A photo-cross-linkable polymeric binder for silicon anodes in lithium ion batteries

Article abstract of DOI:10.1039/c3ra42447b

A new photo-cross-linkable poly(acrylic acid) (PAA) polymer functionalized with a photoreactive benzophenone group (PAA-BP) was synthesized and examined as a binder for Si-based anodes. Upon UV irradiation, the PAA-BP binders formed an irreversible cross-

Full text of DOI:10.1039/c3ra42447b

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A photo-cross-linkable polymeric binder for silicon
anodes in lithium ion batteries3
Cite this: DOI: 10.1039/c3ra42447b
Yuwon Park,{ab Sueun Lee,{a Si-Hoon Kim,c Bo Yun Jang,d Joon Soo Kim,d Seung
Received 16th May 2013,
Accepted 12th June 2013
M. Oh,b Ju-Young Kim,c Nam-Soon Choi,a Kyu Tae Lee*a and Byeong-Su Kim*a
DOI: 10.1039/c3ra42447b
www.rsc.org/advances
A
new photo-cross-linkable poly(acrylic acid) (PAA) polymer
capacity of ca. 4200 mA h g21, which is an order of magnitude
higher than that of conventional graphite anodes.5–8 Despite these
favorable features, silicon based anodes are still far from
commercialization due to significant challenges such as the
substantial volume change (ca. 300%) during lithiation–delithia-
tion and the safety issues of lithiated silicon. In particular, the
volume change causes high stress and pulverization, and
eventually breaks the electrical contact of the electrode, resulting
in degradation of the electrode and a limited cycle life.9,10 Thus,
significant research efforts have endeavored to alleviate the
aforementioned challenges, to improve the electrochemical
performance of Si-based anode materials.11–14 As one representa-
tive solution, nanostructured Si anode materials15–18 with various
morphologies such as nanoparticles,19,20 nanotubes,21 nano-
wires22 and thin films23 have been extensively developed to
overcome the problem of volume change, and to improve cycle
performance. These nanostructured Si anodes offer potential
solutions by providing a smaller absolute volume change, as well
as the additional benefit of the short diffusion path of the Li+ ion
to enhance kinetic behavior.
Although remarkable improvements in the electrochemical
performance of Si-based anodes have been achieved, relatively less
attention has been paid to the development of the inactive, yet still
important component of the battery electrode, such as polymer
binders. However, recent studies have demonstrated that a robust
polymeric binder plays an important role in controlling the
electrochemical performance of batteries by inhibiting the
mechanical fracture of Si anodes during cycling.24–33 In a seminal
example, Yushin and co-workers have recently employed a new
functionalized with a photoreactive benzophenone group (PAA-
BP) was synthesized and examined as a binder for Si-based
anodes. Upon UV irradiation, the PAA-BP binders formed an
irreversible cross-linked structure through the formation of a new
three-dimensional C–C bond network between the benzophe-
none moiety and the PAA backbone. The photo-cross-linked PAA-
BP binder demonstrated a marginal volume expansion (38%)
after full lithiation, compared to conventional binders and this
resulted in an improved cycle performance of the Si anode over
100 cycles with a high reversible capacity of ca. 1600 mA h g21
.
We attributed this phenomenon to the enhanced mechanical
properties of the photo-cross-linked PAA-BP binder, which were
evaluated using nanoindentation and swelling measurements.
