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Investigation on lithium conversion behavior and degradation mechanisms in

Tin based ternary component alloy anodes for lithium ion batteries

Article  in  Journal of Alloys and Compounds · June 2017

DOI: 10.1016/j.jallcom.2017.06.005

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 Journal of Alloys and Compounds 721 (2017) 236e248

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Investigation on lithium conversion behavior and degradation

mechanisms in Tin based ternary component alloy anodes for lithium
ion batteries
Srijan Sengupta a, Arijit Mitra a, Prem P. Dahiya b, Abhinav Kumar a, Manila Mallik a,
Karabi Das a, S.B. Majumder b, Siddhartha Das a, *
a
Department of Metallurgical and Materials Engineering, IIT Kharagpur, Kharagpur, West Bengal, 721302, India
b
Materials Science Center, IIT Kharagpur, Kharagpur, West Bengal, 721302, India

a r t i c l e i n f o a b s t r a c t

Article history: In this article, we investigate into the ternary tin based alloy, thin film anodes for lithium ion batteries,
Received 23 January 2017 specifically into Sn-Sb-Cu system, synthesized via electrodeposition. The alloy electrodes show a stable
Received in revised form discharge capacity of ~600 mAh g
1 discharged at a rate of 200 mA g
1 (~0.3C) for 50 cycles. FESEM
29 May 2017
images show a nano-dendritic, porous microstructure which can help in accommodating high volume
Accepted 1 June 2017
Available online 3 June 2017
expansion during lithiation and prevent the problem of pulverization. The phases present in the pre-
pared anodes are Sn, SnSb and Cu6 Sn5 which are all active towards lithium insertion and extraction. The
behavior of this multi-phase alloy system is examined using X-ray diffraction measurements. At
Keywords:
Composite materials
extremely slow discharge rates, the phases take up lithium at distinct potentials with reactions with
Lithium-ion batteries SnSb, Cu6Sn5 and Sn occurring at 0.86 V, 0.65 V and 0.45 V, respectively. A mechanism, where a lithiated
Electrochemical reactions phase decomposes and internally supplies lithium to the reacting phase, is observed and thereby
Phase transitions lowering the total specific capacity of the anode as a whole when discharged. EIS measurements further
Quantitative X-ray diffraction reveal that there is degradation in the reaction kinetics with increasing cycles. Finally, failure of the
anode is investigated and the cause is identified as the delamination of active material from the current
collector. The problem is successfully removed by replacing Copper current collector with Silver current
collector, where the intermetallic composition reacts at a lower voltage than Tin. Cycling the anode above
this cutoff voltage removes the problem of delamination. However, it is identified that the existing
electrolyte composition in the market, used for graphite anodes, is incompatible with Tin based anodes.
© 2017 Published by Elsevier B.V.

1. Introduction theoretical capacity [1]. The specific capacity of the battery is

With the increasing dependency on high power and energy
demanding portable equipment and devices, Li-ion batteries play a
crucial role as their power sources. Present commercial Li-Ion
batteries based on carbon based anodes fail to meet this
increasing demand due to their lower theoretical capacity
(372 mAh g
1 in case of graphite anode) and hence, new materials
are being developed which can act as suitable anodes with high
* Corresponding author.
E-mail addresses: mukut235711@gmail.com (S. Sengupta), arijmitra@metal.
iitkgp.ernet.in (A. Mitra), ppdahiya@matsc.iitkgp.ernet.in (P.P. Dahiya),
abhinavkumar623@gmail.com (A. Kumar), manila_mallik@metal.iitkgp.ernet.in
(M. Mallik), karabi@metal.iitkgp.ernet.in (K. Das), subhasish@matsc.iitkgp.ernet.in
(S.B. Majumder), sdas@metal.iitkgp.ernet.in (S. Das).
dependent on the specific capacities of both cathode and anode
material, where the battery specific capacity is harmonic mean of
the anode and cathode specific capacities. The capacity of the
battery is generally limited by capacity of the cathode, and
increasing the anode capacity to very high values will not increase
the battery capacity drastically. With the existing state of the art
cathodes present in the market, an anode capacity ranging from
700 mAh g
1 e 1200 mAh g
1 will be sufficient to obtain a high
battery capacity. Tin has a fairly high theoretical capacity of
993 mAh g
1 compared to a graphite anode and hence, is a po-
tential candidate to replace graphite for high energy density bat-
teries [2]. The Nexelion battery developed by Sony Corporation uses
an amorphous tin based anode (Sn-Co-C based) and has increased
the capacity by 30% [3].
Tin takes up lithium via alloying reaction as compared to

