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APPROACHES
Clare P. Grey
1,2
1
Chemistry Department, Lensfield Rd, Cambridge CB2 1EW, UK.
2
Chemistry Department, Stony Brook University, Stony Brook, NY 11794-3400, USA.
cpg27@cam.ac.uk
Keywords: NMR, insitu methods, PDF, diffraction, lithium ion batteries
This talk will focus on the use of NMR methods to
investigate local structure in battery materials, bringing
in other diverse local and long range probes of structure
to complement the characterization.
A brief overview of the use of NMR methods to
investigate local structure and the electronic properties of
paramagnetic materials will be provided, including
recent theoretical studies by groups world-wide to
calculate the NMR responses of these materials and help
in spectral assigment. These methods have now been
applied (for example) to a diverse set of materials, which
include the layered LiMO
2
materials (e.g.,
Li(Co
1/3
Ni
1/3
Mn
1/3
)O
2
, Li(Li
1/3
Mn
2/3
)O
2
, Li(Mn
1/2
Ni
1/2
)O
2
and solid solutions involving these compositions) and a
series of lithium iron (II) and (III) phosphates/silicates.
The development of insitu NMR methods will then be
reviewed. Applications of these approaches to study the
anode material Si, Li dendrite formation, and conversion
materials such as FeF
2
/FeF
3
will then be described.
293
TOWARDS CHEAPER CATHODES FOR LARGE-SCALE LITHIUM-ION BATTERIES
Anti Liivat, Torbjrn Gustafsson & Josh Thomas
ngstrm Advanced Battery Centre,
Department of Materials Chemistry, Uppsala University,
Box 538, SE-751 21, Uppsala, Sweden.
josh.thomas@mkem.uu.se
The development of larger, cheaper and necessarily
greener Li-ion batteries for EV and stationary energy-
storage applications is still presenting an apparently
insuperable challenge. In this context, the absence of
an ideal cathode material with a high energy- and
power-density is arguably the most serious bottleneck.
There are several underlying reasons for this; not least,
the cost of raw materials and the economy of the
synthesis process but, above all, limitations in
available chemistries to provide the desired
improvements in capacity. A breakthrough came with
the development of polyanion-based cathode materials;
typically, LiFePO
4
and Li
2
FeSiO
4
[1,2]. These materials
can be expected to be both cheaper and safer than
conventional transition metal (TM) oxides.
Unfortunately, they tend to exhibit poor electronic
conductivity a problem which must be addressed by
reducing particle-size or promoting conductivity
through some form of surface treatment. Doping
strategies are also highly desirable for these essentially
insulating materials, especially in the context of
promoting >1-electron redox reactions. Typically,
the materials combination on which we are pinning our
greatest hopes is iron-based polyanion compounds,
where the Fe-site is substituted by Mn to exploit the 2-
electron reaction involving a Mn
2+
Mn
4+
transition.
Recent advances in our efforts to address these
challenges will be reported.
This work has been supported by the Global Climate
and Energy Project of Stanford (GCEP), the Swedish
Energy Agency (STEM) and the Swedish Science
Research Council (VR).
[1] A.K. Padhi et al., J. Electrochem. Soc., 144, (1997) 1609.
[2] A. Nytn et al., Electrochem. Commun.,7, (2005)
156.
294
IN SITU RAMAN SPECTROSCOPY OF THIN FILM BATTERY: STRUCTURE CHANGE
AND PHASE BOUNDARY MOVEMENT OF Li
x
CoO
2
N. Kuwata,
1
Y. Matsuda, J. Kawamura,
1
O. Kamishima,
2
1
IMRAM, Tohoku University, Katahira 2-1-1, Sendai, 980-8577, Japan
2
Faculty of Engineering, Setunan University, Neyagawa, Osaka, 572-8508, Japan
kuwata@tagen.tohoku.ac.jp
Keywords: Solid-state battery, in situ Raman microscopy, Pulsed laser deposition, LiCoO
2
Introduction
All solid-state thin-film batteries (TFBs) using an
amorphous solid electrolyte have been expected as power
sources of various microelectronic devices. We report
recently that a thin-film battery of Li/Li
3
PO
4
/LiCoO
2
can
cycle more than 1000 cycles without capacity fading [1, 2].
The solid-state batteries are usually expected to have
a long cycle life. However, some thin-film batteries show
rapid capacity fading, because of a side reaction or an
irreversible reaction [3]. It is very important to know the
structural change during charge-discharge (in situ) for
understanding the mechanism of capacity fading.
In situ Raman spectroscopy is powerful tool to
detect the structure change of the lithium battery cathode
materials such as LiCoO
2
[4, 5]. In this study, we observed
the structural change of Li
x
CoO
2
cathode in the thin-film
batteries. The change of Raman spectra is related to the
electrochemical property.
Experimental
A thin-film battery of Li/Li
3
PO
4
/LiCoO
2
was
fabricated by pulsed laser deposition (PLD) and vacuum
thermal evaporation (VTE) [1]. A LiCoO
2
cathode of 200
nm thick was deposited by PLD using 4e Nd:YAG laser
on a Pt/SiO
2
substrate at 600C. An amorphous Li
3
PO
4
electrolyte of 1.5 m thick was deposited by PLD using
ArF excimer laser. Finally, a lithium metal anode of 3~5
m was grown by VTD. The thin-film battery was
measured by cyclic voltammetry in a vacuum-tight cell
with optical glass window. At the same time, micro Raman
scattering was measured using an Ar-ion laser (514.5 nm).