Introduction
Lithium ion batteries (LIBs) have been in the spotlight as one of
the most promising energy storage devices in the era of an energy
crisis. The potential uses of LIBs in powering future portable
electronics, electrical vehicles and energy utility grids have
prompted the development of novel materials and systems to
enhance the energy density and cycle life of LIBs.1–4 Among these
materials, silicon has received more attention recently as a next
generation anode material due to its superior theoretical specific
aInterdisciplinary School of Green Energy and KIER-UNIST Advanced Center for
Energy, Ulsan National Institute of Science and Technology (UNIST), 100 Banyeon-ri,
Eonyang-eup, Ulju-gun, Ulsan 689-798, South Korea. E-mail: ktlee@unist.ac.kr;
bskim19@unist.ac.kr
type of binder, sodium alginate,
a high-modulus natural
bSchool of Chemical and Biological Engineering, Seoul National University, 1
polysaccharide extracted from brown algae, to yield a remarkably
stable battery anode compared with conventional polymeric
binders such as poly(vinylidene fluoride) (PVDF), poly(acrylic acid)
(PAA), and carboxymethyl cellulose (CMC).29 They proposed that
the strong interaction between the carboxylic acid groups of the
binder and the hydrolyzed thin surfaces of SiO2 covering the Si
particles prevented the anode from disintegrating. As another
approach, Choi and co-workers showed that a thermally cross-
linked PAA–CMC binder improved the cycle performance of the Si
Gwanangno, Gwanak-gu, Seoul 151-742, South Korea
cSchool of Mechanical and Advanced Materials Engineering, Ulsan National Institute
of Science and Technology (UNIST), 100 Banyeon-ri, Eonyang-eup, Ulju-gun, Ulsan
689-798, South Korea
dKorea Institute of Energy Research (KIER), Daejeon 305-343, South Korea
Electronic supplementary information (ESI) available: FTIR spectra of the PAA-BP
3
binder, XRD pattern and TEM images of the carbon-coated silicon active material
and representative load-indentation depth curves of the bare and cross-linked PAA-
BP. See DOI: 10.1039/c3ra42447b
{ These authors contributed equally.
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The mixture was then added dropwise to acetone to form a
precipitate. The solid product was washed twice with acetone. The
pure product was prepared by dialysis against deionized water
adjusted to pH 3, for 3 days to remove any residual byproduct. The
degree of substitution was determined to be around 3.7%, on the
anode due to the improved mechanical properties of the three-
dimensionally interconnected network.32 In a separate report,
Konno and co-workers also investigated whether that PAA binder
could be effective in accommodating the large volume expansion
of the SiO-based anode because of the physical and chemical
cross-linked structures in the PAA polymer layers.33 However, even
though this PAA binder assists in building a cross-linked structure,
the chemical interactions between the carboxylic acid groups are
still reversible in their chemical nature due to their susceptibility
to environmental changes such as humidity and temperature.34
Thus, a reversible chemical de-cross-linking of PAA binders can
occur during the processing of the cell assembly in a practical
situation, which in turn leads to the rapid degradation of the Si
anodes and an increased cell impedance during cycling. Thus far,
however, the majority of efforts on the polymeric binder have been
limited to the use of conventional polymers without the
introduction of a new functionality onto the polymeric binder.
Therefore, we report herein the synthesis of robust PAA polymers
which are functionalized with a photo-cross-linkable benzophe-
none (PAA-BP) as a binder for Si-based anodes and demonstrate
the improved cycle performance of the Si anode (marginal capacity
fading over 100 cycles with a reversible capacity of ca. 1600 mA h
1
basis of the H NMR spectrum.
Synthesis of the carbon-coated Si nanoparticles
Si nanopowder (,100 nm, 0.4 g, Aldrich) was mixed with
phthalocyanine (0.1 g, Aldrich) using a mortar, and then the
mixture was heated at 900 uC for 2 h under Ar. This carbon-coated
silicon powder was used as the active material to evaluate the
performance of the binders.
Electrochemical characterization
Galvanostatic charge and discharge cycling (WonATech WBCS
3000 battery measurement system) was performed in the potential
window from 0.0 to 2.0 V vs. Li/Li+ with a two-electrode 2016 coin-
type half cell, where Li metal foil was used as the counter
electrode. The Si active materials were mixed with carbon black
(Super P) and the PAA-BP binder in an 8 : 1 : 2 weight ratio to
fabricate the working electrodes. The first lithium insertion and
extraction capacities were measured at a current density of 100 mA
g21
) due to the irreversible cross-linked structure of the
g
21, and the cycling performance of the half cells was monitored
benzophenone moiety under UV irradiation (Fig. 1). To the best
of our knowledge, this is the first report of using a photoreactive
polymer as a binder for a Si-based anode in lithium ion batteries.
at a current density of 200 mA g21 at 30 uC. To investigate the rate
performance of the half cells, the lithium deinsertion capacities
were measured at current densities of 0.2–20 A g21 at 30 uC. The
electrolyte was comprised of 1.3 M LiPF6 in a mixture of ethylene
carbonate (EC) and diethyl carbonate (DEC) (30 : 70, v/v) with 5
wt% fluoroethylene carbonate (FEC, Soulbrain Co. Ltd.). A
microporous polyethylene film was used as a separator. The cells
were assembled in an Ar-filled glove box with less than 1 ppm of
both oxygen and moisture present. After cycling, the cells were
carefully opened in a glove box to retrieve their electrodes, and the
electrodes were subsequently rinsed in dimethyl carbonate (DMC)
to remove the residual LiPF6-based electrolyte, and dried at room
temperature. These dried electrodes were utilized for the ex situ
measurement of the thickness change.
