Electrochemical and In Situ X-Ray Diffraction Studies of the

Reaction of Uthium with Tin Oxide Composites

Ian A. Courtney and J. R. Dahn*
Department of Physics, Dalhousie University, Halifax, Nova Scotia, Canada B3H 3J5
ABSTRACT

We report our electrochemical and in situ x-ray diffraction experiments on a variety of tin oxide based compounds;
SnO, Sn02, Li2SnO3, and SnSiO3 glass, as cathodes opposite lithium metal in a rechargeable Li-ion coin cell. These materials demonstrate discharge capacities on the order of 1000 mAh/(g Sn), which is consistent with the alloying capacity
limit of 4.4 Li atoms per Sn atom, or 991 mAh/(g Sn). These materials also demonstrate significant irreversible capacities
ranging from 200 mAh/(g active) to 700 mAh/(g active). In situ x-ray diffraction experiments on these materials show that
by introducing lithium, lithium oxide and tin form first, which is then followed by the formation of the various Li-Sn
alloy phases. When lithium is removed the original material does not reform. The ending composition is metallic tin, presumably mixed with amorphous lithium oxide. The oxygen from the tin oxide in the starting material bonds irreversibly
with lithium to form an amorphous Li20 matrix. The Li-Sn alloying process is quite reversible; perhaps due to the formation of this lithia "matrix" which helps to keep the electrode particles mechanically connected together.
Introduction

Lithium-ion batteries rely on intercalation, which is the

"reversible insertion of guest atoms into host solids such
that the structure of the host is not significantly altered."1
If lithium can be intercalated into a host that is not altered
by many successive lithium insertions and removals, then
this host will probably have good cycle life in electrochemical cells. The amount of lithium that can be intercalated into a host, or its capacity, is as important as the
cycle life for practical applications. Much of the present
materials research done on Li-ion batteries focuses on
finding electrode materials with improved cycleability
and increased capacity for lithium intercalation.
A conventional anode material is graphite2 which can
intercalate one Li per six C under ambient conditions. The
maximum theoretical capacity of graphite is 372 mAh/g
and its volumetric capacity is 800 mAh/ml.

Much research has been done on Li-metal alloys as

anode materials for lithium and Li-ion cells, see, for

examples, Ref. 3-5. Besenhard et al.6 show that some Limetal alloys have similar or, in the case of silicon, higher
lithium atom packing densities than lithium metal itself.
Therefore alloy anodes are attractive both on a volumetric
and gravimetric capacity basis. The difficulty with metal
alloys is that there is a two and sometimes threefold volume change associated with the alloying of lithium. This

lation as the mechanism seemed unlikely to us, so we

decided to investigate four compounds representative of
those studied by Idota et al., that is, SnO, Sn02, Li2SnO3,
and SnSiO3 glass.
Materials

Experimental

preparationThe SnO and Sn02 used

throughout were commercially available (Aesar, 99.9%).

To confirm the crystal structures of the samples they were
analyzed using a Siemens D5000 diffractometer with a Cu
K x-ray tube and diffracted beam monochrometer operating in the Bragg-Brentano (flat plate sample) geometry.
To prepare Li2SnO3, equimolar amounts of Li2CO3 (FMC)

and Sn02 were dry blended, heated in an alumina heating

boat at 10C/mm to 1000C in air in a Lindberg tube furnace, soaked for 7 h, and cooled slowly to room temperature. The resultant white powder was ground in an auto-

grinder for 20 mm, and was then analyzed by x-ray

diffraction (XRD).
To prepare SiSnO3, equimolar amounts of SnO and Si02
(Aesar, 99.6%) were dry-blended and heated in a graphite
heating boat. The sample was heated at 10C/mm to 1000C

in a constant flow of Argon (Linde, Ultra High Pure

can cause the "cracking" and "crumbling" of the alloy

99.999%) inside a quartz reaction tube 4 ft long and 2 in.

diam inside a Lindberg horizontal tube furnace. The material was soaked at 1000C for 12 h and then quenched to
room temperature by taking the tube out of the furnace. The

anode,6 and subsequently the conductivity of the electrode

an auto-grinder for 20 mm and the powder was analyzed

is reduced and the internal resistance of the cell is in-

creased, resulting in poor cycleability.

