction (XRD) analyses, the sintered disks after
removing the side and surface by grinding were crashed into powders.
The powder XRD measurements were performed with Cu Kα
radiation (SmartLab/Rigaku Co., Ltd.). The morphology and element
distribution of the sintered specimens were observed with scanning
electron microscopy/energy dispersive X-ray spectroscopy (SEM/
EDS; JSM-7800F/JEOL Ltd.) for the polished surfaces. For the dense
specimens, the surface was mechanically ground and polished with
abrasive media down to 0.1 μm. On the other hand, the porous
specimens were processed with an Ar-ion milling apparatus (CROSS
SECTION POLISHER (IB-09020CP)/JEOL Ltd.) to prepare a flat
surface. In addition to SEM/EDS, transmission electron microscopy
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(TEM)-based observation and analyses with a TEM/STEM apparatus
(JEM-ARM200F/JEOL Ltd.) were performed on a selected specimen
after sampling and thinning with a focused ion beam (FIB; JIB-4501/
JEOL Ltd.) technique.
3. RESULTS AND DISCUSSION
3.1. Sintering Behavior. The influence of cobalt
introduction into LATP on the sintering behavior is simply
examined by comparing the density of sintered specimens with
various compositions and sintering temperature. It is noted
that the relative density presented here is based on the
theoretical density of LATP, 2.93 g·cm−3.19 Figure 1a shows
the relative density of LATP as well as x = 0.02 and 0.1
specimens of the series (A) fired at various temperatures. The
densification of the LATP specimen begins above 800 °C, and
just approaches 90% relative density after firing at 1100 °C. On
the other hand, significant promotion of densification is
observed for the cobalt-introduced compositions. In particular,
the x = 0.1 specimen shows clear densification through firing
even at 700 °C and is significantly densified at 800 °C to
achieve the relative density approximate to 100%. That is, the
addition of cobalt to LATP reduces the sintering temperature
by ca. 300 degrees. The difference in the densification behavior
between the specimens is also depicted by shrinkage during the
firing process observed with dilatometry. Figure 1b shows the
linear dimensional change of the as-pressed LATP and x = 0.1
specimens during a temperature program simulating the firing
process. Upon heating, the green bodies essentially show
thermal expansion at lower temperatures. The LATP specimen
starts shrinking around 750 °C, indicating the initiation of
sintering, while the shrinkage hardly proceeds even when
holding at 800 °C for 10 h. On the other hand, the shrinkage
of the x = 0.1 specimen starts at a lower temperature of ca. 650
°C and the linear dimensional change reaches −13% at the
onset of temperature holding at 800 °C. Thus, the x = 0.1
composition is significantly sinterable compared with LATP.
Presented in Figure 2 is the influence of cobalt content on
the relative density after firing at 800 °C for 10 h. For series
Figure 2. Relative density of the series (A)
(Li1.3+2xAl0.3CoxTi1.7‑x(PO4)3) (red) and series (B)
(Li1.3−2yCoyAl0.3Ti1.7(PO4)3) (blue) specimens sintered at 800 °C
for 10 h as a function of the cobalt content, x and y. That of LATP (x
and y = 0) is plotted with the black symbol.
(A), the relative density monotonously increases with x and
approximates to 100% at x ≥ 0.1. On the other hand, for series
(B), the dependence of the relative density on the cobalt
content is somewhat complicated. In the smaller y region, the
relative density increases with y, whereas it switches to
decreasing at y > 0.02. It is noted that, in the smaller x and y
regions, the relative densities of series (A) and (B) at a given
cobalt content are almost equivalent to each other. On the
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other hand, the relative density for the larger cobalt content is
significantly different between the two series of composition,
which should be associated with the phase constitution
described below.