Laser power was less than 1mW to avoid annealing.
Results and discussion
Fig. 1 shows a variation of in situ Raman spectra of
TFB where LiCoO
2
, Co
3
O
4
and Li
3
PO
4
are observed. The
LiCoO
2
shows strong Raman bands of A
1g
and E
g
vibrations. The peak intensity and Raman shifts of the
Li
x
CoO
2
cathode varies reversibly depend on the battery
potential. The A
1g
and E
g
peak of Li
x
CoO
2
rapidly
decreases in intensity at around 3.9 V (two-phase region)
and shows lower wavenumber shift. After that, the peaks
are continuously shifted to lower wavenumber at4.0 to 4.4
V.
In addition, the intensity of A
1g
band shows unusual
hysteresis in the two-phase region. This behavior could be
attributed to the phase boundary movement of H1/H2
phases of Li
x
CoO
2
electrode. The heterogeneity of the two-
phase reaction (H1/H2) has been observed by Raman
microscopy.
Fig. 1. In-situ Raman spectra of TFB.
Fig. 2. Raman shift of A
1g
of Li
x
CoO
2
vs. capacity.
References
[1] N. Kuwata, N. Iwagami, Y. Tanji, Y. Matsuda, J.
Kawamura, J. Electrochem. Soc., 157 (4) A521-A527,
(2010).
[2] N. Kuwata, N. Iwagami, Y. Matsuda, Y. Tanji, J.
Kawamura, ECS Transactions, 16 (26) (2009) 53.
[3] N. Kuwata, J. Kawamura, K. Toribami, T. Hattori, N.
Sata, Electrochem. Commun. 6, 417 (2004).
[4] T. Itoh, H. Sato, T. Nishina, T. Matsue, I. Uchida, J.
Power Sources, 68 (1997) 333.
[5] T. Itoh, N. Anzue, M. Mohamedi, Y. Hisamitsu, M.
Umeda, I. Uchida, Electrochem. Commun., 2 (2000) 743.
295
STUDY OF CATHODE MATERIAL FOR LTHIUM ION BATTERY
BY NMR MICRO IMAGING
Yoshiki Iwai,
Daiki Ohno, Junichi Kawamura
Institute of Multidisciplinary Research for Advanced Materials,
Tohoku University, Sendai 980-8577
iy@mail.tagen.tohoku.ac.jp
Keywords: NMR imaging, lithium ion battery, cathode material
Introduction
Imaging techniques are very powerful tool for
scientific research. They provide us new different kind of
aspects from conventional one dimensional spectroscopy.
Recently we have performed NMR micro imaging to
lithium ion battery [1]. We have found out that proton (
1
H)
imaging of electrolyte (propylene carbonate: PC) which
was located near cathode material (LiMn
2
O
4
) showed
characteristic intensity enhancement and distortion. From
several considerations as experimental parameters or
charge-discharge cycling, we concluded the intensity
enhancement and distortion are related to paramagnets in
cathode material; however quantitative approach is not
established yet.
In this study, we consider a theoretical treatment
of intensity enhancement and distortion in NMR imaging
induced by magnetism of cathode material.
Experimental
A LiMn
2
O
4
electrode with polyvinylidene
difluoride (PVDF) and carbon coated on an aluminum foil
was arranged at the center in a glass tube. A polypropylene
(PP) was used as a retainer. The glass tube was filled with
LiClO
4
+PC (1mol/L) electrolyte. Bruker Avance 400 (9.4
T) was used for MRI measurement. The resonance
frequency of
1
H is 400 MHz. A pulse sequence for NMR
imaging is based on spin-echo method (msme), which is
installed in control software (paravision) produced by
bruker biospin. Imaging dimension was 25mm25mm,
spatial resolution and slice thickness was 195m (128128
pixels) and 0.8mm. Echo time (TE) and repetition time
(TR) was 3.495 ms and 300 ms.
Result and Discussion
Fig.1(a) shows NMR imaging of x-z cross section
(left hand side). A white arrow indicates a position of
LiMn
2
O
4
, which is arranged in x-y plane. One can see a
distortion around LiMn
2
O
4
. The intensity profile which is
measured along z-axis (dotted line in Fig.1 (a)) are shown
in Fig.(b). It shows intensity enhancement around center
position; which is also due to magnetism of LiMn
2
O
4
.
In theoretical treatment [2], a density ) (z
measured from NMR imaging is related to NMR
signal
) (t S
,
}
= ) exp( ) ( ) ( t z G i z t S
z
. (1)
where
,
z
G
is gyromagnetic ratio and magnetic gradient.
Basically, the term
z G
z
~ _ (emu/mol) [3]. It
supports the validity of this theoretical treatment. We
believe this technique shows promise as sensitive magnetic
microscope to show distribution of cathode material and/or
inhomogeneous charge-discharge process of lithium
battery.