Recent developments suggest that alloy systems can be
made to work well as anodes for Li-ion cells. For example,
Fujifilm Celltec Co., Ltd., has announced its plans to man-

ufacture and sell a new battery (trademark STALION),

commencing early 1997, whose anode is an amorphous tinbased composite oxide and not carbon. This new anode is

claimed to have theoretical volumetric and gravimetric

capacity advantages over carbon of four and two times,
respectively. Idota et al.,7 in one of approximately 200
patent applications surrounding the Fuji cell, describe the
preparation and electrochemical behavior of hundreds of
tin, as well as other group IV, oxides and oxide composite
glasses. They claim that the mechanism involved in the
reversible reaction of lithium with the anode electrode is
one of intercalation, and that the process does not involve
the formation of tin. The compounds described in Ref. 7

react with about 4 to 7 Li atoms per tin atom, which is

much larger than that normally observed for intercalation
systems, where a reversible range of one or two lithium
atoms per metal atom is more typical. Therefore, interca* Electrochemical Society Active Member.

372 mAh/g X 2.2 g/ml (density of graphite) = 800 mAh/mL

product was yellow glassy SnSiO3. This was then ground in

using XRD. We also prepared a second sample of this type,

but where the melt was allowed to cool slowly by turning

the furnace off and letting the sample cool inside the furnace. The resultant sample was also analyzed using XRD.
Electrochemical testingElectrodes of the four materials and also of tin metal powder (Aldrich, 99.5%) were

prepared by coating slurries of the respective powders

(85% by weight), Super S carbon black (10% by weight),
and polyvinylidene fluoride (PVDF) (5% by weight) dissolved in N-methyl pyrrolidmnone (NMP) on a copper foil

substrate. The thickness of the coated film was about

300 p.m. After coating, the electrodes were dried for 4 h at

106C and pressed between plates at 2.0 X l0 Pa. The

electrodes were cut into 1.44 cm2 squares and weighed.
Coin-type test cells were constructed using these electrodes in 2320 (23 mm diam and 2.0 mm thick) coin cell
hardware. The cells used a polypropylene microporous
separator, an electrolyte (1 M LiPF6 dissolved in a 30:70
volume percent (v/o) mixture of ethylene carbonate (EC)

and diethyl carbonate (DEC)), and a 125 p.m thick,

1.44 cm2 lithium foil for the negative electrode. Cells were

assembled and crimped closed in an argon-filled glove

box. Details of cell assembly can be found in Ref. 8. All
cells were tested with a constant current of 37.2 mA/g and

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2045

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2046

J. Elect rochem. Soc., Vol. 144, No. 6, June 1997 The Electrochemical Society, Inc.

were charged and discharged between fixed voltage limits.

We comment below on the irreversible capacity of these
materials, defined here to be the difference between the
capacities of the first discharge and of the first charge. We
also prepared cells of SnO for cycling tests between various voltage ranges.
In situ x-ray diffraction measurementsTo investigate
the reaction mechanisms that occur in these materials we

used an in situ x-ray diffraction technique.9 "Belicore"

plastic electrodes1 of SnO, Sn02, Li2SnO3, and SiSnO3

uu

z0

2O0J2)snb3L
w uu
L I4-- i-r
z
C.)
LU

glass were made. To prepare a slurry of these materials we

combined the active material [11.6% by weight], Kynar
Flex 2801 (88% vinylidene flouride and 12% hexafluoro-

(I)

propylene) polymer (5.5% by weight), Super S carbon

black (1.4% by weight), EC/PC [ethylene carbonate!

a(I)

propylene carbonate 50:50 volume percent (yb)] (9.5% by

weight), and acetone (72.0% by weight) in a sealed glass
vial with a stirring bar. The slurry was stirred in a water
bath at 50C for 4 h and was then spread on a glass plate
in air using a doctor blade spreader set to 0.025 in. thickness. Squares of the cathode material (1.44 cm2) were cut
and weighed. The squares were then immersed in diethylether for s mm to remove the EC/PC. Coin-type test cells

(a) SISnO3 - Fast Cool

100

0
0

(c)Li 2SnO3

1000

(d) Sn02

500
0

Li

1000 .

