All solid state lithium ion rechargeable

batteries using NASICON structured electrolyte

J. K. Feng
1,2
, B. G. Yan
1,3
, J. C. Liu
3
, M. O. Lai
1
and L. Li*
1
NASICON (Sodium super ionic conductor) structured Li
1?5
Al
0?5
Ge
1?5
(PO
4
)
3
(LAGP) solid
electrolyte is synthesized through a solid state reaction. The total conductivity of the LAGP
electrolyte is 7610
25
S cm
21
with a potential window larger than 6 V. All solid state lithium
batteries are fabricated using LiMn
2
O
4
as a cathode, LAGP as an electrolyte and lithium metal as
an anode. The LiMn
2
O
4
/LAGP/Li cell can deliver a capacity of about 80 mAh g
21
in the first
discharge cycle and increases gradually with charge/discharge cycles, indicating that LAGP can
be used as a promising electrolyte for lithium rechargeable batteries.
Keywords: Lithium ion batteries, Thin film batteries, Solid electrolyte, Sputtering deposition
This paper is part of a special issue on Functional Materials for Device and Energy Applications
Introduction
Li ion batteries have been widely used in almost all types
of electronic products and more recently in electronic
vehicles. The current state-of-the-art Li-ion batteries
consist of cathode and anode electrode separated by a
thin membrane with organic liquid electrolyte. Many
types of structures of cathode materials are used, such as
LiCoO
2
, LiMn
x
Ni
y
Co
(1-x-y)
O
2
,
1
LiMn
2
O
4
,
2
LiFePO
4
,
35
but only graphite is commercially used as the anode
material although a lot of other types of anode are being
studied. One of most noticeable anodes is lithium
titanate.
6,7
Although LiFePO
4
is commonly recognized
to be the safest cathode, possible growth dendrite and
other defects from copper and aluminium substrates
may cause short circuits. Therefore the only way to
design hazard free Li ion rechargeable batteries is
completely replace currently used polymer separator
and organic electrolyte by inammable ionic conductor.
All solid state Li ion rechargeable batteries with
inorganic ceramics as the solid electrolytes have attract-
ed growing interests in recent years since the solid
electrolytes possess many advantages including high
safety, high reliability, and wide potential windows. To
fabricate all solid state batteries, solid electrolytes with
high Li ionic conductivities, wide potential window and
high stability with both the cathode and anode materials
are essential. Several kinds of solid electrolytes with
high ionic conductivity and good electrochemical ability
have been studied, such as LiPON, sulphide glass,
Li
1zx
M
x
Ti
2-x
(PO
4
)
3
, Li-V-Si-O and Li-La-Ti-O et al.
814
Some of these electrolytes show low stability when
contacted with cathodes or anodes, and some of them
are moisture sensitive.
15
NASICON structured Li
1?5
Al
0?5
Ge
1?5
(PO
4
)
3
(LAGP)
has been reported to have a conductivity as high as
10
23
y10
25
S cm
21
with an electrochemical potential
window of about 6 V. It is also known that LAGP is
electrochemically stable when contacted with Li metal.
Therefore LAGP is a promising solid state electrolyte
for all solid state Li batteries.
1622
However, only little
research has been reported using LAGP as the electro-
lyte for the Li metal batteries.
In the present study, all solid state Li batteries using
LiMn
2
O
4
as a cathode, LAGP as an electrolyte and Li
metal as an anode are fabricated. Electrochemical
properties of the all solid state batteries are investigated.
The results show that LAGP can be a good electrolyte
for the all solid state Li batteries.
Experimental
LAGP was synthesised through a typical solid state
method as reported before.
16,20,21
In a typical process,
Li
2
CO
3
(99%), GeO
2
(99%), Al
2
O
3
(99%) and NH
4
H
2
PO
4
(98%) of analytical grade (all from Aldrich, USA) in a
stoichiometric ratio were thoroughly mixed by ball
milling for 48 h and then heated in a platinum crucible
at 700uC for 2 h to release the volatile compounds. The
powder was reground and ball milled again for another
24 h, after which the powder was heated to 1350uC with a
heating rate of 1uC min
21
and homogenised at 1350uC
for 1 h. The melted LAGP was quickly cooled to 500uC
and held for 2 h at 500uC, followed by cooling down to
room temperature. The as synthesised LAGP was then
crystallized at 850uC for 10 h. Finally the sintered LAGP
was shaped to pellets of 8 mm diameter and 1 mm in
thickness.