References
[1] D. Ohno, Y. Iwai, J. Kawamura, Atom Indonesia, 36
(2010), 135-138, to be published
[2] Magnetic Resonance Imaging Physical Principles and
Sequence Design, E. Mark Haacke et al, WILEY-LISS,
p.615
[3] C. M.Julien, A. Ait- alah, A. Mauger, F. Gendron,
Ioncs, 12(2006), 21-32
Fig.1 NMR image of x-z cross section (a) and
intensity profile along z-axis (b)
(a) (b)
z
x
LiMn
2
O
4
A
296
STUDY OF DEFECTS IN LiFePO
4
BY USING PDF ANALYSIS AND MOSSBAUER
SPECTROSCOPY
S. Ferrari,
1
M. Bini,
1
D. Capsoni,
1
V. Massarotti
1
, P. Mustarelli,
1
G. Spina,
2
C. Leonelli
3
1
Dept. of Physical Chemistry, University of Pavia, Via Taramelli, 16 27100 Pavia, Italy
2
Dept. of Physics and Astronomy, Via Sansone, 1 50019 Sesto Fiorentino, Italy
3
Dept. Mat. & Environm. Engineering, Strada Vignolese, 905 41125 Modena, Italy
corresponding: stefania.ferrari@unipv.it
Keywords: lithium battery, LiFePO
4
, pair distribution function (PDF) analysis
LiFePO
4
is a very well known cathode material
for lithium ion batteries. Numerous studies have been
devoted in the last years to the optimization of this
material through the development of new synthesis
routes that favored the formation of particles with
specific morphologies (nanoparticles, hollow sphere,
oriented platelet like shaped) promising for the
electrochemical applications. Olivine prepared by
hydrothermal or precipitation methods has been
recognized as intrinsically defective due to the low
synthesis temperature and time. The most cited defect is
the lithium iron anti-site, which has been determined
both by experimental work [1] and by theoretical energy
calculation [2].
We prepared crystalline LiFePO
4
by means of an
innovative microwave assisted hydrothermal synthesis at
low temperature for few minutes, with the specific aim of
obtaining a defective material. The investigation of the
structural disorder has been carried out, for the first time,
to the best of our knowledge, through the Rietveld
method and the PDF analysis on synchrotron radiation
data (Fig. 1). The defect models have been supported by
Mossbauer spectroscopy, that allowed to characterize the
iron environment and oxidation state. Preliminary results
suggest the presence of Fe
3+
ions and of local disorder
that can be explained on the basis of a lowering of the
symmetry with respect to the orthorhombic Pnmb space
group of the olivine structure. The knowledge of the
defective structure of LiFePO
4
is of primary importance
for an exhaustive comprehension of the electrochemical
properties of this cathode material.
Fig. 1 Graphical comparison between calculated (red
line) and observed (black line) PDF.
References
[1] M. S. Whittingham, Chem. Rev. 104 (2004) 4271
[2] M. S. Islam et al., Chem. Mater. 17 (2005) 5085
297
ELECTROCHEMICAL IMPEDANCE STUDIES OF THIN FILM
COMPOSITE LiFePO
4
/C
G.Bajars, G.Kucinskis, J.Smits, J.Kleperis, A.Lusis
Institute of Solid State Physics, University of Latvia
gunars.bajars@gmail.com
Keywords: electrochemical impedance spectroscopy, LiFePO
4
/C composite, thin film electrode
Introduction
LiFePO
4
is emerging as a promising cathode material for
lithium-ion batteries. In spite of such attractive features
as low cost, environmentally benign and thermal
stability, LiFePO
4
requires further modifications to
overcome limitations involving low electronic
conductivity and slow lithium-ion diffusion. Much effort
has been develop to improve the electrochemical
properties of LiFePO
4
by reducing the particle size, by
coating LiFePO
4
particles with carbon or performing
synthesis of LiFePO
4
/C composite. However, up to now,
it has been difficult to describe the kinetic behavior of
LiFePO
4
materials used for lithium-ion batteries because
many factors including particle size, ionic and electronic
conductivity, as well as phase transition kinetics affect
their electrochemical performance.
Use of thin film electrodes enable to investigate
electrochemical properties of active material in detail.
This is especially useful for poorly conductive materials
because the thickness can be reduced to an extent which
does not significantly affect the electrochemical
behavior. In this study, LiFePO
4
/C composite thin films
prepared by AC magnetron sputtering were investigated
by electrochemical impedance spectroscopy (EIS), which
is a very powerful method to determine the rate of
individual electrode kinetic steps.
Experimental
LiFePO
4
/C thin films were deposited by magnetron
sputtering on polished stainless steel. The target (150
mm in diameter) used for sputtering was obtained by hot
pressing the LiFePO
4
/C powder on a copper pad heated
to 130 C. As-prepared LiFePO
4
/C thin films were
annealed at 550 C for 1 h in the argon atmosphere to
increase the crystallization degree. EIS measurements
were carried out at various states of charge by applying
an AC signal of 10 mV amplitude over the frequency
range from 65 kHz to 1 mHz using a Solartron 1287
electrochemical interface with a Solartron 1260
frequency response analyzer. These tests were performed
using three-electrode cell with metallic Li as counter and
reference electrodes in 1 M LiClO
4
-PC electrolyte.