(e)SnO

metal anodes of 125 p.m thickness and area 1.44 cm2 were

LI1

constructed in an argon-filled glove box. The cathodes

20

were first submersed for 5 mm in 1 M LiPF6 dissolved in a

30:70 (v/o) mixture of ethylene carbonate (EC) and diethyl

beryllium sheet (Brush Weliman Electrofusion Products,

Fremont, CA, material grade PF-60, diam 0.850 in. and
0.010 in. thickness). This beryllium sheet is bonded to a
stainless steel can (2325 coin cell hardware) that has a
0.690 in. diam hole in it by a 1:1 weight percent (w/o) solution of Roscobond pressure sensitive adhesive (Rosco, Port
Chester, NY) in water. A wetted microporous film (Celgard
2502) in electrolyte [1 M LiPF6 dissolved in a 30:70 (v/o)
mixture of ethylene carbonate (EC) and diethyl carbonate
(DEC)] is placed on top of the cathode, and the rest of the
cell is constructed as described in the previous section.
One cell each of SnO, SnO2, Li2SnO3, and SiSnO3 glass was

constructed in this manner.

The SnO in situ cell was discharged to 0.0 V and then
charged to 2.5 V using a constant current of 9,3 mA/g in a
special holder that was designed for this purpose and was
never removed from the diffractometer. The SnO cell was
continuously scanned by a Philips x-ray diffractometer
employing a Cu K source, using consecutive 3 h scans.
The Sn02 in situ cell was discharged to 0.0 V and then
charged to 2.5 V using a constant current of 18.6 mA/g at
a constant temperature of 30.0 0.1C. This cell, which

Cells of both Li2SnO3 and SiSnO3 glass were discharged

to 0.0 V and then charged to 2.5 V using a constant current

of 9.3 mA/g. These cells were scanned continuously by

consecutive x-ray scans (220 mm in length) on a Seimens
D5000 diffractometer employing a Cu K source. The cells
were fixed inside the diffractometer in a holder designed
for the purpose.
Results and Discussion
Figure la shows the XRD pattern of the glassy SiSnO3,
where the melt of SnO and Si02 had been quickly cooled
from 1000C. There is a broad feature at near 25C. Figure lb shows the XRD pattern of a similar melt that was
cooled slowly. Note the appearance of crystalline phases in

. .1 ..A

40

60

80

100

SCATTERING ANGLE (deg.)

Fig. 1. X-ray diffraction patterns for materials used; (a) SiSnO3
glass-quenched sample, (b) SiSnO3 cooled slowly, (c} li2SnO3, (d)
5n02, and (e) SnO.

the glassy SiSnO3. The diffraction patterns of Li2SnO3,

Sn02, and SnO in Fig. lc-e, agree with those reported in

the literature.
Figure 2 shows the voltage profiles of Sn, SnO, Sn02,

SiSnO3, and Li2SnO3 over the first 2.5 cycles. The voltage
profiles of the tin oxides and composite oxides in Fig. 2b-e
are fairly similar in appearance. The irreversible capacity
is approximately proportional to the oxygen (as bonded to

tin) content in the respective materials, and furthermore

2
1

0
2

was not located in the diffractometer throughout the

experiment, was scanned 13 times during this first discharge/charge segment at various times which were dictated by the availability of the Seimens D5000 diffractometer. During a scan, the cell was removed from the
charger and the temperature controlled environment and
placed in a special holder inside the x-ray machine that
was designed for the purpose.