http://dx.doi.org/10.1016/j.jallcom.2017.06.005
0925-8388/© 2017 Published by Elsevier B.V.
 S. Sengupta et al. / Journal of Alloys and Compounds 721 (2017) 236e248
intercalation mechanism in graphite anodes. However, it exhibits
poor cycling behavior due to high volume expansion (~300%) dur-
ing lithium insertion which eventually leads to pulverization and
loss of contact from the current collector, which is a common
problem with group IV elements [2,4,5]. In literature, there are
numerous reports on tin based anodes developed for lithium ion
batteries which employ different strategies at microstructural and
materials level to tackle this problem. However, many of such
strategies report abnormally high specific capacity values (higher
than the theoretical specific capacity of tin) for which suitable ex-
planations are not provided by the authors, and hence should be
considered erroneous at this point [6,7]. Among the strategies
which showed some prospect in combatting this specific problem,
a viable one is to alloy tin with a suitable element which is active
towards lithium insertion and extraction, and form an intermetallic
compound which gives a lower volume expansion than tin during
lithium insertion [5]. Intermetallics with the second element as
inactive component can also work and such intermetallics have
been studied extensively for their application as anodes [8e16]. A
further modification to this active-active system can be made by
adding a third element into the system which is inactive towards
lithium insertion and extraction, and can accommodate the volume
expansion in the form of plastic deformation (plastic strain) and
thus, reducing pulverization. This whole strategy can be called as an
active-active-inactive component strategy and is believed to be a
good prospect to be implemented in lithium ion battery anodes.
Antimony is another element which has a higher theoretical ca-
pacity than graphite (~667 mAh g
1) and can be used as the second
active element in the active-active-inactive strategy. Copper, being
a very ductile metal can be used as the inactive element to
accommodate plastic strain.
The problem of volume expansion in Sn based anodes can also
be tackled by microstructural engineering. An open, porous, 3D
nano-dendritic microstructure is favored as a microstructure for
lithium ion battery electrodes due to shorter diffusion lengths of
lithium ions, connected pathways for electron transport, high sur-
face area per unit volume for reaction, facile electrolyte transport
and ample space to accommodate for volume expansion during
lithiation reactions. 1D nanowire microstructure can offer such
advantages, but the width of the nanowires limit the cross sectional
area of electron transport. Superior performance of such 3D ar-
chitectures in lithium ion batteries can be found in the literature
[17e19]. Arpacik et al. have investigated the effect of microstruc-
ture on performance of anode and have reported 3D architecture to
be better than the 0D architecture [18]. The superior electro-
chemical performance of 3D architecture has also been reported by
other scientists [19e21]. The review by Li et al. on the dimension-
ality of nanostructures of Si, Sn, Ge etc based anodes on their per-
formance provides a very good background to determine the
optimum microstructural characteristics [22].
From the processing point of view, Sn-based alloys can be pre-
pared using various synthesis techniques like ball milling [23,24],
reductive co-precipitation [25,26], carbo-thermal reduction [27],
solid-state reduction [10], hydrogen plasma-metal reaction [28]
and electrodeposition [8,9,17,18,29e32]. In general, due to the
volume expansion problem in Sn based anodes, powders are not
preferred as they would require binders to form films over the
current collector. The volume expansion of the anode might cause
the particles to lose contact with the binder and the current col-
lector, causing a capacity fade. Electrodeposition is a suitable
bottom-up method that can be used to synthesize metals and alloys
in a wide range of nanostructures or microstructures. The method
is cheap, fast, simple and environmental friendly [32]. Binder-free
Sn based anodes can be easily prepared with various morphol-
ogies and composition using Electrodeposition. Synthesis of such
237
3D anodes using electrodeposition offers the flexibility in preparing
such a microstructure which is not offered by other synthesis
techniques. Even the composition of the material can tuned very
accurately in the Electrodeposition process. In literature, there are
only a few reports on synthesis of ternary Sn-Sb-Cu alloys for po-
tential applications as anodes for lithium ion batteries
[23,25,26,30]. Various other ternary Sn-M-X alloys (M, X ¼ Sb, C, Co,
Ni etc) have also been investigated to validate the potential of
active-active-inactive component strategy in anodes for lithium ion
batteries [17,24,31,33e38]. Among the Sn-Sb-Cu alloy anodes
studied and proposed in the literature, the Sn65Sb28Cu7 composi-
tion with a dendritic microstructure has the best electrochemical
properties, and has been prepared using electrodeposition [18].
Logically, the compositional (active-active-inactive component)
and microstructural strategy should eliminate a lot of the problems
which are commonly encountered in Sn based anodes. Yet, the
performance of the anodes employing such strategies has improved
marginally. In fact, no attempt has been made till now to identify the
problems with these strategies and propose solutions to mitigate
them. It is extremely important to first identify the reaction
mechanisms in these strategies and understand how this compo-
nent system behaves, which has not been reported yet to best of our
knowledge. A ternary component system of Sn-Sb-Cu consists of
two active elements, Sn and Sb, which take up lithium and an
inactive element Cu which can easily accommodate the volume
expansion during lithium insertion in the form of plastic strain.
However, the behavior of the ternary component system depends
on the phases which are present in it. In general, the anodes con-
taining Sn, Sb and Cu consists of intermetallic compounds of Sn, Sb
and Cu like SnSb, Cu2Sb, Cu6Sn5, etc. along with elemental Sn, Sb and
Cu [8,10,23,25,26,28,30,39]. Lithiation insertion mechanisms in
pure Sn, pure Sb and intermetallic of Sn, Sb and Cu like Cu6Sn5, and
Cu2Sb etc. have also been previously studied via computational
calculations as well as through various spectroscopy techniques
[40e43]. Since the previous studies were made with pure single
phases present in the system, their behavior towards lithium
insertion and extraction when several of them are present in the
system cannot be extrapolated as such. It is reasonable to assume
that the behavior towards lithium insertion and extraction will be
different when several such active phases are present in one system.
The lithiation mechanism in such a multiphase system has not been
reported in the literature to the best of our knowledge and thus
understanding the mechanism of lithium insertion and extraction in
the Sn-Sb-Cu system is one of the prime focuses of this article.
In this manuscript, we have prepared Sn-Sb-Cu active-active-
inactive component alloy anode having a 3D dendritic architecture
and studied the reaction mechanism in this alloy system. Lithiation
mechanism in such Sn-Sb-Cu anodes is studied using ex-situ X-ray
diffraction measurements and Rietveld Refinement. X-ray diffrac-
tion measurements have been used previously for investigations on
behavior of battery electrodes. However, a quantitative validation
using X-ray diffraction was never performed to the best of our
knowledge. The anodes are discharged to specific potentials and
using X-ray diffraction, the phases present at those anodes are
identified. Furthermore, a reaction chart is prepared based on the
information obtained from the X-ray diffraction studies. We have
correlated the lithiation mechanism with the various degradation
mechanisms in these anodes, and proposed a viable solution to