Results and discussion
Three element equivalent circuit was constructed to
analyze the properties of LiFePO
4
/C electrode -
electrolyte interface (Fig.1). The dependence of
equivalent circuit parameters, such as charge transfer
resistance R
ct
, Warburg impedance Z
W
and constant
phase element CPE on the state of charge were obtained
during the charge-discharge processes. It was found that
during the charging (as well as discharging) processes a
simplified equivalent circuit without Warburg impedance
is obtained (Fig.2) meaning that under the polarization
conditions the Li
+
ion diffusion is not limiting stage.
Fig.1 Nyquist plots and equivalent circuit model for
LiFePO
4
/C 50 nm thin film at OCP (3.4 V)
Fig.2 Nyquist plots and equivalent circuit model for
LiFePO
4
/C 50 nm thin film with applied charging current
(100 A cm
-2
)
The minimum value of charge transfer resistance is
acquired in discharged state which corresponds to
maximum concentration of Li
+
ions in lithium iron
phosphate. During charging Li
+
ions are extracted from
LiFePO
4
/C electrode which is accompanied with increase
of R
ct
. Obviously, the highest charge transfer resistance
should be when FePO
4
phase is dominating in
LiFePO
4
/C electrode.
Conclusions
Well-crystallized LiFePO
4
/C composite thin films were
prepared by AC magnetron sputtering in combination
with successive annealing. The kinetic behavior of
LiFePO
4
/C thin films were measured by the EIS. The
analysis shows that the charge transfer resistance
increases in relation with an appearance of the FePO
4
phase. Obtained results gave evidence that during the
charge-discharge process the Li
+
ion diffusion is not
limiting stage in thin film LiFePO
4
.
298
SYNTHESIS, STRUCTURE AND ELECTROCHEMICAL PROPERTIES FOR
RUTHENIUM-SUBSTITUTED LITHIUM MANGANESE OXIDE
Daisuke Mori,
1
Hikari Sakaebe,
2
Masahiro Shikano,
2
Hiroshi Kojitani,
1
Kuniaki Tatsumi,
2
Yoshiyuki Inaguma
1
1
Department of Chemistry, Faculty of Science, Gakushuin University,
1-5-1 Mejiro, Toshima-ku, Tokyo 171-8588, Japan
2
Research Institute for Ubiquitous Energy Devices, National Institute of Advanced Industrial Science and
Technology (AIST), 1-8-31 Midorigaoka, Ikeda, Osaka, 563-8577 Japan
daisuke.mori@gakushuin.ac.jp
Keywords: Lithium manganese oxide, Cathode material, Lithium battery
Introduction
Lithium batteries have attracted much attention
as the key issue for hybrid electric vehicle (HEV) and
electric vehicle (EV) because of an interest in reducing
emission of carbon dioxide and use of alternative energy
sources. In order to meet these demands, the
development of cathode materials having higher capacity
and energy density is necessary. Layered manganese
oxide, Li
2
MnO
3
, is a promising candidate as an
alternative cathode material having higher voltage, larger
theoretical capacity and lower cost. Li
2
MnO
3
has similar
layered structure to the practical cathode materials
represented as LiMO
2
(M = transition metal) with
layered- rock salt type structure. It consists of lithium
layer and lithium-manganese mixed layer situated
alternately between closed packing oxygen layers.
Li
2
MnO
3
synthesized at low temperature shows
moderately high specific capacity of 260 mAh g
-1
but
poor cycling performance [1]. These were attributed to
low electronic conductivity and structural instability of
during lithium de-intercalation. Whereas, Li
2
RuO
3
with
the similar layered structure to Li
2
MnO
3
shows relatively
high specific capacity and good reversibility because of
the tightly composed host lattice [2]. In addition, it
exhibits lower electronic resistivity of 10 cm at room
temperature. In the present study, we synthesized the
ruthenium-substituted Li
2
MnO
3
to enhance the cycling
performance by stabilizing the host structure during the
lithium (de-)intercalation and the electrochemical
activity due to a decrease in electrical resistivity. The
relationship between synthesis condition, phase relation,
structure and electrochemical properties was
investigated.
Experimental
The ruthenium-substituted lithium manganese
oxide was synthesized by solid-state reaction. Li
2
CO
3
,
MnO
2
and RuO
2
used as starting materials were mixed,
pelletized and then sintered at 600-1200 C for 6-48 hours
in an oxygen gas flow. The powdered samples obtained
were identified by X-ray diffraction method. The sample
composition analysis was performed by SEM-EDS. The
electrochemical properties were investigated using a flat-
type HS cell. The positive electrode comprised the
sample, acetylene black, and PVdF binder coated onto
aluminum current collector. 1 M LiPF
6
in EC/DMC with
a volume ratio of 1:2 and lithium metal were used as the
electrolyte and the negative electrode, respectively.
Results and discussion
Li
2
Mn
1-x
Ru
x
O
3
was synthesized at 1200 C. It
formed two solid solutions in the whole composition
range with a structural transition from Li
2
MnO
3
type to
Li
2
RuO
3
type structure between x = 0.6 and 0.8, although
Li
2
Mn
1-x
Ru
x
O
3
synthesized at 800 C clearly separated
into two phases except for the narrow composition range
of 0 x 0.05. The electrical resistivity of Li
2
Mn
1-
x
Ru
x
O
3
decreased with increasing ruthenium content and
exhibited the lowest resistivity of 5.7 10
2
O cm at room
temperature with the composition of x = 0.8. The
ruthenium substitution would induce to increase the
overlap integral composed of transition metal t
2g
orbitals
and oxygen 2p orbitals in edge-shared MO
6
octahedra.