Experimental
Materials
Poly(acrylic acid) (Mw of 50 000 g mol21) was purchased from
Polysciences, N,N9-dimethyformamide (DMF), 4-hydroxybenzophe-
none, 6-bromo-1-hexanol, N,N9-(dimethylamino)pyridine and 1-[3-
(dimethylamino)propyl]-3-ethylcarbodiimide methiodide were pur-
chased from Sigma-Aldrich. A carbon coating process was used to
provide additional conductivity for the silicon powder.
Synthesis of 4-(6-hydroxyhexyloxy)benzophenone
Photo-cross-linking
4-Hydroxybenzophenone (2.01 g, 10 mmol) and K2CO3 (2.07 g, 15
mmol) were dissolved in 20 ml of DMF, and the solution was
stirred for 30 min at 100 uC. To this solution, 6-bromo-1-hexanol
(1.99 g, 11 mmol) in 10 ml of DMF was added dropwise and the
final solution mixture was stirred overnight at 100 uC. The mixture
was cooled to room temperature and the solvent was evaporated
under reduced pressure. Excess water was added to the solution to
precipitate a white powder, and the product was dried. The
product was recrystallized from ethanol.
The electrodes with the PAA-BP binder were irradiated for 30 min
in air by a UV lamp (UVP, 100 W) at a distance of 15 cm. The
electrodes were placed at the center of the box having dimensions
of 15.5 6 16.5 6 15 cm3. The UV intensity was 391 mW cm22
.
Nanoindentation test of the bare and cross-linked PAA-BP
binders
Nanoindentation experiments were conducted at room tempera-
ture using an XP module of a G200 (Agilent, Santa Clara, CA)
instrument with a three-sided pyramidal Berkovich indenter. Tests
were carried out at a constant indentation strain rate of 0.05 s21
and the thermal drift was maintained below 0.05 nm s21. Sixteen
tests were conducted for each testing condition, so as to obtain
statistically significant data sets. The maximum indentation
depths were maintained at 600 nm, which was less than 1/10 of
the sample thickness. While the continuous stiffness measure-
ment (CSM) data do not show stable trends at very shallow
Synthesis of PAA substituted with the photo-cross-linkable
benzophenone (PAA-BP)
Poly(acrylic acid) (1.0 g, 14 mmol), N,N9-(dimethylamino)pyridine
(DMAP) (0.34 g, 2.8 mmol) and 4-(6-hydroxyhexyloxy)benzophe-
none (0.84 g, 2.8 mmol) were dissolved in 50 ml of DMF at 0 uC. 1-
[3-(Dimethylamino)propyl]-3-ethylcarbodiimide methiodide (EDC)
(1.67 g, 5.6 mmol) was added to the solution. After 30 min, the
mixture was warmed to room temperature and stirred overnight.
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indentation depths, due to intrinsic issues in the nanoindentation
analysis, the data collected at indentation depths greater than 100
nm show stable trends that are nearly constant for both the
hardness and elastic modulus.
However, the cross-linked structure enables us to limit the
deformation of the composite electrode due to the strong
irreversible covalent chemical bond formed between the linear
polymers. It is known that the PAA binder forms a cross-linked
anhydride structure by a dehydration reaction between carboxylic
groups at high temperature (150 uC), which results in the
improvement of the cycle performance due to the effectively
suppressed volume expansion of the Si particle.32,33 However, this
thermal cross-linking of carboxylic acid groups is still reversible
and susceptible to environmental changes such as humidity and
Swelling test of the bare and cross-linked PAA-BP binders
A PAA-BP solution was deposited on Si wafers using a spin-coating
method. The thickness of every film was measured independently
before soaking the film in the diethyl carbonate (DEC) solution
and the average thickness was around 20 nm. The PAA-BP films
were irradiated for 30 min by a UV lamp. The bare PAA-BP films
and cross-linked PAA-BP films were placed in a container filled
with the DEC solution. The film thickness was measured at
predetermined time points (5, 15, and 30 min) by ellipsometry.
temperature, as proved by FTIR measurements (Fig. S1, ESI ).
