Solid state lithium ionic conducting thin lm Li

1.4
Al
0.4
Ge
1.6
(PO
4
)
3
prepared by tape casting
Ming Zhang
a
, Zheng Huang
a
, Junfang Cheng
a
, Osamu Yamamoto
b
, Nobuyuki Imanishi
b
, Bo Chi
a,
,
Jian Pu
a
, Jian Li
a
a
Center for Fuel Cell Innovation, State Key Laboratory of Material Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of
Science and Technology, Wuhan 430074, China
b
Department of Chemistry, Faculty of Engineering, Mie University, Tsu, Mie 514-8507, Japan
a r t i c l e i n f o
Article history:
Received 18 October 2013
Received in revised form 11 December 2013
Accepted 11 December 2013
Available online 18 December 2013
Keywords:
Solid electrolyte
LAGP
Lithium air batteries
Tape casting
Water stable lithium electrolyte
a b s t r a c t
Solid-state lithium ionic conducting ceramic thin lm Li
1.4
Al
0.4
Ge
1.6
(PO
4
)
3
is prepared by tape casting
method. The thermal decomposition of the green tape is investigated by TG/DTA analysis. And the sinter-
ing parameters are optimized in air. The resultant sample shows a total lithium ionic conductivity of
3.38 10
4
S cm
1
at 25 C and activation energy of 30.57 kJ mol
1
. The thickness of the tape sheet
can be controlled to be about 75 lm. The ionic conductivity of the prepared sample reported in this study
is comparable with those reported for commercial LATP plate, showing the potential application for lith-
ium-air batteries.
2013 Elsevier B.V. All rights reserved.
1. Introduction
Recently rechargeable lithium air batteries have attracted a
wide focus all over the world due to the requirement for develop-
ing electrochemical energy storage devices with high energy den-
sities that can promote the mass production of hybrid electrical
vehicles and electrical vehicles [13]. Two types of lithium air bat-
teries have been developed recently [4], aqueous and non-aqueous
electrolyte systems lithium air batteries. The non-aqueous type
lithium-air battery shows a high weight-specic energy density
[5], but it has some several problems that must be overcome, such
as lithium corrosion by water and CO
2
ingression when operated in
air, precipitation of high resistance reaction products on the porous
air cathode electrode, and high polarization during the charge and
discharge processes. However, these problems observed for the
non-aqueous electrolyte lithium air system could be removed in
the aqueous electrolyte lithium air battery. While it is impossible
to ignore that lithium metal can react vigorously with water to
produce LiOH and hydrogen gas in aqueous electrolyte lithium
air battery. Therefore, Visco et al. [6] and Imanishi et al. [7] have
proposed the water stable lithium electrode, which consists of a
lithium metal anode, a lithium conducting polymer electrolyte
consisting of polyethylene oxide based lithium ion polymer
electrolyte, and a water stable lithium ion conducting solid
electrolyte Li
1+x
Al
x
Ti
1x
(PO
4
)
3
(LATP). The polymer electrolyte
was used as an interlayer to prevent the direct contact of lithium
metal with solid state lithium ion conducting electrolyte LATP,
because LATP is unstable in contact with lithium metal.
The key material of the water stable lithium electrode is the
water stable lithium ion conducting solid state electrolyte. Re-
searches on solid state lithium ion conducting electrolytes have
been attracting more and more attention in the past several years
due to the wide range of potential important technological applica-
tions in the high energy density rechargeable lithium air batteries
and other lithium metal batteries. But most lithium batteries are
coupling a polymer membranes (such as PP, PE) with a plasticizing
organic solvent (such as EC, DMC, EMC) which may bring the usual
drawbacks related to the presence of safety problems, for instance,
liquid electrolyte leakage, lithium anode corrosion and limitations
for miniaturization [810]. Some inorganic solid state lithium ion
conductor can overcome those problems, such as LIPON [11,12],
LISICON [13], NASICON glass ceramic [4,14,15], perovskite
Li
0.53x
La
0.5+x
TiO
3
[1618]. However, the conductivity of LIPON
was reported to be 3 10
6
S cm
1
at room temperature [12].
Thio-LISICON Li
2
SP
2
S
5
glass has a high conductivity at room
temperature while it is difcult to fabricate and shows poor chem-
ical durability [19]. The ionic conductivity of Li
0.53x
La
0.5+x
TiO
3
was
reported only to be 4 10
7
S cm
1
by lm deposited using
radio-frequency magnetron sputtering [20] and it was observed
0925-8388/$ - see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jallcom.2013.12.100

Corresponding author. Tel./fax: +86 27 87558142.