3.2. Phase Relation in the Li1.3+2xAl0.3CoxTi1.7‑x(PO4)3
System (Series (A)). Figure 3 shows the XRD patterns of
series (A) after firing at 800 °C for 10 h. The XRD pattern of
LATP (x = 0), which is the end-member of the two series of
compositions, indicates majority of the intended NASICON-
type LATP phase in the specimen. It is noted that weak
reflections from AlPO4 are also observed, which probably
originates from imperfections in the solid-state reaction during
powder synthesis. For the x = 0.01 and 0.02 specimens,
predominant NASICON, small LiTiO(PO4), and slight AlPO4
peaks are observed. On the other hand, in the XRD pattern of
the x = 0.05 specimen, weak reflections from LiCoPO4 and
LiTiO(PO4) are observed in addition to the peaks of the
NASICON phase. The XRD patterns of the x ≥ 0.1 are
essentially similar to the x = 0.05 case, while the intensities of
LiCoPO4 and LiTiO(PO4) reflections increase with increasing
x.
In order to further identify the phases in the specimen, the
polished surface of the x = 0.1 specimen was analyzed with
SEM-EDS. Figure 4 shows the secondary electron (SE) image,
backscattered electron (BSE) image, and elemental mapping
images for Ti, Al, Co, P, and O. Bright particles are noticeable
in the BSE image, which designates the relative heaviness of
the particles to imply its cobalt-rich composition. As indicated
by the yellow-circled area, the BSE-bright particles are
associated with the high concentration of cobalt as well as
the absence of titanium and aluminum, which is well consistent
to the identification of LiCoPO4 with XRD. In addition, the
titanium image includes several bright spots as shown by the
white circle, where decreased brightness is observed in the
aluminum and phosphor maps; these particles are considered
to correspond to LiTiO(PO4) in accordance with the XRD
analyses. It is also noted that all of the X-ray spectra from
several selected areas away from the LiCoPO4 and LiTiO-
(PO4) particles show the small but distinct peak of the Co
characteristic X-ray. That is, it is suggested that the LATP
phase accepts a slight dissolution of cobalt in the crystal
structure, which is consistent with the absence of any peaks
from cobalt-including secondary phase(s) in the XRD patterns
for x = 0.01 and 0.02. Thus, the XRD and SEM-EDS analyses
are consistent with each other in the phase identification of the
x = 0.1 specimen: the slightly cobalt-dissolved LATP,
LiCoPO4, and LiTiO(PO4). However, supposing the con-
servation of the total composition in the specimen, the
identification of LiTiO(PO4) implies the existence of any
substances with phosphorus-rich anions; that is, a dispropor-
tionation of orthophosphoric anion is anticipated. Such
compounds are missing in the above identification.
Further inspecting the images, it is noticed that, in the BSE
image, there are many dark spots at triple points of grains and
some dark slabs between grains. Comparison with the SE
image shows that some of the dark spots are accompanied by
pores. However, the area of the dark spots in the BSE image is
clearly larger than the corresponding pores recognized in the
SE image. Therefore, it is suggested that any substances
composed of light elements are present around such triple
points and grain boundaries. Considering the constituent
elements of the specimen, the cationic species in the substance
are supposedly mainly lithium.
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Figure 3. (a) XRD patterns of series (A) (Li1.3+2xAl0.3CoxTi1.7‑x(PO4)3) sintered at 800 °C for 10 h and (b) patterns in (a) magnified. The
intensities are as-normalized relative to the maximum intensity in each pattern. Also presented are the peak position and relative intensity from the
database: LATP (ICSD 14588), LiCoPO4 (ICSD 400625), LiTiO(PO4) (ICSD 78106), and AlPO4 (ICSD 97546). The main peak of the
secondary phase identified in each pattern is indicated with an arrow of the color corresponding to the database pattern.

Figure 4. Secondary electron (SE), backscattered electron (BSE) and EDS elemental mapping images (Ti, Co, Al, P, and O) of the x = 0.1
specimen of series (A) (Li1.3+2xAl0.3CoxTi1.7‑x(PO4)3) sintered at 800 °C for 10h.