mitigate them.
2. Experimental section
2.1. Sample preparation
The Sn-Sb-Cu alloy anodes were prepared from an electrolyte
238 S. Sengupta et al. / Journal of Alloys and Compounds 721 (2017) 236e248
bath of composition containing L-Tartaric Acid (0.2 mol dm
3),
Antimony (III) Chloride (2.5 mmol dm
3), Tin (II) Chloride Dihy-
drate (10 mmol dm
3) and Copper (II) Sulphate (0.5 mmol dm
3).
The pH was adjusted to 1.5e1.75 using concentrated H2SO4 [18].
Potentiostatic electrodeposition was carried out in AUTOLAB
PGSTAT 302N (Metrohm, Netherlands) with rectangular shaped
battery grade copper foil of area 6 cm2 as cathode and platinum
electrode of area 1 cm2 as anode in a two electrode setup. Similar
setup was employed for potentiostatic Electrodeposition over Silver
Foil (99.95% Purity, Alfa Aesar) with exposed area of 6 cm2. A high
cathodic overpotential of 3 V and 10 V respectively was applied
between the anode and cathode for 1800 s without any convection
in the electrolytic bath so that all the ions (Sn2þ, Sb3þ, Cu2þ and Hþ)
are reduced to 0 oxidation states. The material charging was
0.92 mg. Material charging was kept around 1.9e2.2 mg for the
samples used for mechanism studies to ensure good intensities
during X-ray measurements by increasing the deposition time to
2100 s. The prepared alloys were thoroughly rinsed with distilled
water after synthesis and dried in argon purged oven at 80  C for
24 h to remove any traces of electrolyte and distilled water. The
deposits over silver foil were annealed at 180  C in vacuum furnace
for 3 h before cell preparation to ensure good growth of the
intermetallic interface, as room temperature formation of the
intermetallic interface does not occur.
2.2. Structural characterization
The prepared alloys were structurally characterized using X-ray
diffraction (Bruker D8 Discover, Germany), FESEM (FEI Quanta FEG
250, Netherlands) and Transmission Electron Microscope (FEI
Tecnai G2 operating at 200 kV). The XRD measurements for all the
samples used for mechanism studies were carried out in a two-
theta mode with the source angle kept fixed at 7. The step size
for measurements was taken to be 0.03 . The XRD measurements of
the as-prepared Sn-Sb-Cu alloy over copper current collector were
performed by removing the deposits from the current collector so
as to completely eliminate its signals. Rietveld Refinement was
performed using TOPAS 4 (Bruker, Germany) with background
corrections using Chebyshev Polynomial [44]. Ru et al. have pre-
viously shown that for SnSb (distorted cubic), filling up of all the
interstitial sites of SnSb by lithium(Li2SnSb) results in an increase in
volume by 35% and hence an equal increase in lattice parameter by
~10% [43]. By taking this result as our starting point, we have
assumed that same increase in lattice parameter occurs for SnSb
(rhombohedral) when all its interstitial sites are filled with lithium
to form Li3SnSb in this case. For generating the CIF for Li3SnSb, the
CIF of SnSb (Rhombohedral) (JCPDS e 00-033-0118) was given as
input in JEMS [45]. The Li atoms were added at Wyckoff position e
and the new lattice parameters were taken as a ¼ 4.75761 A and
c ¼ 5.863836 A . The resulting CIF was generated for our starting
point and used for refinement in TOPAS. For Li2SnSb (partially filled
interstitial sites of rhombohedral SnSb), the CIF of SnSb (Rhombo-
hedral) was used as it is during the refinement as partial filling of
interstitial sites of SnSb by Li would not cause a significant change
in lattice parameters or a distortion in the lattice. The CIF files for all
the other phases were obtained from ICDD PDF e 4 database and
used for refinement as it is.
2.3. Coin cell preparation and characterization
The electrochemical characteristics of the synthesized alloy
electrodes were investigated by fabricating CR2032 type coin cells.
Disks of 15 mm diameter were punched out (MSK-T06 MTI Cor-
poration, USA) and used as cathodes in our coin cell. The active
material was weighed in digital balance (Afcoset) with a least count
of 0.1 mg. Lithium metal foils were used as counter and reference
electrodes. LiPF6 (1M) in a 1:1 (by weight) mixture of ethylene
carbonate and diethyl carbonate was used as electrolyte. Celgard
2400, soaked with electrolyte was used as a separator between the
anode and cathode. To fabricate CR2032 type coin cell, the cathode,
separator, and anode were crimped together using a crimping
machine (MT-190e20, MTI Corporation, USA) kept inside a mois-
ture and oxygen controlled (<1.0 ppm) glove box (Labstar, Mbraun
Inc, Germany). Galvanostatic charge-discharge cycling in the po-
tential range 0 and 2 V was carried out with an automated battery
tester (BST8-MA, MTI Corporation, USA). Electrochemical perfor-
mance of anode deposited over copper foil was done at a constant
discharge rate of 200 mA g
1. Electrochemical performance of
anode deposited over silver foil was done at a constant discharge
rate of 175 mA g
1, which corresponds to the same C-Rate as that
done for the electrodeposits over copper foil. Cyclic Voltammetry
was performed between 0 and 2 V at scan rate of 0.1 mV s
1. For
lithiation and extraction mechanism studies, the coin cells were
cycled at an extremely slow rate of 50 mA g
1 till 2nd charge cycle
to identify the redox couples from the differential capacity vs po-
tential plots. The voltages were noted just after the peaks. The coin
cells were then discharged to those potentials at the third cycle and
broken for X-ray measurements.
3. Results and discussions
3.1. Structural and electrochemical characteristics
Fig. 1(a) and (b) show SEM images of the as prepared sample
deposited at 3 V and 10 V respectively. The microstructures in both
the cases reveal a dendritic morphology, which interconnect
themselves around spherical pores which develop due to the evo-
lution of hydrogen bubbles. In case of any tin-based anodes, it is
extremely important to provide porosities in the electrodes to
allow space for the material to expand during lithium insertion. We
observe that the spherical pore size around the dendrites is bigger
in 3 V deposits as compared to 10 V deposits, which indicates that
more space is present for the dendrites to expand during lithium
insertion in case of 3 V electrodeposits. The reason for such an
observation is due to the fact that the rate of Hþ reduction for 3 V
case is lower than that in 10 V case, which in turn increases the
residence time of H2 bubbles over the deposits. The SEI Layer
inherently covers the active material in case of tin based anodes
when discharged for the first time, which are inorganic and brittle
in nature [46]. By allowing such porosities in the sample, we can
reduce the stresses generated during lithiation, which will not
allow the SEI Layer to crumble away. Hence, we have chosen 3 V
samples as the ideal samples for further studies.
Such a microstructure has evolved due to the unique method-
ology employed during electrodeposition. There is a reduction of
Hþ ions at the cathode to molecular H2 gas, which act as a mask
cutting off the contact of electrode and electrolyte at those regions.
Since the contact is removed between the electrolyte and electrode
at the regions where bubbles are formed, no deposition occurs till
the bubble is released. This is observed from the fact that the pores
are spherical which is the shape assumed by a gas bubble in a
liquid. Furthermore, a high cathodic overpotential causes the cat-
ions, which are at the surface of the electrode, to reduce at a much
faster rate than their rate of transport to the surface from the bulk
electrolyte as there is no convection in the electrolyte. This causes a
concentration gradient to be developed in the electrolyte which in
turn is responsible for the phenomena of diffusion limited aggre-
gation and dendritic growth of the deposits. Since diffusion limited
aggregation already occurs, a further increase in overpotential will
result in just more Hþ reduction, due to its large concentration in
 S. Sengupta et al. / Journal of Alloys and Compounds 721 (2017) 236e248 239