Fig. 1 shows charge and discharge properties of initial
cycle for Li
2
Mn
1-x
Ru
x
O
3
. The charge and discharge
capacities increased with increasing ruthenium content.
Li
2
Mn
0.4
Ru
0.6
O
3
exhibited a discharge capacity of 192
mAh g
-1
in the first cycle and 169 mAh g
-1
in the tenth
cycle, which indicates a relatively good cycle retention
[3]. The ruthenium substitution is quite effective to
improve electrical conductivity and charge-discharge
performance.
Fig. 1. Charge and discharge profiles of Li
2
Mn
1-x
Ru
x
O
3
in the voltage range of 2.0-4.8 V at 1/10C rate.
References
[1] D.Y.W. Yu, K. Yanagida, Y. Kato, H. Nakamura, J.
Electrochem. Soc. 156 (2009) A417A424.
[2] H. Kobayashi, R. Kanno, Y. Kawamoto, M. Tabuchi, O.
Nakamura, M. Takano, Solid State Ionics, 82 (1995) 25.
[3] D. Mori, H. Sakaebe, M. Shikano, H. Kojitani,
K. Tatsumi, Y. Inaguma, J. Power Sources, in press.
299
Sn@C Nanoparticles in Hollow Carbon Fibers: A Novel Powerful Anode for Li-based Batteries
Yan Yu,
1
Joachim Maier
2
1
School of Material Science & Engineering, Beihang University, Xueyuan Rd. 37#, Beijing,100191, China.
2
Max Planck Institute for Solid State Research, Heisenbergstreet 1, D-70569, Germany
corresponding_yanyu@buaa.edu.cn
Keywords: Li-based BatteriesAnode, Tin
Introduction
As an anode material for Li-based batteries, metallic tin
(Sn) has attracted tremendous interest owing to its huge
theoretical capacity of about 990 mAh/g associated with
the formation of Li
4.4
Sn, which is significantly higher than
that of graphitic carbon (372 mAh/g corresponding to
LiC
6
)
[1]
. However, substantial capacity fading after cycling
is a major obstacle especially for Sn-based materials due to
the enormous volume change during Li alloying and
dealloying. These volume changes caused severe
mechanical strain that induces cracks in the electrode
structure and loss of electrical contact at the anode.
[3]
Many
efforts have been made to increase its performance, such as
modifying electrode configuration, decreasing the particle
size,
[4]
using thin-films,
[5]
and selecting an optimized
binder.
[6]
Recently, the most relevant results have been
obtained by preparing nanostructured tin dispersed in a
carbon matrix
[7]
and carbon-encapsulated hollow tin
nanoparticles.
[8]
It has been demonstrated that in order to
improve the electrochemical performance, this tin anode
materials should be designed with higher content of
metallic tin, smaller particle size, hollow structure, and
only thinner carbon coating layer. Here, we fabricated Sn-
C composite hollow nanofibers as anodes for Li-ion
batteries by coaxial electrospinning technique.
[9]
Experiment
Two viscous liquids were simultaneously fed through the
inner (core, containing tributyltin (TBT) and mineral oil
solution) and outer (sheath, containing polyacrylonitrile
(PAN) solution) capillaries, respectively. The average
diameter of as-spun nanofibers is about 200~300 nm. Then,
the nanofibers were soaked in n-octane overnight to extract
the mineral oil. Finally, they were carbonized at 1000
o
C in
Ar/H
2
atmosphere to obtain the Sn nanoparticles
encapsulated in carbon hollow nanofibers. The obtained
Sn-C composite was investigated by X-ray diffraction
(XRD), scanning electron microscopy (SEM), and
transmission electron microscopy (TEM). Electrochemical
behavior of the test materials was examined via swagelok-
type cells with lithium metal counter electrode, celgard
2400 membrane separator, and electrolyte of 1 M LiPF
6
dissolved in a mixture of ethyl carbonate (EC) and
dimethyl carbonate (DMC) (1:1 in volume ratio). They
were cycle in the voltage range between 3.0 V and 0.01 V
with a battery test system (Arbin MSTAT).
Conclusion
The Sn-C hollow nanofibers offer a buffer zone to
compensate the large volume change during the Li-Sn
alloying and de-alloying process, which result in the
improvement of electrochemical cycle life. Whats more,
the hollow carbon nanofibers also improve the electrical
contact during the cycling. This Sn-C composite is a
promising as a potential anode material for Li-based
Batteries. Moreover, coaxial electrospinning has proved
itself to be a powerful routine for the preparation of
nanomaterials with hollow core/shell architectures.
Acknowledgements
Dr. Yan Yu is grateful for the scholarship from the
Alexander von Humboldt foundation.
References
[1] Y. Idota, T. Kubota, A. Matsufuji, Y. Maekawa, T.
Miyasaka, Science 276, 1395 (1997)
2] O. Mao, R. L. Turner, I. A. Courtney, B. D.
Fredericksen, M. I. Buckett, L. J. Krause, J. R. Dahn,
Electrochem. Solid-State Lett. 2, 3 (1999).
[3] N. Li, C. R. Martin, J. Electrochem. Soc. 148, 164
(2001).
[4] J. O. Besenhard, J. Yang, M. Winter, J. Power Sources
68, 87 (1997).