E-mail address: chibo@hust.edu.cn (B. Chi).
Journal of Alloys and Compounds 590 (2014) 147152
Contents lists available at ScienceDirect
Journal of Alloys and Compounds
j our nal homepage: www. el sevi er . com/ l ocat e/ j al com
that the LLTO-10 wt% Al
2
O
3
composite electrolyte exhibited a high
bulk conductivity as high as 9.33 10
4
S cm
1
, but the grain
boundary conductivity was only to be 2.38 10
5
S cm
1
by an
ceramic processing route including tape casting and relatively
low-temperature calcination [16]. Recently, NASICON glass cera-
mic LATP (OHARA Inc., Japan) was reported to have a conductivity
3.3 10
4
S cm
1
at room temperature. While it is a little more
expensive to use on a large scale because of the high preparation
cost, and it is very difcult to prepare large size LATP sheet because
of the preparation process [13,21]. We have reported NASICON
lithiumion conductor Li
1.4
Al
0.4
Ge
1.6
(PO
4
)
3
(LAGP) with a maximum
total conductivity of 1.22 10
3
S cm
1
at room temperature
using a citric acid as precursor prepared by the solgel method,
and the all-solid-state Li
7
Ti
5
O
12
/Li
1.4
Al
0.4
Ge
1.6
(PO
4
)
3
/LiCoO
2
can
charge and discharge normally with a current 1 lA cm
2
at 60 C,
while the discharge capacity of the battery was only 5 lAh, which
was little lower than the charge capacity. And the thickness of this
LAGP was about 2 mm, which was too thick for application.
Thus although LAGP pellets made by dried-pressing method
have a high conductivity, it is very difcult to prepare for a large
scale and the decrease of the thickness is difcult to carry out.
Alternative route for large-scale preparation and the attempt to de-
crease the thickness of the electrolyte are desired. In this research,
we have attempted to prepare for a thin LAGP lm (micron-grade)
by using tape casting method to scale up the productivity and re-
duce the preparation cost. The preparation and the performance
of the products will be discussed in detail.
2. Experimental
Li
1.4
Al
0.4
Ge
1.6
(PO
4
)
3
powders were prepared using a precursor from the solgel
method with citric acid, as reported previously [4]. Stoichiometric amounts of
Ge(OC
2
H
5
)
4
(Aldrich), LiNO
3
, Al(NO
3
)
3
9H
2
O, and NH
4
H
2
PO
4
were dissolved into a
0.2 M aqueous solution of citric acid and stirred continuously with a magnetic stir-
rer to obtain a homogeneous solution. A certain volume of ethylene glycol (citric
acid: ethylene glycol molar ratio = 1:1, and (citric acid + ethylene glycol):(Li
+
+ -
Al
3+
+ Ge
4+
) molar ratio = 4:1) was added to the mixed solution in order to prevent
the formation of hard agglomerates and promote the poly-esterication and poly-
condensation. The mixed solution was kept at 80 C for several hours during the
solgel preparation process. After the formation of the homogeneous solution, the
gel was kept at 170 C for 24 h to allow the evaporation of water and promote
the esterication and polymerization between ethylene glycol and citric acid, and
then heated at 500 C for 4 h to obtain an organic metal salt powders. The obtained
powders were ground with an agate mortar and pestle before sintering at 800 C for
5 h to prepare LAGP powders.
Then the as-prepared LAGP powders were ball-milled with ZrO
2
balls for 6 h
using high energy mechanical milling (HEMM) (Fritsch Planetary Micro Mill) with
ethanol (95%) as solvent, dried in air, and then dispersed in ethanol (95%) and tol-
uene mixed solution (3:7 volume ratio). Menhaden sh oil (2 wt% to LAGP) was
added into the slurry as a dispersant. Then the mixed slurry was ball-milled again
for 24 h using HEMM. Then a certain amount of poly (vinyl butyral) (Aldrich, Butvar
B-98, 7 wt% to LAGP) as a binder and butyl benzyl phthalate (7 wt% to LAGP) as the
plasticizer were added into the mixed slurry, and the slurry was ball-milled using
HEMM for another 24 h. Before tape-casting, the slurry was de-foamed for 3 min
to remove the air bubbles by using a planetary vacuum mixer (Thinky, Japan).