Fig. 1. Shows the morphological features of the electrodeposits deposited at (a) 3 V

Overpotential and (b) 10 V Overpotential. The dendritic morphology is observed in
both the cases, though the structure is more open in (a) than in (b).

the electrolyte, which will cause more residual stress and brittle Fig. 2. (a) XRD pattern of the sample with the substrate (Cu), a Sn-Sb intermetallic
deposits and it is not desirable. The phase composition is expected phase (JCPDSe 00-033-0118), Cu6 Sn5 intermetallic phase (JCPDS e 00-045-1488) and
pure tin phase (JCPDS e 01-086-2265) are obtained. (b) X-ray diffractogram after
to remain the same as the increase in overpotential will not
performing Rietveld Refinement indicating the weight fractions of the phases.
significantly affect the concentration gradient of other ions, which
are already having very low concentration in the electrolyte.
Fig. 2 shows the X-ray diffraction pattern of the as prepared alloy Table 1
without the copper substrate along with the refined X-ray pattern. Crystallographic Data of the refined phases.
Rietveld refinement shows SnSb, Cu6Sn5, Sn and Cu phases with Phase Space group Lattice parameters
61.1, 9.9, 22.9 and 6.1% (weight %), respectively. The crystallographic
SnSb R -3m: H a ¼ b ¼ 4.300479 A ; c ¼ 5.297134 A
parameters of the individual phases after refinement are presented Cu6Sn5 C 2C a ¼ 11.027698 A ; b ¼ 7.298571 A ; c ¼ 9.773467 A
in Table 1. The GOF ¼ 1.87 with Rwp ¼ 13.7. The ratio of Sn content to b ¼ 98.869
Sb content in the sample is 1.9. On comparison with the respective Sn I41/a m d a ¼ b ¼ 5.834661 A ; c ¼ 3.17229 A
star patterns in ICDD database, we observe that the lattice is slightly Cu Fm-3m a ¼ 3.615454 A

distorted which is caused due to residual stress from the electro-

deposition. The evolution of hydrogen gas during the deposition is
believed to be the cause for this residual stress as hydrogen atom
can diffuse into the lattice after its formation and thereby causing a
strain in the lattice. During the vacuum drying process, most of this
absorbed hydrogen is ejected out but some residual strain still re-
mains in the lattice. From the calculated weight fractions in the
material, the theoretical capacity is estimated to be 794.2 mAh g
1.
Cyclic Voltammetry of the prepared alloy, shown in Fig. 3, in-
dicates three redox couples, i.e., 0.52 & 0.534 V; 0.713 & 0.977 V;
0.873 & 1.099 V for the lithiation reactions of the active phases Sn,
Cu6Sn5 and SnSb, respectively from 2nd cycle onwards. These
phases are known to be active towards lithium insertion and
extraction, as reported in literature [1,29,42,43,47]. A slight devia-
tion is observed in the region 0.9e1.7 V during discharge in the first
cycle which does not occur in subsequent cycles. A probable reason
for this is the formation of a Solid-Electrolyte Interphase (SEI Layer)
which gives rise to an irreversible capacity during first discharge.
Here no distinct peak is observed in cyclic voltammetry plots for
the SEI formation and hence, its formation is either not associated
with oxide or carbonate formation, or the peaks are convoluted so
that they are not distinctly visible. In case of LiPF6 in EC-DMC
electrolyte, the decomposition reactions of Ethylene carbonate
occurs at around 0.9 V [48]. Another probable reason for this
behavior is the decomposition of residual water present in the
electrolyte after purification [49].
Fig. 4(a) shows the voltage profile of the prepared alloy anode
for the first three cycles discharged at 200 mA g
1 (0.3C-Rate),
240 S. Sengupta et al. / Journal of Alloys and Compounds 721 (2017) 236e248

Fig. 3. Cyclic voltammetry of the anode along with the potential values at the peaks.
Three redox couples are identified for the anode, which corresponds to the reactions of
the three phases present. SEI formation regions extend from 1.1 to 1.7 V and no distinct
peaks are observed as they appear convoluted.