The structures of the as synthesised LAGP pellets
were measured using Shimadzu XRD-6000 X-ray dif-
fraction with Cu Ka radiation (l51?5406 A

), at a scan
rate of 2 deg/min. Surface morphologies of the LAGP
1
Materials Science Group, Department of Mechanical Engineering,
National University of Singapore, Singapore 117576
2
School of Materials Science and Engineering, Shandong University,
China
3
Institute of Advanced Shaping and Surface Engineering, Hunan
University, China
*Corresponding author, email luli@nus.edu.sg
2013 W. S. Maney & Son Ltd.
Received 15 April 2013; accepted 25 April 2013
DOI 10.1179/1753555713Y.0000000085 Materials Technology 2013 VOL 28 NO 5 276
pellets before and after coating LiMn
2
O
4
were char-
acterized with a Hitachi S-4100 eld emission scanning
(FE-SEM) electron microscopy.
Ionic conductivity was measured using AC impedance
(Solartron1287 electrochemical interface combined with
a Solartron1260 frequency response analyser) in the
frequency range between 10
21
and 10
6
Hz based on
Chowdari et al.
11
To study the ionic conductivity of the
LAGP electrolyte, the LAGP powder was pressed into a
pellet of 1mm thickness and 50 mm
2
area at 10 MPa,
and the pellets were then sintered at 850uC for 10 h. Pt
was coated on both sides of the LAGP electrolyte pellet,
followed by heating the Pt coated specimens to 400uC
for half an hour. The Pt coated pellets in the form as Pt/
LAGP/Pt were assembled into a cell using stainless steel
(SS) as a current collector to test the AC impedance.
All solid state battery was prepared by deposition of a
300 nm thick LiMn
2
O
4
layer on the LAGP pellet by
radio frequency (rf) magnetron sputtering at 600uC. The
sputtering was carried out in an Ar/O
2
(9 : 1) atmosphere
at a working pressure of 1?4 Pa and a sputtering power
of 100 W. A Pt lm was sputtered on the LiMn
2
O
4
surface as a positive current collector.
A Li metal foil was directly pressed onto the LAGP
pellet, forming a LiMn
2
O
4
/LAGP/Li all solid state cell
in the glove box. The battery performance of the Li/
LAGP/LiMn
2
O
4
cells was characterised by galvano-
static cycling between 2 and 4?5 V and cyclic voltam-
metry (CV) at a scanning rate of 0?1 mV s
21
with a
Solartron 1287 and 1256 two-terminal cell test system
with a Lab-made cell.
Results and discussion
Figure 1 shows the XRD pattern of as prepared LAGP.
Although 25% percentage of Ge
4z
ion is replaced by
Al
3z
ion, the XRD diffraction can be indexed as pure
NASICON structure LiGe
2
(PO
4
)
3
(JCPDS41-0034)
since ionic radii of Ge
4z
(0?053 nm) and Al
3z
(0?050 nm) are similar, which is similar with those
reported before.
1621
Sharp diffraction peaks of the
NASICON structure indicate a good crystallinity after
crystallization at 850uC. The scanning electron micro-
graphs of the as synthesised pellet are shown in Fig. 2. It
can be seen that the as synthesised LAGP was well
compacted together without appearance of porosity and
cracks and no clear crystalline grain can be observed.
This type of morphology was observed before.
16
To measure the conductivity of the as-prepared
LAGP, AC impedance measurement was performed
using a Pt/LAGP/Pt electrode. Typical impedance
spectrum of the LAGP electrolyte pellet is shown in
Fig. 3. The spectrum is composed of only one semicircle
in the high frequency range and a straight line in the low
frequency range, which is well known due to the bulk
resistance and the Warburg resistance. No second
semicircle due to the grain boundary resistance is
observed, indicating extremely low grain boundary
resistance of the LAGP electrolyte. It is known that
the LAGP will form a glass-ceramic structure during
fast cooling.
16,20
The lower grain boundary resistance
will greatly facilitate the Li ions transportation during
the charge and discharge processes. The total ionic
conductivity can be calculated from
s~
L
R
tot
S
where R
tot
is the total resistance which is equal to sum of
bulk resistance, R
b
and grain boundary resistance, R
gb
of the samples, L is the thickness of the electrolyte pellet,
S is the cross sectional area of the electrolyte. The R
tot
can be obtained from the right intercept of the semicircle
with the real axis ray. If R
tot
is taken to be 2700 V, S is
50 mm
2
, and L is 1 mm, the total conductivity, s is
7610
25
S cm
21
which is a little lower than the best
1 XRD spectrum of as prepared LAGP
2 Surface morphology of as prepared LAGP
3 AC impedance of LAGP pellet
Feng et al. Solid state lithium ion rechargeable batteries
Materials Technology 2013 VOL 28 NO 5 277
reported data
16,20
but higher than that of the widely used
LiPON.
8
Figure 4 shows the cyclic voltammetry (CV) spectrum
of the solid electrolyte (Pt/LAGP/Li) measured at room
temperature with a scan rate of 0?1 mV s
21
in the
voltage range from 20?4 to 6 V. Figure 4 reveals that
the Li metal can reversibly be deposited and dissolved
between 20?4 and 0?6 V. No other reactions are
observed even at 6 V, indicating that LAGP can work
at least up to 6 V potential while for most of cathode
materials the highest potential is only up to 5 V. The
result is also consistent with previous reports.