Tape-casting was performed on a silicon coated polyethylene substrate foil with
double blades of gap heights of 700 lm and 400 lm. The casting speed was con-
stant at 60 cm min
1
. After tape-casting, the green sheets were left to dry at room
temperature for 24 h in air. Then the green sheets were cut into small pieces of 1.2
1.5 cm 1.21.5 cm. Then two or three pieces of the green sheets were hot pressed
together at 90 C for 10 min and sintered at various temperatures under air. The
owchart for LAGP tape-sheet preparation is shown Fig. 1.
Scanning electron microscope (SEM, Hitachi SEM S-4000) is used to analyze the
micro-morphology of the as-prepared LAGP powders and LAGP sheets. Differential
thermal analysis (TG-DTA) was carried out using a Rigaku Thermo-Plus TG8120 to
analyze the sintering temperature. The crystal structure of the samples was ana-
lyzed using X-ray diffraction (XRD; Rigaku RINT 2500) with Cu Ka radiation in
the 2h range from 10 to 90 at a scanning step rate of 0.02 deg s
1
. Gold lm
was sputtered on both sides of the sintered pellets as the blocking electrodes in or-
der to evaluate the electrochemical properties of the LAGP sheet. The gold coated
LAGP specimen was assembled into a sealed sandwich cell using a stainless steel
as a current collector in a dry chamber with silica-gel which was slightly lower than
that under air to test the electrochemical impedance spectra (EIS). EIS measure-
ments of the LAGP were carried out using an impedance analyzer (Solartron 1260
and 1287) in the temperature range from 20 C to 80 C and the frequency range
of 0.01 Hz to 1 MHz. At each different temperature, the specimen was equilibrated
for 20 min before the impedance measurement. A nonlinear instant t program in
the Z-View software was used to analyze the impedance proles.
3. Results and discussion
Fig. 2 shows SEM images of the powders. It conrms that ne
powders without agglomeration are obtained after HEMM. The
BET surface area of the powders increases from 1.46 m
2
g
1
to
6.67 m
2
g
1
after ball-milling.
To exhibit the decomposition proles of the organics in the
LAGP casting tape, the TG and DTA results are presented in Fig. 3.
The rst weight loss occurs at around 200
o
C, due to the oxidation
loss of organic addition. This process lasts to about 500
o
C until all
the organics are completely eliminated. The weight loss and exo-
thermic peaks could be attributed to the oxidization reaction com-
bined with the evaporation of volatile products such as H
2
O and
CO
2
. When the temperature exceeds 600
o
C, no further weight loss
can be observed since all the organic additives have been con-
sumed. When the temperature is above 1050
o
C, an apparent endo-
thermic peak appears because of the evaporation of Li at the high
temperature along with the side reactions.
Fig. 4 shows the XRD patterns of the LAGP green sheet sintered
at 900 C (a), 950 C (b), and 1000 C (c) for 5 h. Sample sintered at
900 C for 5 h shows a dominating LAGP phase and a small but
unobvious impurity GeO
2
phase as in Fig. 4a. The impurity phases
AlPO
4
can be found at 27, 28, 36 and GeO
2
phase at 2h of 21 as
shown in Fig. 4b and c, which matches well with the reported re-
sult for LAGP sintered above 950
o
C [4]. The AlPO
4
phase is an elec-
trically insulating phase and its existence can decrease the
electrical conductivity of the specimen. Thus, the sintering temper-
ature should be controlled to be below 950
o
C in order to get a rel-
ative pure LAGP phase with a high conductivity.
XRD patterns of the LAGP green sheet sintered at 900
o
C for 8 h,
12 h, and 15 h are shown in Fig. 5. All the main diffraction peaks
match well with the NASICON-type LiGe
2
(PO
4
)
3
structure
(PDF#80-1924). The crystal lattice parameters are calculated by
using the Jade cell renement program. The a-lattice constant de-
creases from0.8280 nm to 0.8259 nm and the c-lattice constant in-
creases from 2.0474 nm to 2.0625 nm for the samples treated at
900
o
C for 8 h and 12 h respectively. While the c-lattice constant
decreases to 2.0450 nm and a-lattice constant increases to
0.8270 nm for the sample LAGP treated at 900
o
C for 15 h. Wen
et al. [22] reported that c-lattice of Li
1.5
Al
0.5
Ge
1.5
(PO
4
)
3x
Li
2
O,
(x = 0.00.20) decreased with the lower Li
2
O content. The decrease
of the c-lattice parameter for LAGP sintered for 15 h may be due to
the evaporation of Li
+
.