[5] A. M. Wilson, J. R. Dahn, J. Electrochem. Soc. 142,
326 (1995).
[6] M. Wachtler, M. R. Wagner,M. Schmied, M. Winter, J.
O. Besenhard, J. Electroanal. Chem. 510, 12 (2001).
[7] G. L.Cui, Y. S. Hu, L. J. Zhi, D. Q.Wu, I. Frieberwirth,
J. Maien, K.Mllen, Small 3, 2066 (2007).
[8] W. M. Zhang, J. S. Hu, Y. G. Guo, S. F. Zheng, L.S.
Zhong, W.G. Song, L. J. Wan, Adv. Mater. 20, 1160
(2008).
[9] I. G. Loscertales, A. Barrero, I. Guerrero, R. Cortijo, M.
Marquez, A. M. Ganan-Calvo, Science 295, 1695 (202).
300
GRAPHITE PARTICLES EMBEDDED IN SiCO CERAMIC MATRIX: NEW STABLE
HIGH-POWER ANODE MATERIALS FOR LITHIUM-ION BATTERIES
M. Graczyk-Zajac, L.Toma, C. Fasel, R. Riedel
Institut fr Materialwissenschaft, Technische Universitt Darmstadt, Petersenstr. 23, 64287 Darmstadt, Germany
graczyk@materials.tu-darmstadt.de
Keywords: Li-ion battery, anode, SiOC-graphite composite
Introduction
In the recent years continuous work has been devoted to
the search for new electrode materials in lithium ion
batteries. Currently, mostly graphitic materials are used
as negative electrodes due to low price and high
reversibility, despite relatively low capacity (372 mAh/g)
and inadequacy for high power applications. SiOC
(silicon oxycarbide) and SiCN (silicon carbonitride)
ceramic anode materials have been intensely studied in
the middle of nineties by Dahns group [1]. Nowadays,
there is a genuine interest in electrode materials based on
SiOC and SiCN polymer-derived ceramics (PDCs)
because their chemical and physical properties can be
designed by varying the chemical composition of the pre-
ceramic polymer [2,3,4]. Recently, it has been
demonstrated that the SiCN-graphite composites display
outstanding properties for high current charge/discharge
applications [5].
Results and discussion
In the present work we investigated the SiOC-graphite
composite material. A commercially available siloxane
resin (Polyramic RD-684, from Starfire Systems) was
used as ceramic precursor. The polymer was mixed in
3:1 and 1:1 starting ratio with graphite (SLP 50 graphite
from Timcal Ltd.) and pyrolysed at 1100 and 1300 C.
We studied two series of composites, one pyrolysed
directly after mixing (series R) and second for which the
thermal treatment was preceded by UV-initiated cross-
linking step (series CR). This second experimental
procedure leads to higher carbon content in the SiOC
ceramic matrix as compared to the first series [6]. The
final powders were tested electrochemically in
conventional two electrodes cells by means of cyclic
voltammetry and constant current charging. Elemental
analysis indicated that the Si-O-C composite material is
considerably free carbon rich. The higher amount of free
carbon has been found for CR samples. XRD
measurements confirmed that R und CR ceramic
composites have amorphous nature. Raman spectroscopy
experiment allowed us to determine the form of
disordered carbon present in the samples. We have found
that both types of composite, R und CR, demonstrate
excellent electrochemical behavior in terms of capacity
and cycling stability. In Fig.1 the comparison of cyclic
voltammograms obtained for composite materials,
graphite and pure SiOC ceramic is presented. The best
electrochemical activity resulting in the highest capacity
has been registered for CR 1:1 1100C sample. Due to
the presence of disordered carbons a significant part of
capacity is recovered between 1 and 2V. Fig. 2 presents
the galvanostatic cycling of CR composites and pure
Polyramic ceramic with increasing charge/discharge
current. The highest capacity has been recovered for
sample CR 1:1 1100C, which demonstrates also the best
high rate capability.
Fig. 1 Cyclic voltammogram (2
nd
cycle) of composite
materials (CR), graphite and pure ceramic, 50V/s
Fig. 2 Galvanostatic charge/discharge of composite CR
1:1, 3:1 and pure Poly R pyrolysed at 1100C
Almost 300mAh/g is recovered within 2 hours
charge/discharge. In similar conditions commercial
graphite electrodes recovers only about 150mAh/g.
Conclusion
Our study shows that composite materials based on
graphite and SiOC polymer-derived ceramics are
excellent candidates for anodes in Li-ion batteries. The
presence of high amount of disordered carbons increases
the lithium insertion capacity of composite. Studies
aiming to explain the high rate capability of these
composites are currently in progress.
Acknowledgments
The financial support of SFB595 and SPP1473 DFG
programs is acknowledged.
References
[1] W. Xing et al, J. Electrochem. Soc., 144 (1997) 2410.
[2] D. Ahn et al, J. Power Sources, 195(2010) 3900
[3] M. Graczyk-Zajac et al, J. Eur. Ceram. Soc. 30
(2010) 3235.
[4] H. Fukui et al, ACS Appl. Mater. Interfaces, 2 (2010)
998.
[5] M. Graczyk-Zajac et al, submitted to J. Power
Sources.