3
Accordingly, the irreversible cross-linking, regardless of environ-
mental changes, is required for the long-term storage of the
electrodes under practical conditions. The benzophenone (BP)
moiety has been traditionally employed in chemical and industrial
applications as a photo-responsive unit.35,36 The BP moiety of the
PAA-BP polymer provides an irreversible cross-linked structure by
the formation of a covalent bond between BP and the backbone of
PAA upon UV irradiation, leading to the enhanced mechanical and
chemical stabilities that endures environmental changes. More
specifically, an excited BP forms a biradical species under UV
irradiation (lex = 365 nm) that can abstract hydrogen from the
neighboring PAA backbone (C–H) to form a cross-linked structure
by a new C–C bond.
Characterizations
Powder X-Ray diffraction (XRD) data were collected on a Rigaku D/
MAX 2500V PC powder diffractometer using Cu-Ka radiation (l =
1.5405 Å) operated from 2h = 10–80u. The carbon coating
morphology was examined using a field emission transmission
electron microscope (TEM; JEOL JEM-2100F) operating at 200 kV.
1H NMR spectroscopy (VNMRS 600 spectrometer 600 MHz,
Varian, USA) was performed with CDCl3 and DMSO-d6 as the
solvents. The morphology of the electrode was monitored using a
field emission scanning electron microscope (SEM; Nano230, FEI,
USA). The photo-cross-linking process was investigated by ultra-
violet-visible (UV-vis) spectroscopy (Varian, Cary 5000) and Fourier
transform infrared (FTIR) spectroscopy (Varian). The change in the
thickness of the PAA-BP thin film on the SiO2 substrates was
measured by ellipsometry (EC-400 and M-2000 V, J. A. Woollam
Co., Inc.).
In this study, PAA-BP was prepared as shown in Fig. 2(a).35 The
successful conjugation of BP along the backbone of PAA was
characterized using 1H NMR spectroscopy with the degree of
substitution determined to be around 3.7% (Fig. 2(b)). Although
the degree of functionalization can be easily tuned up to 16%, we
limited the degree of functionalization to 3.7% in the current
study, due to the low solubility of the highly functionalized
polymer in water. Polymeric binders should be soluble in solvents
such as water and N-methyl-2-pyrrolidone (NMP) for the prepara-
tion of Si composite electrodes, to obtain a slurry of the active
materials. The photo-cross-linking process of PAA-BP is proposed
as shown in Fig. 3(a), and this process can be clearly investigated
Results and discussion
The schematic diagram in Fig. 1 shows our strategy for how the
PAA-BP binder can accommodate the huge volume change of the
Si anode during lithiation and delithiation. The role of the three-
dimensionally interconnected binder structure is to efficiently
accommodate the repetitive volume changes upon cycling.
Without the cross-linked binders, the composite electrode is
gradually deformed on cycling, due to the linear polymeric
structure of the binders and finally loses the electrical contact
between the electroactive powders.
Fig. 2 (a) Synthetic approach for the preparation of the functionalized PAA-BP
binder. (b) 1H NMR spectrum of the PAA-BP in DMSO-d6 with the corresponding
peak assignments. The degree of BP functionalization was calculated to be 3.7%.
Fig. 1 Schematic illustration of the irreversible cross-linked structure of the PAA-BP
binder to accommodate the volume expansion of the Si anode during charging–
discharging cycles.
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Fig. 3 (a) Proposed mechanism of the cross-linking of the PAA-BP binder. (b) UV-vis
spectra of the PAA-BP binder at different UV-irradiation times. Inset: decrease in
absorbance of BP moiety at 294 nm upon UV-irradiation. (c) FTIR spectra of the PAA-
BP binder (blue solid line) before and (red dotted line) after UV irradiation for 30
min. The characteristic BP peaks at 1600 cm21 (aromatic ring CLC) and 1641 cm21
(carbonyl group CLO) decreased upon UV irradiation. For the IR measurements, PAA
substituted with 16.7% BP was employed to measure the peaks of PAA-BP clearly.