The identical specimen was further analyzed with STEM-
EDS after cutting and thinning with FIB. Figure 5 shows the
STEM dark-field (DF) and bright-field (BF) image as well as
the EDS elemental maps. The view field includes two junctions
of three grains, which are accompanied by dark triangles in the
DF image. Judging from the morphology, it is considered that
the two dark triangles are involved with closed pores while the
pores do not go through the FIB-thinned specimen. The low
DF-brightness of the two triangles at triple points is in
agreement with the above BSE image about presence of any
substances composed of light elements. The EDS elemental
maps show that, at the DF-dark triangles, titanium is clearly
absent and aluminum also appears to be significantly diluted.
Considering the expected presence of any substances with
phosphorus-rich anions as discussed above, LiPO3 or Li4P2O7
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is probably responsible for the dark triangles in the STEM-DF
image as well as dark spots and slabs in the BSE image.
The phase relation in the Li1.3+2xAl0.3CoxTi1.7‑x(PO4)3
system (series (A)) is summarized as follows. At a small x
(0.01 and 0.02), essentially all of the cobalt in the system
occupies the lithium or titanium site of the NASICON-type
structure, while the distinction of the site is difficult due to the
coexistence of the lithium-containing and lithium-free second
phases, LiTiO(PO4) and AlPO4. Upon further increase of x
(>0.02), the cobalt content exceeds the solubility limit and the
excess cobalt is separated to form LiCoPO4. In the total
composition of series (A), the lithium content is as increased
by doubling the introduced cobalt content relative to the
LATP composition. Therefore, the equimolar separation of
lithium and cobalt by forming LiCoPO4 from series (A) leads
to a surplus of lithium with respect to the stoichiometry of the
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Figure 5. STEM dark field (DF), bright field (BF), and EDS elemental mapping images (Ti, Co, Al, P, and O) of the x = 0.1 specimen of series (A)
(Li1.3+2xAl0.3CoxTi1.7‑x(PO4)3) sintered at 800 °C for 10 h. Dark field image after EDS mapping is also presented.

Figure 6. (a) XRD patterns of the series (B) (Li1.3−2yCoyAl0.3Ti1.7(PO4)3) sintered at 800 °C for 10 h, (b) patterns in (a) magnified. The intensities
are as-normalized relative to the maximum intensity in each pattern. Also presented are the peak position and relative intensity from the database:
LATP (ICSD 14588), LiCoPO4 (ICSD 400625), LiTiO(PO4) (ICSD 78106), AlPO4 (ICSD 97546), Co(TiO)2(PO4)2 (ICSD 418197), and
Co2(P2O7) (ICSD 2830). The main peak of the secondary phase identified in each pattern is indicated with an arrow of the color corresponding to
the database pattern.

LATP-based phase. The surplus of lithium is compensated by
equimolar separation of LiTiO(PO4) and LiPO3 (or Li4P2O7);
the Li/Ti ratio in their sum is two (or five), being more
lithium-rich than the LATP-based phase.
3.3. Phase Relation in the Li1.3−2yCoyAl0.3Ti1.7(PO4)3
System (Series (B)). Figure 6 shows the XRD patterns of the
series (B) specimens after firing at 800 °C for 10 h, which does
not achieve significant densification irrespective of the cobalt
content, y. The XRD patterns of the y = 0.01 and 0.02
specimens are almost similar to each other and to the x = 0.01
and 0.02 specimens of series (A); that is, predominant
NASICON, small LiTiO(PO4), and AlPO4 peaks are observed
and no other secondary phases are identified. It is considered
that, within the small y range, cobalt is introduced in the
NASICON-type structure of LATP similarly to the series (A)
with a small x.
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Upon the increase of y to 0.05 and 0.1, the peaks of
LiCoPO4 appear similarly to those of series (A). At the same
time, the intensities of the AlPO4 peaks increase and the peaks
of LiTiO(PO4) become so weak as to be difficult to recognize;
the behavior of the secondary phases is different from that of
the series (A). A further increase of y to 0.2 and 0.3 leads to
the change of the cobalt-containing secondary phase to
Co(TiO)2(PO4)2 and Co2(P2O7) as well as to a further
increase of the AlPO4 intensities.