along with the differential capacity plot for the 2nd cycles in
Fig. 4(b). Voltage Profile shows slope changes at around 0.9 V and
0.6 V during discharge, which are caused by the lithium insertion
reactions with different phases. Each electrochemical reaction can
be associated with an equilibrium potential, which derives its roots
from the thermodynamics of the reaction. During Discharge, the
electrons are being supplied to our alloy anode, where lithiated
phases are formed due to lithium-ion reduction. Since, the forma-
tion potential of each of these phases will be constant as it is gov-
erned by this equilibrium potential, we can observe nearly flat
plateaus in the voltage profile. This will be better manifested in the
differential capacity plots, where the phenomenon will be attrib-
uted to a peak around the formation potential. Similar attributes
will be observed in the case of charging, where the lithiated phases
lose lithium ions along with electrons. In our differential capacity
plots, we observe two reduction peaks, but four oxidation peaks.
Due to the high discharge rate of this alloy anode, the reduction
peaks are convoluted in the 0e0.7 V region. A slow discharge rate
will reveal these reduction peaks. It is worthwhile to notice that
there are several redox couples present in the alloy, which corre-
Fig. 4. (a) Voltage Profile for the anode charged and discharged at a rate of 200 mA g
1
spond to different reactions occurring in the alloy system. These along with (b) differential capacity plot for the 2nd cycle. Only two distinct peaks for
reactions schemes will be discussed later in detail in this manu- the reduction half is observed and the other peaks are convoluted. The oxidation half
script along with experimental evidences. reveals several peaks, indicating that the de-lithiation occurs in multiple steps.
Fig. 5 (a) shows the cyclic performance of the prepared alloy
anode at discharge rate of 200 mA g
1 (0.3C). The prepared alloy
shows good cyclic behavior due to the structural integrity attributed to the low frequency region, where the Li diffusion is
contributed by the porous microstructure for 50 cycles. However, responsible for this behavior. Similarly, in mid-frequency region,
there is a sharp drop in the capacity after 60 cycles whose causes the charge transfer reaction at the active material surface is
are investigated and reported later in this manuscript. It is worth- responsible for the semicircle. Finally, the semicircle at high fre-
while to note that the coulombic efficiency is observed to be greater quencies corresponds to the characteristics of the SEI layer. The two
than 100% in the alloy anode. Fig. 5 (b) shows the rate capability of semicircles in the Nyquist plots are overlapping with each other.
the prepared anode at different discharge rates of 100, 200, 400, The Nyquist plots are fitted according to the equivalent circuit di-
and 600 mA g
1 respectively. There is a specific capacity drop in the agram presented in Fig. 5 and the values of the circuit elements are
alloy anode due to shorter reaction times as the rates are increased. presented in Table 2. The electrolytic conductance and the recip-
There is a ~40% drop in capacity between the specific capacities at rocal of Warburg coefficient are virtually unaffected as the number
discharge rates of 100 and 600 mA g
1 in spite of the fact that high of cycles is increased. However, the charge transfer resistance in-
surface area for reaction and shorter diffusion lengths are provided creases progressively, which indicates that the kinetics of the
by the dendritic microstructure. This shows that there is inherent Faradaic reactions is progressively going slower. The slower kinetics
slow reaction kinetics of the phases which are present in the anode has been speculated from the rate capability of the anode as pre-
which contribute to a low power density of the anode in spite of viously mentioned. Due to the slow kinetics of lithium extraction
high energy density offered by them. and insertion in the subsequent cycles, the initial porosity in the
Fig. 6 shows the impedance spectra of the prepared anodes anode is no longer achieved when lithium extraction cycle is
measured at initial stage, after 10th, 30th, and 50th cycles, respec- ongoing. It is also justified by a drop in the double layer capacitance.
tively in the form of a family of Nyquist plots. Each Nyquist plot Therefore, rather than behaving as a porous electrode each time,
consists of two semicircles and a sloping line. The sloping line is the electrode slowly transforms into a flat one with reduced
 S. Sengupta et al. / Journal of Alloys and Compounds 721 (2017) 236e248
Fig. 5. (a) Cycleability curve for the prepared alloy anode discharged at a rate of
200 mA g
1. (b) Rate Capability of the prepared alloy anode at different discharge rates
of 100 mA g
1, 200 mA g
1, 400 mA g
1, and 600 mA g
1.
Fig. 6. Nyquist Plot for the anode for 10th, 30th, and 50th Cycles.
241
porosity after each cycle. The drop in double layer capacitance
values and the increase in charge transfer resistance also imply that
due to decay in kinetics of the reactions some of the lithium is not
extracted reversibly during charging and this result in a small drop
in the capacity after each cycle.
3.2. Studies on lithium insertion and extraction mechanism
For studying the lithiation mechanism via X-ray diffraction, it is
necessary to have good diffractograms of the alloy anode at
different lithiation potentials. Thus, a higher weight of the active
material is required such that the intensity of the underlying cop-
per current collector peaks is not too high compared to other
phases. Also, the alloy anodes must be discharged to different po-
tentials at a very slow discharge rate to allow time for reactions to
complete. For this reason, the samples are electrodeposited under
for longer duration (þ3 V cathodic overpotential, 2100 s) to achieve
higher weight of the deposits. The coin cells are discharged at a low
rate of 50 mA g
1. Also, the diffractograms are obtained with the X-
ray source angle kept fixed at 7. This maintains a constant volume
of irradiation which is necessary for Rietveld Refinement and also
reduces the X-ray penetration depth which results in less intense
peaks of copper current collector. Fig. 7(a) shows the potentials at
which the coin cells are broken during the studies at third cycle
after observing their behavior at 2nd cycles.
During calculation of capacity from the weight fractions ob-
tained using Rietveld Refinement, it is essential to exclude the
weight fraction of Cu as it is mostly from the current collector
which is not a part of active material and furthermore does not take
lithium. Suitable modifications have to be made to the weight
fractions of other phases.
For the phase analysis and Rietveld Refinement to be accurate,
the following conditions must be satisfied:
 The calculated specific capacity from the weight fractions of the
phases must match with the observed capacity obtained in the
third discharge cycle.
 The ratio of total tin to antimony content obtained after
refinement must be the same for all the samples used for the
lithiation mechanism studies since the samples are prepared
under identical conditions.
 After each peak in the differential capacity vs potential plots,
there should be a drastic change in the phase composition of the
sample.
Fig. 7(b) shows the refined X-ray diffractogram for the cell dis-
charged and broken at 0.75 V in the 3rd cycle. The weight fractions
after removing Cu from calculation are presented in Table 3. The
observed and calculated capacities for this sample are 132.76 and
127.32 mAh g
1, respectively with Sn: Sb ratio of 2.37. From the
refined XRD pattern of sample broken at 0.75 V, the phases Li2SnSb
(lithium being inserted in few of the interstitial sites leading to
distortion of the lattice), Cu6Sn5, Sn, Li3Sb (Hexagonal), Li2SnCu and
Li2Sb, respectively are present. This confirms that the peak in
Fig. 7(a) at 0.86 V corresponds mainly to the lithiation reactions of
SnSb. Also, the presence of lithiated compounds of Sb like Li3Sb in
the refinement raises a speculation that free antimony might be
formed after 1st discharge cycle due to some breaking down of
SnSb into Sn and Sb. The expected capacity from the weight frac-
tions of the constituents nearly matches with the actual capacity
obtained in the 3rd discharge cycle. This suggests the presence of
these phases with the weight fractions indicated in Table 3. There is
a slight increase in weight fraction of Cu6Sn5 and slight reduction in
weight fraction of Sn. The reason is believed to be the fact that some
of the tin in the alloy reacts with Cu from the collector due to high
242 S. Sengupta et al. / Journal of Alloys and Compounds 721 (2017) 236e248

Table 2
Values of Equivalent circuit elements from Nyquist Plots.

Cycle RELEC (U) CPE1(U
1 cm
2 s1/2) RCT(U) ZW(U
1 s1/2) CDL(mF) RSEI(U)

0 2.805 1.238  10
4 651.9 0.0001718 3.03  10
5 565.6

10 4.34 1.162  10
3 17.67 0.0108 49.92 9.791
30 4.094 7.93  10
4 22.83 0.015 72.95 9.243
50 4.514 1.33  10
4 48.14 0.0107 4.8 2.453

Fig. 7. (a) Derivative of charge-discharge profile for 2nd cycle when discharged at a rate of 50 mA g
1. The blue lines highlight the discharge potentials in the third cycle for x-ray
measurements, where the refined X-ray diffractograms are presented for (b) 0.75 V Discharged sample, (c) 0.6 V Discharged Sample, (d) 0.3 V Discharged sample and (e) Fully
Discharged Sample in the right hand side of the figure along with their phase fractions. (For interpretation of the references to colour in this figure legend, the reader is referred to
the web version of this article.)

Table 3
Weight fractions for different phases observed at different discharge potential after correction by removing the weight of Copper current collector.