[6] S. Martinz et al, J. Eur. Ceram. Soc., (2010), doi:
10.1016/j.jeurceramsoc.2010.11.019.
301
SELF-ASSEMBLY OF LITHIUM BATTERIES WITH 3D ARCHITECTURE
Phil Johns,
1
Matthew J. Lacey,
1
Matthew R. Roberts,
1
Gaber Enany
2
and John R. Owen
1
1
School of Chemistry, University of Southampton, Highfield, Southampton, SO17 1BJ, United Kingdom
2
University of
J.R.Owen@soton.ac.uk
Keywords: 3D-Microbattery, Electrodeposition
Self Assembly of a Battery Cell.
Conventional battery manufacture is a complex operation
involving the processing of materials to achieve a small
particle size, coating onto thin metal foil current collectors,
laminating across a separator and then rolling or folding
into a compact package. This is fine for conventional
batteries, but far from optimum when the requirement is for
unusual shapes and sizes or placement into an inaccessible
location. Self-assembly is described here as a process
which deposits a complete battery cell on a surface of any
shape to fill the available volume. The 3D microbattery
below is an example of an application where self-assembly
is the best technique.
3-D battery concepts have been described [1] as vertical
extensions of thin film (1D) cells to increase the energy
stored per area of footprint, E
f
. The extra dimensions refer
to the direction of the current, which in a 3D cell does not
need to be in the direction perpendicular to the film.
Decoupling the current path (L) from the film thickness
thus allows a short electrolyte path between cathode and
anode, thus reducing the diffusion time (~L
2
/D) that
determines the power density (P
f
~ E
f
/ ). This is important
because it enables the use of poorly conducting electrolytes
in high power applications.
The self-assembly technique described here requires:
- A conducting substrate of arbitrary shape
and processes for:
- Conformal deposition of one electrode.
- Conformal deposition of a solid electrolyte
- Volume-filling deposition of the other electrode.
Electrodeposition of a lithium-ion electrode
The deposition of manganese dioxide by anodic oxidation
of Mn
2+
salts is well known, forming Electrolytic
Manganese Dioxide (EMD). In this work we have
demonstrated conformal deposition of this material onto
Reticulated Vitreous Carbon (RVC) as shown in Fig. 1.
The samples were calcined following Thackeray [3] to
avoid contamination of the lithium electrolyte and to give
structural stability under cycling in LiPF
6
/EC/DME
electrolyte. Some cycling data are given in Fig. 2.
Electrodeposition of Polymer Electrolytes
Polymer electrolytes have been deposited onto MnO
2
coated RVC by electropolymerisation of vinyl monomers
such as acrylonitrile. (See further details in another paper at
this meeting [3].)
RVC A RVC A
RVC A
RVC | EMD
B
RVC | EMD
B
B RVC | EMD
Fig. 1 RVC coated with EMD.
Cycling of MnO
2
-coated RVC in lithium electrolyte.
Acknowledgement
The authors would like to thank the EU FP7 project
Superlion for continued support.
References
[1] J. Long, B. Dunn, D. Rolison, H. White, Chem. Rev.
104 (2004), 4463
[2] El-Enany, G.; Lacey, M. J.; Johns, P. A.; Owen, J. R.
Electrochemistry Communications. 11 (2009), 2320-
2323
[3]Thackeray, M. Progress in Solid State Chemistry. 1997,
25, 1-71.
[4]Matthew J. Lacey,
1
Maciej Sosna,
1
Matthew R.
Roberts,
1
John R. Owen
1
, this meeting.
Superlion
0.00 0.04 0.08 0.12 0.16
2.0
2.5
3.0
3.5
4.0
E
/
V
v
s
.
L
i
Discharge capacity / mAh cm
-2
0.1 C
0.2 C
0.4 C
302
TOWARDS A BETTER UNDERSTANDING OF THE SURFACE REACTIVITY OF
LAYERED LITHIUM OXIDES
N. Andreu, H. Martinez, I. Baraille, R. Dedryvre, D. Gonbeau
*
IPREM/ECP (UMR 5254), University of Pau, Hlioparc, 2 av. P. Angot, 64053 Pau cedex 9, France
*
danielle.gonbeau@univ-pau.fr
Keywords : layered oxides, Li-ion batteries, DFT calculations, surface reactivity
Introduction
LiCoO
2
is the most widely used positive electrode material
of todays lithium-ion batteries. Its theoretical capacity is
272 mAh.g-1, but only ~ 140 mAh.g-1 capacity is reached
in practical cells. This value corresponds to the
deintercalation of half of the Li
+
ions from LiCoO
2
to
Li
0.5
CoO
2
upon charging the battery up to a 4.2 V cutoff
voltage. To obtain higher capacities with LiCoO2 the cells
have to be charged at higher voltages than 4.2V, to remove
more Li
+
ions from the structure. However, increasing the
charge cutoff voltage can lead to structural degradation of
LiCoO
2
and dissolution of cobalt in the electrolyte [1].
Both phenomena result in an increased capacity fading
upon cycling. These last years, it was shown that
modifying the surface of LiCoO
2
particles by application of
a metal oxide or phosphate coating (especially by
aluminium based coating as Al
2
O
3
or AlPO
4
) can
significantly improve the capacity retention upon cycling at
high voltages without loss of the initial reversible capacity.