Shown in Figure 7 are the SEM-EDS images of the y = 0.1
specimen: the SE, BSE, and elemental mapping images for Ti,
Al, Co, P, and O. A porous morphology is observed in the SE
image in consistency with the low relative density of ca. 74%.
The corresponding BSE image indicates the presence of
particles higher and lower brightness than the matrix.
According to comparison of the BSE image with the elemental
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Figure 7. Secondary electron (SE), backscattered electron (BSE), and EDS elemental mapping images (Ti, Co, Al, P, and O) of the y = 0.1
specimen of series (B) (Li1.3−2yCoyAl0.3Ti1.7(PO4)3) sintered at 800 °C for 10h.
mappings, the BSE-bright particles (e.g., the yellow-circled
one) are accompanied by intense brightness in the cobalt map,
corresponding to LiCoPO4 identified with the XRD analysis.
Similarly, the BSE-dark particles (e.g., the white-circled one)
are enriched with aluminum and deficient in titanium, which
should be relevant to AlPO4. It is also noted that, for the BSE-
dark (AlPO4) particles, the brightness in the cobalt map is
clearly lower than the matrix, which signifies the absence of
cobalt in AlPO4 and thereby the presence of cobalt in the
specimen matrix, LATP phase. This observation again confirms
a certain solubility of cobalt in the LATP phase as inferred by
the absence of LiCoPO4 peaks in the XRD of the y = 0.01 and
0.02 specimens. Thus, the results of the SEM-EDS analyses are
well consistent to the XRD analyses.
Overall, the phases in the Li1.3−2yCoyAl0.3Ti1.7(PO4)3 system
(series (B)) undergo the following transition with y increasing.
Similarly to series (A), cobalt in a small y composition (0.01
and 0.02) is essentially introduced in the LATP structure,
while it is difficult to specify its crystallographic site due to
coexistence of the lithium-containing and lithium-free second
phases, LiTiO(PO4) and AlPO4. At a larger y (0.05 and 0.1),
the NASICON phase is saturated with cobalt and the excess
cobalt forms LiCoPO4. The separation of lithium and cobalt
from the Li1.3−2yCoyAl0.3Ti1.7(PO 4)3 system involves a
deficiency of lithium in the remaining composition. Since
occupation of the Ti4+ site by Al3+ is attained by an increase of
the lithium content for charge compensation, the NASICON
phase ejects some portion of Al3+ so as to balance with the
decreased lithium content. Therefore, the composition of the
NASICON phase changes to be less aluminum-doped,
resulting in separation of AlPO4. A further increase of y (0.2
and 0.3) leads to continuous ejection of aluminum from the
NASICON phase to increase AlPO4, resulting in an aluminum-
free NASICON phase at a certain y. Then even titanium starts
to separate from the NASICON phase, and thereby the cobalt-
including secondary phase switches from LiCoPO4 to a
combination of Co2(P2O7) and Co(TiO)2(PO4)2. It is noted
that the anionic species in the cobalt-containing secondary
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phases, P2O74− and O2−, can be formed via disproportionation
of PO43−.
3.4. Consideration on the Sintering Behavior.
According to the cobalt-content dependence of the relative
density after firing at 800 °C (Figure 2), both of series (A) and
(B) exhibit a clear promotion of densification even with a small
amount of cobalt; x and y = 0.01 and 0.02. Furthermore, in the
small x and y range, the relative density values of both systems
are quite close to each other at a given x and y value; 70% at x
and y = 0.01:78% at x and y = 0.02. The specimens of both
systems for x and y = 0.01 and 0.02 coexist with the same
secondary phases, LiTiO(PO4) and AlPO4, and they are
observed also for the cobalt-free LATP specimen, which shows
negligible densification at the same firing condition. These
observations suggest that the promotion of densification in this
small x and y range is not ascribed to an assisting effect of any
coexisting phases but to the property of the cobalt-doped
LATP phase. As mentioned before, it is difficult to distinguish
the crystallographic site occupied by cobalt ion from the
current experimental results. The information on ionic radii20
seems to be hardly helpful for the distinction; the effective
ionic radius of Co2+ in 6-fold coordination is 0.65 and 0.745 Å
for low- and high-spin states, respectively, which are
intermediate between 0.605 Å of Ti4+ and 0.76 Å of Li+.