Phases 0.75 V discharged 0.6 V discharged 0.3 V discharged Full discharged

SnSb e e e e
Cu6Sn5 23.0 4.0 e e
Sn 20.6 9.0 e e
Li2SnSb 51.7 16.3 e e
Li3SnSb e 43.6 31.4 e
Li3Sb 4.4 3.8 13.4 5.5
Li2Sb 0.3 e 3.9 22.6
Li2SnCu e 23.3 31.4 e
Li7Sn2 e e 21.3 e
Li22Sn5 e e e 61.8
Cu (only for last column) e e e 10.1
Total Sn 58.4 52.5 50.1 49.1
Total Sb 28.8 31.1 25.8 25.0
Sn/Sb 2.02 1.7 1.94 1.96
Calc. Cap 122.01 238.22 446.36 749.8
Obs. Cap 132.76 250.4 538.64 755.198

diffusivity of copper in tin to form Cu6Sn5 during electromigration
[50e52].
Fig. 7(c) shows the refined X-ray diffractogram for the cell dis-
charged and broken at 0.6 V in the 3rd cycle. The weight fractions
after removing Cu from calculations are presented in Table 3. The
observed and calculated capacities for this sample are 261 and
275 mAh g
1, respectively. The calculated ratio of Sn: Sb in this
sample is 1.7. The refined XRD plot shows the presence of Cu6Sn5,
Li3SnSb, Li2SnCu, Li3Sb (Hexagonal), Li2SnSb and Sn, respectively.
This indicates that the peak at 0.65 V in Fig. 7(a) corresponds to the
lithiation reaction of Cu6Sn5 as weight fraction of Cu6Sn5 is
decreasing along with an increase in weight fraction of Li2SnCu. It is
observed here that the weight fraction of Li3SnSb is increasing due
to more lithium intake by Li2SnSb. Also, there is a sharp drop in the
weight fraction of Sn this time, which can be explained by its re-
action with Cu collector to form Cu6Sn5 and its subsequent lith-
iation reaction to form Li2SnCu. The slight difference in capacity
which is coming up is well within the experimental errors arising
due to refinement and also due to the presence of other compounds
which are not included in Rietveld Refinement, or due to the error
in active material weight measurement.
Fig. 7(d) shows the refined X-ray diffractogram for the cell dis-
charged and broken at 0.3 V in 3rd cycle. The weight fractions after
removing Cu from calculations are presented in Table 3. The
observed and calculated capacities for this sample are 538.64 and
467 mAh g
1, respectively. The calculated ratio of Sn: Sb in this
sample is 1.93. The phases at this potential are identified to be
Li7Sn2, Li2SnCu, Li3SnSb, Li3Sb and Li2Sb, respectively. This peak
corresponds to the lithiation reaction involving Sn. All the inter-
stitial sites of SnSb are filled and Cu6Sn5 has completely reacted
with lithium to form Li2SnCu. Even the weight fraction of Li3SnSb
has not increased to the expected value and some of it has ejected
out its tin atoms to form Li3Sb, causing a change in crystal structure
along with its increase in weight fraction. This is possible as
 S. Sengupta et al. / Journal of Alloys and Compounds 721 (2017) 236e248 243

rhombohedral to hexagonal transformation is favorable due their

similar symmetry, where Li3SnSb is rhombohedral and Li3Sb is
hexagonal. An interesting fact to notice here is the formation of
Li2Sb, which is thought to be caused due to high stress generation in
the system during lithiation. The stress causes an ejection of
lithium from Li3Sb to form Li2Sb, which then enters into tin to form
lithiated tin compounds. The expected capacity obtained from this
refinement is lower than what is observed at this potential. How-
ever, the cause of this could not be concluded from the Rietveld
Refinement and we believe this is purely due to weight measure-
ments of the deposits which are matching with the range of error
for weighing instrument. Also, Cu is being ejected out as Li2SnCu is
formed, which cannot be distinguished from Cu current collector in
any manner. Thus, the weight fractions obtained from Rietveld
refinement also contribute to the error.1
Fig. 7(e) shows the refined X-ray diffractogram for the cell fully
discharged and broken in 3rd cycle. The weight fractions after
removing Cu from calculations are presented in Table 3. Here the
copper of the active material and copper from the current collector
Fig. 8. X-Ray Diffractogram of the fully charged sample showing residual Li3Sb phase.
have to be separated to get correct weight fractions, where Cu from
material is simply the initial Cu content in alloy. The observed and
calculated capacities for this sample are 755.2 and 750.7 mAh g
1, the first charge peak at 0.46 V corresponds to Li ejection from
respectively. The calculated ratio of Sn: Sb in this sample is 1.96. The Li22Sn5 to form Li7Sn2. The peak around 0.21 V in the discharge
only phases found are the lithiated phases Li3Sb, Li2Sb and Li22Sn5, cycle is diffused due to the fact that Sn and Cu atoms are also
respectively. This implies that tin is completely ejected out from knocked out simultaneously from the lattice of Li3SnSb and
Li3SnSb and also Cu is ejected out of Li2SnCu. Furthermore, the Li2SnCu, respectively.
stress induced decomposition of Li3Sb explained earlier is clearly
 
evident. A point which is to be noted here is that Sn and Sb are VOx ¼ 0:46
2:5 Li7 Sn2 þ 4:5 Liþ þ 4:5 e
4Li22 Sn5 (3)
separated in the form of their respective lithiated compounds. So, VRed ¼ 0:21
after lithium is extracted during charging, this Sn and Sb again
recombine to form SnSb. Similar behavior of the ejection of Cu It is evident from the phase analysis and Rietveld refinement
atoms during lithiation occurs for Cu6Sn5. X-ray diffractogram of that the discharge peak at 0.45 V in differential capacity vs potential
full charged sample presented in Fig. 8 shows that complete plot corresponds to the Li-Sn reaction, where Sn reacts with Li to
extraction of lithium is not achieved and some lithium still remains form Li7Sn2. The corresponding delithiation peak in the charge
in the system in the form of Li3Sb. cycle is 0.61 V. The direct formation of Cu6Sn5 from de-lithiated tin
The redox couples in Fig. 7 can be identified from the Rietveld is not possible as the reaction for lithiation of Cu6Sn5 is found to be
refinement data. Since the X-ray diffractogram of a fully charged at 0.65 V in discharge cycle and a certain overpotential is required
sample shows the presence of Li3Sb remaining, the lithium is to cause the backward reaction or in this case the delithiation/
extracted from Li3Sb at the end during the charge cycle. Also, oxidation reaction. This is evident from the shift in the oxidation
lithiated antimony compounds are seen after the first discharge peaks during charge cycle to higher potentials. Thus in this case, the
peak in Fig. 7. However, after the first peak in discharge cycle, re- formation of Cu6Sn5 (delithiated state) is at a lower potential than
actions of SnSb have also occurred. On resolving the first discharge the potential of lithiation for Cu6Sn5. So the oxidation reaction/
peak, we find it to be composed of two peaks at 0.87 V and 0.86 V. delithiation reaction of Li7Sn2 does not yield free Sn directly.
This concludes that the redox couple corresponding to (0.87 V) Red Instead, as Li7Sn2 is getting oxidized, Cu can enter into its lattice to
e (1.06 V) Ox is essentially for Li-Sb reactions and (0.86 V) Red e form Li2SnCu. Furthermore, it is observed from X-ray studies that
(0.97 V) Ox is essentially for Li-SnSb reactions. Li2SnCu ejects Cu atoms between 0 and 0.3 V during discharge. A
high overpotential is present for Cu atoms to enter into the lattice of
  Li7Sn2. However, the amount of Sn generated from oxidation is
VOx ¼ 0:97
SnSb þ x Liþ þ x e
4Lix SnSb ð0 < x  2Þ (1) higher than the amount of nearby Cu. A similar explanation follows
VRed ¼ 0:86
where Sn enters into Li3Sb to form Li3SnSb. The justification for this
explanation lies in the fact that it is already established that 0.96 V
  is the oxidation potential for Li-SnSb reaction. Hence, Li-SnSb
VOx ¼ 1:06
Sb þ x Liþ þ x e
4Lix Sb ðx ¼ 2 = 3Þ compounds have to be present below 0.96 V during charge cycle.
VRed ¼ 0:87
(2)  
VOx ¼ 0:61
7 Liþ þ 2 Sn þ 7e
4Li7 Sn2 (4)
Considering the phases present in full discharged state and VRed ¼ 0:45
phases present in 0.3 V discharged state, it is observed that Li7Sn2
has taken up Li to form Li22Sn5 at ~0.21 discharge potential. Hence, Li7 Sn2 þ 2 Cu/2 Li2 CuSn þ 3Liþ þ 3e
ðVOx ¼ 0:61Þ (5)