Fig. 4 (a) Cycle performance of (circle) the bare PAA-BP electrode and (triangle) the
cross-linked PAA-BP electrode under UV irradiation. Voltage profiles of (b) the cross-
linked PAA-BP electrode and (c) the bare PAA-BP electrode at various cycle numbers.
(d) Rate performance of (red) the cross-linked and (blue) bare PAA-BP electrodes at
different current rates. The electrochemical experiments for the cycle and rate
performance were performed in the voltage range 0–2 V and 0–3 V vs. Li/Li+,
respectively.
by UV-vis spectroscopy (Fig. 3(b)). The absorbance of the BP moiety
at 294 nm decreased with increased UV irradiation time, due to an
increase in the number of n–p* transitions in the carbonyl group,
resulting in the loss of the carbonyl group. To cross check the
process of photo-cross-linking in the film state, FTIR spectroscopy
measurements were performed (Fig. 3(c)). Before UV irradiation,
the characteristic BP peaks at 1600 cm21 (aromatic ring CLC),
1641 cm21 (carbonyl group CLO), and the PAA peak at 1710 cm21
(carboxylic acid group) were observed. Upon UV irradiation,
however, the peaks corresponding to the BP moiety significantly
decreased, indicating the successful formation of cross-link-
ing.35,36
supported by the negligible thickness change of the cross-linked
PAA-BP electrodes at the first cycle. For that purpose, the thickness
change of the electrodes after full lithiation and delithiation was
measured via an ex situ thickness measurement (Fig. 5). The cells
were disassembled after cycles of full lithiation–delithiation and
the electrode thickness was measured manually. As shown in
Fig. 5(a), after full lithiation until the redox potential of the
working electrodes reached 0 V vs. Li/Li+, the thickness of the
cross-linked PAA-BP electrode increased by 38%, whereas the bare
PAA-BP electrode expanded by 63%. To our surprise, the thickness
of the cross-linked PAA-BP electrode was almost fully recovered to
the original state after full delithiation until the redox potential of
the working electrodes reached 2 V vs. Li/Li+, but the bare PAA-BP
electrode remained as the expanded state, even after full
delithiation, although the volume expansion decreased from 63
to 38%. In spite of the cross-linked PAA-BP electrode showing a
negligible volume change during the first cycle, it was found that
the electrode expanded by 230% after 60 cycles. In the case of the
bare PAA-BP electrode, however, the electrode was too deformed
and eventually detached from the surface of the Cu foil, while the
cross-linked PAA-BP electrode was retained conformally on the Cu
foil, as shown in the inset of Fig. 5(a). The electrode thickness
change of the bare and cross-linked PAA-BP binders was further
examined in the cross-sectional SEM images of the electrodes after
60 cycles, as shown in Fig. 5(b) and (c), respectively. It was clearly
demonstrated that the bare PAA-BP binder showed a more
expanded electrode after cycling, with larger cracks on the surface
of the electrode. This feature also indicates that the cross-linked
PAA-BP binder exhibited a significantly smaller volume change
during cycling, compared to the bare PAA-BP binder, highlighting
the improved structural integrity of the cross-linked system.
The electrochemical performance of the carbon-coated Si
nanopowder with the PAA-BP binder was evaluated (Fig. 4).
Commercial Si nanopowder (,100 nm) was mixed with phthalo-
cyanine and heated at 900 uC for 2 h under an Ar atmosphere to
obtain the carbon-coated Si nanopowder (Fig. S2, ESI ).14 The Si
3
composite electrodes were first prepared with PAA-BP binders, and
then the photo-cross-linking reaction of the BP groups was
performed via the exposure of the electrodes to UV irradiation. As
expected, the cross-linked PAA-BP electrode via UV irradiation
shows a significantly improved capacity retention over 100 cycles,
while a gradual capacity fading was observed in the case of the
bare PAA-BP binder electrode without UV irradiation (Fig. (4a)).