Fig. 6 shows the SEM images of the samples sintered at 900 C
for different time. The grain sizes increase with the sintering time,
along with the grain boundary sizes decrease. LAGP sintered for 8 h
has the smallest grain size and the largest grain boundary as
shown in Fig. 6a. With the increase of the sintering time, the grain
size increases and the grain boundary decreases as shown in
Fig. 6b, together with the cracks, as shown in Fig. 6c.
Typical EIS proles measured at room temperature are shown
in Fig. 7 for LAGP tape sheets sintered at 900 C for various time.
The impedance proles consist of a semicircle in the high fre-
quency and a linear region at the lowfrequency, and the equivalent
circuit is inserted into Fig. 7. The intercept of the semicircle in the
high frequency represents the bulk resistance R
b
, and the diameter
of the semicircle is attributed to the grain boundary resistance R
gb
.
R
b
values are 3045.81 Xcm, 2746.05 Xcm, 2981.87 Xcm, and R
gb
values are 318.88 Xcm, 213.46 Xcm, and 284.1 Xcm for LAGP
sample sintered at 900 C for 8 h, 12 h and 15 h, respectively. All
the resistance values are obtained from the simulated results by
148 M. Zhang et al. / Journal of Alloys and Compounds 590 (2014) 147152
using the equivalent circuit with a nonlinear instant t program in
the z-view software. The result conrms that R
b
and R
gb
are depen-
dent on the sintering time. Variation of initial resistance at high
frequency region depends on the density of the prepared casting
sheets. With a long heat treating time, R
b
and R
gb
decrease along
with the increasing density of the sheets. The calculated electrical
conductivity shows an obvious temperature and time dependence.
The relative densities are measured to be 83%, 88%, and 87% for the
samples sintered at 900 C for 8 h, 12 h, and 15 h, respectively. The
Fig. 1. Flowchart for LAGP tape-sheet preparation process.
Fig. 2. SEM pictures for LAGP powder before (a) and after (b) using the HEMM.
Fig. 3. TGDTA curves for LAGP green tape-sheet.
Fig. 4. XRD patterns of LAGP tape-sheet sintered at (a) 900 C, (b) 950 C, (c)
1000 C for 5 h.
M. Zhang et al. / Journal of Alloys and Compounds 590 (2014) 147152 149
highest conductivity is observed for LAGP sintered at 900
o
C for
12 h along with the highest relative density. The bulk and grain
boundary conductivity measured at 25 C of LAGP sintered at
900 C for 12 h are calculated to be 3.64 10
4
S cm
1
and
4.68 10
3
S cm
1
, respectively, and the total conductivity r
t
is
3.38 10
4
S cm
1
at 25 C, this value is comparable to the com-
mercial solid state lithium ion conductor LATP [23] (Ohara Inc., Ja-
pan) with the electrical conductivity of 3.3 10
4
S cm
1
. The total
conductivities of LAGP sintered at 900 C for 8 h and 15 h are
2.97 10
4
S cm
1
and 3.06 10
4
S cm
1
, respectively. The dis-
crepancy could be explained as a result of different density derived
from the sintering time.
The activation energy (E
a
) and conductivity (r) for different
samples are found to t the Arrhenius equation.
r Ae
Ea
RT
1
log r log A
E
a
2:3RT
log A
B
T
2
where E
a
is the activation energy; A is the pre-exponential factor; T
is the absolute temperature and R is the gas constant. The parame-
ters, as the slope B and log A, are determined in Fig. 8. E
a
can be cal-
culated from the slope of the conductivity dates measured in the
temperature range from 20 C to 80 C. The corresponding E
a
for
Fig. 5. XRD patterns and lattice parameters of LAGP tape-sheets sintered at 900 C
for (a) 8 h, (b) 12 h and (c) 15 h.
Fig. 6. SEM pictures for LAGP tape sheets sintered at 900 C for (a) 8 h, (b) 12 h and
(c) 15 h.
Fig. 7. Impedance proles of LAGP tape-sheets sintered at (j) 900 C for 8 h, (d)
12 h and (.) 15 h at 25 C.
Fig. 8. Arrhenius plots for LAGP tape-sheets sintered at (j) 900 C for 8 h, (d) 12 h
and (.) 15 h between 20 C to 80 C.
150 M. Zhang et al. / Journal of Alloys and Compounds 590 (2014) 147152
the samples sintered at 900 C for 8 h, 12 h, and 15 h is
31.76 kJ mol
1
, 30.57 kJ mol
1
, and 30.96 kJ mol
1
, respectively.