1 Sn þ Li3 Sb/Li3 SnSb ðVOx ¼ 0:61Þ (6)

Different Structure models can be used for fitting the X-ray data. A model which
gives an ideal fitting with GOF ¼ 1 might not be supported by other experimental The next redox-pair which has been identified consists of diffuse
data whereas a model with a slightly higher GOF might give an exact match with
other experimental data. For more details, please refer to discussion on Rietveld
region 0.48 Ve0.6 V in discharge cycle and 0.71 V - 0.75 V in charge
Analysis by Brian. H. Toby [53]. B.H. Toby, R factors in Rietveld analysis: how good is cycle of Fig. 7. It is concluded that 0.48 Ve0.6 V is essentially the
good enough?, Powder diffraction, 21 (2006) 67e70. region where Li2SnSb takes up more lithium to form Li3SnSb and
244 S. Sengupta et al. / Journal of Alloys and Compounds 721 (2017) 236e248

the reverse occurs in 0.71e0.75 V region. In this region, we also

expect Sn is reacting with Li2Sb (Hexagonal) which is also present
(in full discharge state, Li2Sb is also present) to form Li2SnSb
(Rhombohedral):
 
VOx ¼ 0:71
0:75
Li3 SnSb4Li2 SnSb þ Liþ þ e
(7)
VRed ¼ 0:48
0:6

Sn þ Li2 Sb/Li2 SnSb ðVOx ¼ 0:71
0:75Þ (8)

Finally, the redox pair comprising of (0.65 V) Red e (0.78 V) Ox
corresponds to lithiation e delithiation of Cu6Sn5.
 
VOx ¼ 0:78
Cu6 Sn5 þ 10Liþ þ 10e
45Li2 SnCu þ Cu
VRed ¼ 0:65
(9)
The lithiation-delithiation behavior is summarised below in
Fig. 9.