16,17
The
high ionic conductivity and high potential window make
the LAGP be a promising electrolyte for the all solid
state Li batteries.
Figure 5 shows the surface morphology of the
LiMn
2
O
4
layer deposited on the LAGP pellet. The
cathode lm appears smooth, dense, and free of cracks
and pin holes. The grain diameter is about 40 nm. The
insert in Fig. 5 shows the LAGP pellets before (white)
and after (black) deposition of the cathode, showing that
the LAGP electrolyte is fully covered by black LiMn
2
O
4
.
As shown in Fig. 6, a pure LAGP phase (Fig. 6a) can
be seen before LiMn
2
O
4
deposition. After deposition a
new diffraction peak at 2h 518?6uC appears and the
diffraction can be indexed to be the spinel LiMn
2
O
4
(111) diffraction.
23
The week LiMn
2
O
4
diffraction peak
is due to thin LiMn
2
O
4
lm character. There is no
distinguished change in the diffraction from the LAGP
pellet, implying that the LAGP structure is stable and no
reaction with LiMn
2
O
4
at the present deposition
conditions.
To test the electrochemical performance of the
LiMn
2
O
4
/LAGP/Li cell, CV measurement was carried
out between 2 and 4?5 V. Figure 7 shows a typical CV
curve of the LiMn
2
O
4
/LAGP/Li cell at a scan rate of
0?1 mV s
21
. From Fig. 7, two separated pairs of peaks
can clearly be seen, which are resulted from the typical
lithium intercalation and de-intercalation feature of
LiMn
2
O
4
. The slightly large separated distance between
anodic and catholic peaks is mainly due to large
polarization caused by the relatively lower conductivity
of the LAGP compared with the liquid electrolytes as
well as low conductivity of the cathode material since
there is no conductive additive is used as the traditional
bulk Li ion rechargeable batteries. It is also noted that
the pairs of anodic and cathodic peaks are week and
broad which are resulted from large polarization.
Figure 8 gives the 150 typical charge/discharge curves
of the LiMn
2
O
4
/LAGP/Li cell at a constant current of
4 Potential window of LAGP pellet
5 SEM of LiMn
2
O
4
deposited on LAGP pellet with insert
showing overview of LAGP pellets before (white) and
after (black) LiMn
2
O
4
deposition
6 XRD spectra of LAGP pellets a before and b after
LiMn
2
O
4
deposition
7 CV curve of LiMn
2
O
4
/LAGP/Li cell at scan rate of
0?1 mV s
21
Feng et al. Solid state lithium ion rechargeable batteries
278 Materials Technology 2013 VOL 28 NO 5
25 mA g
21
in a potential range from 2 to 4?5 V due to
the fact that polarization was very high resulting in large
drop in discharge voltage and increase in charge voltage.
The voltage proles show an expected potential plateau
for LiMn
2
O
4
with the rst charge capacity of 80 mAh g
21
which is due to the well known lithium intercalation and
de-intercalation reaction of LiMn
2
O
4
.
2325
The subse-
quent cycles show a similar shape with an increased
capacity as well as coulombic efciency. We ascribe the
increased capacity to be caused by activation and
reduction in impedance between the electrode layers and
electrolyte. When a Li metal foil is pressed directly onto
the electrolyte, interface impedance is high due to the
formation of solid interface lm (such as Li
2
O).
25,26
In
addition, the Li metal foil is also unable to fully contact
with the electrolyte. With cycling, the impedance layer
may be broken and the contact area between the Li metal
and the electrolyte may also increase. After 150 charge/
discharge cycles, the capacity increases from 80 to
115 mAh g
21
, which is also reported in other papers.
24
The charge/discharge spectra of the LiMn
2
O
4
/LAGP/Li
full cell are almost similar during cycling demonstrating
that the LiMn
2
O
4
/LAGP/Li cell has a good cyclability.
The reason for the high capacity retention in the current
study may be contributed reduced Mn
2z
disslovation
when the solid electrolyte is used.
27,28
Conclusions
NASICON structured LAGP was prepared and tested
as the electrolyte for all solid state lithium batteries. The
results show that LAGP has a 6 V potential window and
an ionic conductivity of 7?5610
25
S cm
21
. For the rst
time, a LiMn
2
O
4
/LAGP/Li cell was constructed and
tested. The cell showed an 80 mAh g
21
rst charge
capacity and 115 mAh g
21
after 150 cycles, suggesting
that LAGP can be used as a promising electrolyte for
high performance lithium metal rechargeable batteries
and an electrolyte for test high potential cathode
materials.
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8 First 150 charge/discharge curves of LiMn
2
O
4
/LAGP/Li
cell at current density of 25 mA g
21
Feng et al. Solid state lithium ion rechargeable batteries
Materials Technology 2013 VOL 28 NO 5 279