The distinction of the cobalt site as well as the mechanism of
the moderately enhanced sinterability are left open in the
present paper and will be addressed in future work.
A further increase of x and y beyond 0.02 leads to different
densification behavior between the two series. The relative
density of series (A) continues to increase, approximating
100% at x = 0.1. On the other hand, that of series (B)
significantly decreases; 74% at y = 0.1 and 62% at y = 0.3. The
coexisting secondary phases are also different between the two
systems: LiCoPO4, LiTiO(PO4), and LiPO3 (or Li4P2O7) in
series (A) and LiCoPO4 and AlPO4 in series (B) (y = 0.05 and
0.1). In general, promotion of sintering after introduction of
foreign species is often associated with the formation of a
liquid phase. In Table 1, the melting points of the second
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Table 1. Melting Points (°C) of the Second Phases Related
to the x = 0.1 Specimen of Series (A) and y = 0.1 Specimen
of Series (B)
LiTiO(PO4) LiCoPO4 LiPO3 Li4P2O7 AlPO4
108521 >80014 66521 88521 ∼200022
phases are summarized.14,21,22 Among the second phases,
LiPO3 has the lowest melting point.21 LiPO3 is the second
phase specific to the series (A) with significant sinterability,
and the melting point of 665 °C is consistent with the onset of
sintering observed with the dilatometry (Figure 1b). In
addition, from a comparison of the STEM-DF images of the
x = 0.1 specimen before and after EDS mapping (Figure 5), it
is suggested that the DF-dark triangles, where titanium and
aluminum are absent, underwent some structural change due
to electron beam irradiation, implying its unrefractory nature.
Thus, the origin of the significantly high sinterability of the
Li1.3+2xAl0.3CoxTi1.7‑x(PO4)3 system (series (A), x > 0.02) is
most likely the assistance of the liquid phase involving LiPO3,
which forms together with LiCoPO4 and LiTiO(PO4) as the
second phase of the cobalt-doped LATP. While some
hindrance to ionic conduction may be anticipated for such
multiphase materials, the total conductivity of the series (A)
specimen (x = 0.1) sintered at 800 °C is tentatively evaluated
to be 3 × 10−4 S·cm−1 at 25 °C, which is a reasonable value for
polycrystalline LATP. The detailed investigation of the
conduction behavior including separation of bulk/grain-
boundary conductivity and evaluation of electronic conductiv-
ity will be reported elsewhere.
The composition which shows significant sinterability with
the assistance of LiPO3 formation can be illustrated by the
quasi-ternary phase diagram shown in Figure 8. In the diagram,
orthophosphates of Li+, Ti4+, and Co2+ are taken as the
constituents and aluminum is omitted for simplicity. The stable
compounds and end-member are marked with closed black
circles, and the other chemical formulas merely indicate
nominal compositions, with which any stable phases are not
commonly recognized. It is also noted that since orthophos-
Figure 8. Expected compositions that are highly sinterable due to the
assistance of LiPO3 (red-shaded region) illustrated in a Li3PO4−
Ti3(PO4)4−Co3(PO4)2 quasi-ternary diagram. It is noted that the
figure is not drawn as a complete phase diagram. The stable
compounds and end-member are indicated with closed black circles,
and the other chemical formulas are shown solely as nominal
compositions. The nominal composition of Li2Ti(PO4)2 is the sum of
LiPO3 and LiTiO(PO4), of which the former is responsible for the
significantly high sinterability. The examined compositions of series
(A) and (B) are indicated with closed red and blue circles together
with respective composition lines.