The appearance of a LiCo
1-x
Al
x
O
2
solid solution between
the material and the Al-based coating has been proposed
and then evidenced by X-ray photoelectron spectroscopy
(XPS) [2,3]. Compounds of this solid solution have been
the subject of structural and electrochemical studies.
Although they show lower reversible capacities due to the
presence of electrochemically inactive Al
3+
ions they show
higher lithium intercalation potentials than LiCoO
2
and are
effective to limit cobalt dissolution at 4.5V (vs Li
+
/Li)[4].
Since dissolution phenomena are linked to acid-base
interactions at the electrolyte/electrode interface, we have
explored the surface acid-base properties of these materials
as compared to LiCoO
2
. In this way, we carried out
adsorption experiments of gaseous probes (NH
3
or SO
2
)
followed by XPS analyses which allow the identification of
active sites (except the weakest ones) and a quantitative
determination of their concentration. The results obtained
evidenced that the initial great basicity of LiCoO
2
decreases
significantly in LiCo
1-x
Al
x
O
2
compounds as a function of x
, which makes these materials less sensitive to acidic attack
in the electrolyte than LiCoO
2
[5].
Results
In this work, our aim was to understand, through a
theoretical approach, the large difference in surface
behavior due to Al/Co substitution and experimentally
evidenced. In this way, we have investigated the adsorption
of gaseous molecules (SO
2
, CO
2
) on layered lithium oxides
such as LiCoO
2
and LiAlO
2
, considering both (001) and
(110) surfaces corresponding to the plane of stacking and
to the densest plane. The calculations have been performed
using the ab-initio total-energy and molecular program
VASP developped at the Universitat Wien [6], a plane
wave basis set (kinetic energy cut-off at 400 eV), PAW
potentials [7] and the generalized gradient approximation
with the Perdew-Wang functional [8]. In each case, the
positions of all the atoms were optimized with a fixed
volume cell. Different adsorption modes are compared and
reveal some complex processes with the coexistence of
several interactions with the electron transfers occurring.
Adsorption on LiAlO
2
surfaces clearly differ from those on
LiCoO
2
for which, for example, SO
2
binds to (110) surface
generating sulfite or sulfate species in relation with the
coverage increase. This study contributes to a better
understanding of the influence of the nature of the cations
and of the cristallographic planes on the surface reactivity.
Fig. 1: SO
2
adsorption on (110) surface of LiCoO
2
References
[1]G.G. Amatucci, J-M. Tarascon, L.C.Klein, Solid State
Ionics, 83 (1996) 167
[2] S. Verdier,L. El Ouatani, R. Dedryvre, F. Bonhomme,
P. Biensan, D. Gonbeau, J. Electrochem. Soc. 154 (2007)
A1088
[3]A.T.Appapillai, A.N.Mansour, J.Cho, Y.Shao-Horn,
Chem. Mater. 19 (2007) 5748
[4] S. T. Myung, N. Kumagai, S. Komaba, H. T. Chung,
Solid State Ionics 139 (2001) 47
[5] L.Daheron, R. Dedryvre, H. Martinez, D. Flahaut, M.
Mntrier, C. Delmas, D. Gonbeau, Chem. Mater. 21
(2009) 5607
[6] G. Kresse, J. Furthmller, Phys. Rev. B 54, 11 169
(1996) / G. Kresse, J. Hafner, Phys. Rev. B 47 (1993) 558
[7] G. Kresse, J. Joubert, Phys. Rev. B 59 (1999) 1758
[8] J. P. Perdew,Y. Wang, Phys. Rev. B 45 (1992) 13244
303
INFLUENCE OF Li-ION DIFFUSION DISTANCE ON THE NEGATIVE ELECTRODE
PROPRIES OF Si THIN PLATELETS FOR Li SECONDARY BATTERIES
Morihiro Saito,
1
Tomoyuki Yamada,
1
Chihiro Yodoya,
2
Akika Kamei,
2
Masato Hirota,
2
Toshio Takenaka,
2
Akimasa Tasaka,
1
and Minoru Inaba
1
1
Department of Molecular Chemistry and Biochemistry, Doshisha University, Kyotanabe, Kyoto, 610-0321, Japan
2
Frontier Center, Oike & Co., Ltd., Kamitoba, Minami-ku, Kyoto, 601-8121, Japan
Email: minaba@mail.doshisha.ac.jp
Keywords: Si thin platelets, high capacity, cycleability, effects of thickness
Introduction
Li-Si alloy systems have attracted much attention as the
negative electrodes in lithium-ion cells because of its high
theoretical capacity (ca. 4200 mAh g
-1
) [1]. However, the
capacity retention of Si is poor, and it shows a high
irreversible capacity in the first charge/discharge cycle.
The poor retention is ascribed to a large volume expansion
and contraction during the charge/discharge cycling, which
causes particle fracture and electrochemical pulverization
(Fig. 1 (a)). Therefore, relaxation of the stress caused by
the large volume change is important to obtain a good
cycleability. Though this concept has been realized by
using Si thin films, such the nano-order thin films limit the
capacity of the cells (Fig. 1 (b)). In the previous study, we
proposed thin platelet-type Si particles (Fig. 1 (c)) and
demonstrated that the shape of thin platelet was quite
effective to improve the cycleability [2-4].
In this study, we prepared five Si thin platelets (Si leaf
Powder