3.3. Degradation mechanism and mitigation strategy

Fig. 10(a) shows a SEM image of the anode taken after being
cycled for 5 cycles. It is observed that the initial porosity is reduced
due to the SEI formation. The initial dendritic morphology is intact,
although coated with SEI Layer which protect them from corrosion
and provide additional rigidness. The cracks are observed between
these SEI Layers due to the volume expansion stress, which
essentially isolate the whole coating into individual sections. This
phenomenon is what is commonly known as pulverization. These
individual sections are not in electrical contact with each other
directly, but can very well be connected to each other via the cur-
rent collector. It is very important that the pulverized sections
remain in contact with the current collector as we are tapping out
and pumping the electrons to the active material through the
current collector. However, if these pulverized sections are no
longer in electrical contact with the current collector, there will be
active material loss. This degradation mechanism is known as
delamination. Delamination electrically isolates the active material
Fig. 9. Schematic of (a) lithiation and (b) delithiation behavior of Sn-Sb-Cu anode.
Fig. 10. (a) SEM image of anode after 5 cycles and (b) Image of failed anode showing
the delamination of active material from copper current collector.
and hence, electrons can no longer be pumped into or tapped out of
them during cycling. This will lead to rapid capacity fading and the
battery will cease to be operational. We have encountered this
exact problem with the alloy anodes when deposited over copper
foil, as shown in Fig. 10(b). We encountered a sharp drop in capacity
as shown in Fig. 5(a), which is completely due to delamination of
active material from the current collector. The active material is
delaminated from the current collector, which is visible with naked
eye and also in SEM image. The sections which have not yet
delaminated continue to participate in the lithiation and de-
lithiation process even after pulverization as there is still a
pathway for electrons to reach them.
The presence of an SEI layer over the particles is further
confirmed with the help of TEM. The TEM images of the as-
deposited alloy and the alloy having undergone electrochemical
cycling clearly indicate that the particles are coated with a solid
electrolyte interphase layer, as shown in Fig. 11. In some of the
particles, the inorganic components of the SEI layer such as Li2CO3
and Li2O are present (Fig. 11(b)), whereas in some of the particles
the SEI is composed of amorphous organic components (Fig. 11(c)).
The lattice fringes with an inter-planar spacing of 0.26 nm,
0.395 nm and 0.32 nm can be assigned to the (1 1 0) planes of Li2O
(JCPDS 00-012-0254), (1 1 0) planes of Li2CO3 (JCPDS 00-022-1141)
and (1 0 1) planes of SnSb (JCPDS 00-033-0118). The diffraction
peaks corresponding to Li2CO3 and Li2O are not observed in the X-
ray spectrum of the cycled electrodes obtained for mechanism
studies, probably due to their low weight fractions compared to
other phases.
In our alloy anode material deposited over copper current
 S. Sengupta et al. / Journal of Alloys and Compounds 721 (2017) 236e248
Fig. 11. The TEM images of the (a) as-deposited alloy; and (b), (c) alloy anode after
electrochemical cycling. The high magnification images of the circled regions in (b) and
(c) are provided in the inset. The lattice fringes in (b) correspond to the (1 1 0) and (1 1
0) planes of Li2O and Li2CO3 respectively. In some particles as shown in (c), the SEI is
found to be amorphous, which come from the organic components of the SEI.
collector, the interface between the current collector and active
material is composed largely of Cu6Sn5. Cu6Sn5 itself is an active
phase which participates in the lithiation and de-lithiation re-
actions. During lithiation reaction, it forms Li2CuSn, whose crystal
volume is more than Cu6Sn5. This indicates that the interface swells
245
up during lithium intake and shrinks down when lithium is
extracted. This continuous swelling and shrinking of the interface
will ultimately lead to fatigue failure. Moreover, the reduction re-
action of Cu6Sn5 is earlier than Sn, which is a major component of
our active material. This implies that stopping the interface from
reacting will lithium will lead to a huge capacity to be sacrificed.
For this purpose, we must choose such a current collector,
where the intermetallic interface formed between the current
collector and Sn reacts with lithium at a lower voltage than Sn. This
way, we can stop the cycling at such a voltage where Sn has reacted
with lithium but the intermetallic interface has not. We can never
realize any intermetallic interface containing Sn which does not
react with lithium, and this is the best strategy to prevent delam-
ination. If we use other active materials as current collectors like Al,
Ag, Mg, Au etc, which have a lower lithiation potential than Sn, then
their intermetallics formed at the interface with Sn too will have a
lower lithiation potential than Sn. This will enable us to cutoff the
cycling before the intermetallic interface reacts, while deriving a
high capacity from our active material. Of all the elements
mentioned above, Ag is a suitable current collector for testing this
hypothesis as Al and Mg react with electrolyte used for deposition
and Au is a costlier compared to Ag.
Fig. 12(a) shows the X-ray diffractogram of the alloy deposited
over Ag Foil. New phases Ag3Sn and Ag3Sb have been identified,
which will constitute the interface between the active material and
current collector. The differential capacity plot shown in Fig. 12(b)
reveals that these intermetallics react with lithium at around 0.1 V
vs Liþ/Li couple. Hence, 0.2 V as a cutoff voltage for cycling is ideal
such that the Sn in the active materials react completely with
Lithium whereas the intermetallic interface does not. Fig. 12(c)
shows the cycleability curve for this alloy, when cycled at ~0.3C
Rate (175 mA g
1). We find a similar cycleability behavior with our
alloy anode deposited over Cu Current collector, but the columbic
efficiency recorded is greater than 100%, which indicate that some
parasitic reactions of the electrolyte is occurring with our electrode
when discharge cycle is taking place, and the electrolyte is
incompatible with this electrode. In our case, the coulombic effi-
ciency of nth cycle is defined as the discharge capacity in the nþ1th
cycle divided by charge capacity in the nth cycle, as the discharge
occurs prior to charging in the first cycle. A coulombic efficiency
greater than 100% implies that we are pumping more electrons
during discharge cycle, than what we have tapped out in the pre-
vious charge cycle. Only parasitic reactions like decomposition of
electrolyte, impurity ion reduction etc. will cause an increase in the
consumption of electrons. Continuous Decomposition of the elec-
trolyte will cause a slow fading in capacity with increase in cycle
number. Similar anomaly where the discharge capacity is greater
than charging capacity has also been observed Silicon anodes,
which can only be attributed to incompatibility of existing elec-
trolyte with Group IV elements [19,54].
Fig. 13 shows the condition of the electrode after 50 cycles with
the Cu current collector replaced with Ag Current Collector. No
delamination is observed at all in the electrode and the active
material remains in contact with the silver foil. SEM images in
Fig. 13(b) and (c) indicate pulverization of the electrode material,
which is due to cracking of SEI Layer, but with no signs of active
material loss (delamination). This strategy solved the problem of
delamination encountered earlier. However, the electrochemical
characteristics are still not upto the mark with the existing market
technology, which is mainly due to the electrolyte incompatibility
with this material.
4. Conclusion
The active-active-inactive component strategy based the Sn-Sb-
246 S. Sengupta et al. / Journal of Alloys and Compounds 721 (2017) 236e248
Fig. 12. (a) Refined X-Ray Diffractogram of the alloy prepared over Ag foil indicating
the phases present along with their phase fractions, (b) Differential Capacity plot of the
alloy for the first cycle to identify the reaction potential of the new intermetallic, (c)
Cycleability curve of the alloy anode discharged and charged at 175 mA g
1 (~0.3C-
Rate).
Cu alloy anodes, with 3D nano-dendritic microstructure prepared
using electrodeposition, consists of phases like SnSb, Cu6Sn5, and
Sn, and shows three potentials for lithium intake corresponding to
reactions of three phases with lithium when discharged at
extremely slow rate. The rate capability and EIS results show a slow
reaction kinetics exhibited by such an anode, which limits its
application to low-power devices. During reduction cycle, lithium
intake first occurs in SnSb followed by Cu6Sn5 and Sn, respectively.
Fig. 13. (a) Visual Inspection of the anode after 50 cycles reveal no delamination of the
active material from the current collector, (b) Low magnification image of the anode
reveal pulverized sections to be present in the sample which are in contact with the
current collector (c) High magnification image of the pulverized islands.
SnSb (Rhombohedral) takes up lithium in its interstitial sites after
which further lithium intake occurs by ejection of Sn atoms from its
sites. Similarly, lithium intake in Cu6Sn5 ultimately results in a
knocking out of Cu atoms from their sites. Due to a high stress
generation during lithium intake by Sn, there is a decomposition
reaction of Li3Sb where Li is thrown out of Li3Sb which then enters
into Sn, to form Li-Sn compounds. The slower reaction kinetics
hinders the recombination of Sb-Sn and Sn-Cu, which were sepa-
rated due to ejection of Sn and Cu atoms respectively. The problem
 S. Sengupta et al. / Journal of Alloys and Compounds 721 (2017) 236e248
of pulverization common in group IV based anodes is solved by the
microstructural and compositional features of the anode. However,
delamination mode of failure remains due to reaction of interface
between the current collector (Cu) and the active material, which
causes stress generation and ultimately failure. This problem is
solved by employing Ag current collector, where the intermetallic
interface (Ag3Sn) reacts at a lower voltage than Sn. By cutting off
the cycling before the intermetallic interface reacts, the problem of
delamination is solved while still obtaining a high specific capacity.
The existing market electrolytes are incompatible with this elec-
trode system as they are causing other parasitic reactions at the
electrode surface, which affect the cycleability of this electrode
system.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jallcom.2017.06.005.
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