The high conductivity of the sample sintered at 900 C for 12 h
may be due to the increasing of the relative density by the properly
heat-treating process, which mainly contributes to decrease the
resistance of grain bulk and grain boundary impedance. And the
conductivity decrease of the sample sintered at 900 C for 15 h
may be due to the formation of the cracks in the grain boundary
and the evaporation of Li
+
at a high temperature for a long sinter-
ing time (as shown in Fig. 6c), which can also cause the increase of
E
a
of the sample from 30.57 kJ mol
1
to 30.96 kJ mol
1
compared
to that for sample sintered for 12 h. The relationship of sintering
time, relative density, conductivity and the activation energy is
summarized in Fig. 9. It can be found that LAGP sheet sintered at
900 C for 12 h exhibits the highest conductivity and relative den-
sity, together with the lowest activation energy among all the
samples.
Temperature dependence impedance plots for LAGP (with
thickness of 228 lm) sintered at 900 C for 12 h are shown in
Fig. 10. The resistance decreases with the testing temperature from
20 C to 80 C, and no charge transfer effect is found because of the
test environment in a dry chamber with silica-gel. At 60 C, the to-
tal resistance is only 18.31 Xcm
2
, and r
t
at 60 C is calculated to
be 1.25 10
3
S cm
1
, which is comparable to that of LAGP
(1.22 10
3
S cm
1
, 25 C) pellet prepared by dried-pressing and
sintered at 900 C for 11 h. Imanishi et al. [7,23] reported aqueous
lithium air batteries by using a water stable lithium anode con-
sisted of lithium metal, LiPON or polymer interlayer, and LATP so-
lid state membrane. LAGP pellet has been proven to be stable in
saturated LiOH and LiCl aqueous solution in our previous report
[4]. Thus the prepared casting sheet can be used as a solid state
membrane for aqueous lithium air batteries to protect lithium an-
ode from reacting with aqueous electrolyte solution. Meanwhile, it
is necessary to reduce the thickness of the ceramic electrolyte so as
to reduce the weight of the cell to meet the requirement of appli-
cation. Philippe et al. [24] reported thin membranes with thickness
about 50 lm were preferred with a signicant reduction in area
specic resistance and cell weight. We have tried to make a thin
LAGP sheet about 75 lm in thickness (shown in Fig. 11). The dif-
culty is to keep both a good mechanical stability and high lithium
ion conductivity for the membrane. The average three-point bend-
ing strength of LAGP lms was measured to be 48.02 N mm
2
,
which is lower than that of commercial LATP as 154 N mm
2
. Fur-
ther optimization in preparation process will be going onto modify
the densication of electrolyte, ionic conductivity and hence
mechanical properties of LAGP sheet. Several approaches could
be adopted to enhance the ambience temperature conductivity as
well as to improve the mechanical stability, such as adding some
epoxy resin to ll the micro-porous of the lm [25], or Nano cera-
mic llers [26] to decrease the sintering temperature and improve
the density of the lm.
4. Conclusions
A low cost solid-state lithium ion conductor LAGP sheet has
been prepared by tape casting method. LAGP sintered at 900 C
for 12 h shows a total lithium ion conductivity of 3.38 10
4
-
S cm
1
at 25 C and activation energy of 30.57 kJ mol
1
, with rela-
tive density of 88%. The ionic conductivity is similar with that
reported for commercial LATP plate (3.3 10
4
S cm
1
) of Ohara
Inc., Japan. The thickness of the tape sheet can be controlled to
about 75 lm. The method adopted in this research can be scaled
up easily, which makes it possible for LAGP as potential solid-state
lithium ion conductor in lithium-air batteries.
Fig. 9. Relationship for the sintering time with (j) conductivity r
t
, (d) the relative
density and (.) the activation energy E
a
.
Fig. 10. Temperature dependence impedance plots for LAGP annealed at 900 C for
12 h.
Fig. 11. Photographs of different sizes LAGP tape-sheet after sintering at 900 C for 12 h, and a thin one with a thickness 75 lm.
M. Zhang et al. / Journal of Alloys and Compounds 590 (2014) 147152 151
Acknowledgements
The authors would like to thank Program for Changjiang Schol-
ars and Innovative Research Team in University (PCSIRT No.
IRT1014) for nancial support and Materials Characterization Cen-
ter of Huazhong University of Science and Technology for samples
characterization assistance.
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