7521
www.acsaem.org Article
phate ions may undergo uptake and release of oxygen to form
various anions, the presented diagram is not complete as an
equilibrium phase diagram but an orthophosphate cross
section of the Li2O-TiO2−CoO-P2O5 quasi-quaternary tetra-
hedron. In the diagram, the two-phase line of LiCoPO4−
LiTi2(PO4)3 is drawn, since their equilibrium coexistence is
reported in the previous study.11,14,15 The composition line of
Li1+2xCoxTi2−x(PO4)3, which simulates the series (A) compo-
sition, is indicated with the red dashed line starting from
LiTi2(PO4)3 (x = 0) toward Li5Co2(PO4)3 (x = 2). Also
indicated is the composition of Li2Ti(PO4)2, which is the sum
composition of LiPO3 and LiTiO(PO4) as the counterpart of
the second phase LiCoPO4. It is considered that the four-phase
coexistence tetrahedron of LiTi2(PO4)3-LiCoPO4−LiPO3−
LiTiO(PO4) exists in the quasi-quaternary system, in which
the composition is possible to show the LiPO3-assisted high
sinterability. In the orthophosphate plane (Figure 8), the
triangle of LiTi2(PO4)3−LiCoPO4−Li2Ti(PO4)2 is the cross
section of the four-phase coexistence tetrahedron, which
includes the series (A) composition line. Considering the x-
dependence of the relative density, the highly sinterable
composition on the orthophosphate plane is semiquantitatively
illustrated by the red-shaded area in Figure 8.
4. CONCLUSIONS
LATP accepts dissolution of cobalt in the crystal structure up
to a few molar percent, which provides a moderate promotion
of sintering and densification. The introduction of more cobalt
beyond the solubility limit leads to equilibrium formation of
LiCoPO4 and the other second phases. When the total
composition of the system is more Li3PO4-rich than LATP,
which can be distinguished with the help of the phase diagram,
the separation of LiCoPO4 involves the formation of a low
melting-point compound, most likely LiPO3, to significantly
assist sintering via liquid phase formation.
■
AUTHOR INFORMATION
Corresponding Author
Shogo Miyoshi − Center for Green Research on Energy and
Environmental Materials, National Institute for Materials
Science, Tsukuba 305-0044 Ibaraki, Japan; orcid.org/
0000-0003-0375-1187; Phone: +81-29-860-4754;
Email: MIYOSHI.Shogo@nims.go.jp; Fax: +81-29-854-
9061
Authors
Yoshihiko Nishihara − Center for Green Research on Energy
and Environmental Materials, National Institute for
Materials Science, Tsukuba 305-0044 Ibaraki, Japan
Kazunori Takada − Center for Green Research on Energy and
Environmental Materials, National Institute for Materials
Science, Tsukuba 305-0044 Ibaraki, Japan; orcid.org/
0000-0001-7568-1806
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsaem.2c00996
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors are grateful to Ms. Sonoko Kakui, Ms. Makiko
Oshida, and Mr. Keisuke Shinoda for the sample preparation
https://doi.org/10.1021/acsaem.2c00996
ACS Appl. Energy Mater. 2022, 5, 7515−7522
ACS Applied Energy Materials www.acsaem.org Article

and analyses. This work was financially supported by Materials
Processing Science project (“Materealize”) of MEXT, Grant
Number JPMXP0219207397, the Advanced Low Carbon
Technology Research and Development Program, Specially
Promoted Research for Innovative Next Generation Batteries
(ALCA-SPRING, Grant Number JPMJAL1301), JST Grant
Number JPMJPF2016, and JSPS KAKENHI Grant Numbers
JP17H01317, JP19K05020. The SEM/EDS and TEM/EDS
analyses were carried out at National Institute for Materials
Science (NIMS) Battery Research Platform.
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Stevenson, K. Correlating structure and transport properties in
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(20) Shannon, R. D. Revised effective ionic radii and systematic
studies of interatomic distances in halides and chalcogenides. Acta
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■
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