Their corresponding voltage profiles are presented in Fig. 4(b) and
(c), respectively. Moreover, the cross-linked PAA-BP electrode
shows a better rate performance than the bare PAA-BP electrode,
showing that ca. 1420 mA h g21 is delivered even at a specific
current density of 20 A g21 (ca. 12.5 C-rate) (Fig. 4(d)). This
improvement in cycle stability and rate performance, realized
through UV irradiation, is attributed to the three-dimensionally
interconnected binder structure, resulting in a lower deformation
of the composite electrode on volume change. This interconnected
structure allows a sustained electrical contact between the Si and
conducting agent of carbon. The low degree of deformation is also
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Fig. 5 (a) Ex situ measurements for the thickness trace of the PAA-BP electrodes at
full lithiation, delithiation and after 60 cycles. Inset image shows the (left) bare and
(right) cross-linked electrodes after 60 cycles, indicating disintegration of the bare
PAA-BP electrode. The thickness of the bare PAA-BP electrode after 60 cycles was
measured with the film residue. Corresponding SEM images of (b) the bare and (c)
cross-linked PAA-BP electrodes after 60 cycles. The arrows in the SEM images
represent the thickness of the electrode, showing a clear difference between the
samples.
However, it is still highly desirable to alleviate the swelling effect
for the commercialization of Si-based anodes, although the cross-
linked PAA-BP binder efficiently accommodates the volume
change of the Si-based electrodes. This work will be the subject
of our further research.
Fig. 6 (a) and (b) Mechanical properties, hardness and elastic modulus of the bare
and cross-linked PAA-BP electrodes measured by nanoindentation. (c) Swelling of
the bare PAA-BP and cross-linked PAA-BP binders in the DEC solution. The change in
the cross-linked PAA-BP binder is lower than for the bare PAA-BP, resulting in stable
mechanical properties upon wetting in the aprotic electrolyte solution.
Finally, the mechanical properties of the bare and cross-linked
PAA-BP binders were evaluated using a nanoindentation method
bare PAA-BP and cross-linked PAA-BP polymer films were soaked
in the DEC solution, and the thickness change was measured at
various soaking times. According to a report by Yushin and co-
workers, little, to no interaction between the polymeric binder and
the electrolyte is required to achieve stable mechanical properties
in the electrolyte. In accordance with that report, our cross-linked
PAA-BP binder showed little wetting (101.8%) in the DEC solution,
whereas the bare PAA-BP films displayed a relatively larger wetting
(104.9%), suggesting a good mechanical stability of the cross-
linked binder in the electrolyte solution.29
(Fig. 6(a) and (b) and S3, ESI ). The bare PAA-BP electrode showed
3
hardness and elastic modulus values of 0.41 and 6.66 GPa,
respectively, at an indentation depth of 100 nm. Upon cross-
linking, however, the PAA-BP electrode exhibited significantly
enhanced hardness and elastic modulus values of 0.56 and 7.87
GPa, respectively, demonstrating that the effective cross-linking
created the interconnected network within the electrode. Also, the
observed elastic modulus values are superior to those reported in
the case of other conventional polymeric binders such as CMC
and alginate (3–5.5 GPa), and PVDF (0.1 to 1.2 GPa).29 In addition,
the three-dimensionally interconnected structure of the PAA-BP
binders was further confirmed through the wetting behavior of the
binder films in the diethyl carbonate (DEC) solution (Fig. 6(c)). The
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13 N. Liu, H. Wu, M. T. McDowell, Y. Yao, C. Wang and Y. Cui,
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Conclusions
In conclusion, we have demonstrated that a PAA-BP binder
accommodates the volume expansion of a Si-based electrode via
an irreversible cross-linked structure under UV irradiation.
Without UV irradiation, the bare PAA-BP binder shows a
significant deformation of the electrode, resulting in an unstable
cycle stability. Upon UV irradiation, however, the irreversible cross-
linked PAA-BP binder exhibits an improvement in its electro-
chemical performance with a high reversible capacity of 1600 mA
h g21. We believe that this study on the functionalized polymeric
binder will impact on the development of the next generation
lithium ion batteries.
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Acknowledgements
This work was supported by the WCU (World Class University)
program (R31-2008-000-20012-0), Korea Institute of Energy
Research (No. GP2012-0024-03), New & Renewable Energy of
the Korea Institute of Energy Technology Evaluation and
Planning (KETEP) grant funded by the Korea government
Ministry of Knowledge Economy (20113020030060), the ITRC
(Information Technology Research Center) support program
supervised by the NIPA (National IT Industry Promotion
Agency) (NIPA-2012-C1090-1200-0002), and by the National
Research Foundation of Korea (NRF) grant funded by the
Korea Government (MEST) (NRF 2010-0019408).
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