500

employing cathodes of the stated materials opposite Li

carbonate (DEC) and were then centered on a circular

I4.1ijl

>

LU

1
0
>

0
2
1

0
2
1

400

800

1200

1600

CAPACITY (mAh/g)

the latter, which are reported in Ref. 11. The SnO-Si02

phase diagram12 shows a eutectic at approximately

equimolar amounts and 900C, so by quenching we form

Fig. 2. Voltage profiles for the first 2.5 cycles of the studied materials; (a) Sn, (b) SnO, (c) 5n02, (d) SiSnO3, and (e) Li2SnO3.

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2047

J Electrochem. Soc., Vol. 144, No. 6, June 1997 The Electrochemical Society, Inc.

the tin oxides and composite oxides appear to cycle better

than tin metal. These observations lead us to surmise a

universal reaction where on the first discharge the lithium

bonds to the oxygen (that was initially bonded to tin),

thereby breaking up the oxide and leaving tin metal and
Li20 (for the case of SiSnO,, there is also Si02). These
regions of Sn can then alloy with Li up to the theoretical
limit of Li4 4Sn. The charge process would be the reverse

with the exception that only some small fraction of the

lithium could be removed from the Li,O. This scenario is

>

summarized by the following reactions

Initial
4.4Li + Sn

Fully discharged Charged again

4.4Li + Sn [1]
Li44Sn
- Li,O + Li4 ,Sn Li,O + 4.4Li + Sn [21

6.4Li + SnO
8.4Li + SnO, - 2Li,O + Li4 .,Sn

IC

>
.5
E

2Li,O + 4.4Li + Sn [3]

6.4Li + SiSnO3 -' Li,O + SiO, + Li445n

Li,O + SiO, + 4.4Li + Sn [4]

8.4Li + Li,Sn03 - 3Li,O + Li4 4Sn

-5.0
0.0

3Li.,O + 4.4Li + Sn [5]

We have assumed that the reversible portion, for the most

part, is the alloying/dealloying of lithium with tin.
In Table I we record the actual discharge capacities (per
gram active) of both the first and second discharges, where
for the second discharge we assume that only capacity less
than 1.0 V corresponds to the alloying of Li with Sn and

that any capacity at voltages higher than 1.0 V results

from the fonnation and deformation of Li,O. The capacities of Eq. 1-5 for the full discharge can be easily calculat-

ed. These are compared to the experimental discharge

capacities, in columns 2 and 4 of Table I. There is a good
agreement. The capacity for the reverse reaction of the cell
in Eq. 1-5 is compared to the second discharge capacity
(below 1.0 V) in columns 3 and S of Table I. Again there is

a reasonable correlation between the calculated and

observed quantities.
Figure 3 shows the differential capacity vs. voltage for
the same materials. The dashed line represents the first
discharge in each case and the solid line is the subsequent
charge and discharge. After the first discharge, the differential capacity of the materials in Fig. 3 are similar which
suggests that a common mechanism exists. This suggests
that these tin oxides and tin oxide composites obey a similar mechanism during lithium insertion, that is, the formation of Li20 followed by the subsequent alloying/dealloying of lithium with tin. In the cases of SnO and 5n02

1.2

0.8

0.4

1.6

VOLTAGE (V)
Fig. 3. Derivative voltage curves (V vs. Ah/gV) for the studied
materials; (a) Sn, (b) SnO, (c) 5n02, (d) SiSnO3, and (e) Li25n03.
Broken line indicates first discharge and solid line represents subsequent charge and discharge.

containing SnSiO, are cycled five times between 1.3 and

0.0 V, peaks in the differential capacity corresponding to

bulk Li-Sn phases emerge, suggesting that aggregation of
the tin atoms still eventually occurs. In order to confirm
that tin and Li-Sn alloys are formed in all of these systems
we carried out in situ XRD experiments.
Figures 4-8 show a sequential report of selected XRD
scans from the SnO cell. At the bottom of each figure there
is a voltage profile (scan number vs. voltage) so one can
identify the point on the cycling curve represented by a
particular XRD pattern. The Li-Sn binary phase diagram'3
dictates that at room temperature there are eight distinct
phases (not including metallic lithium) ranging from lowest to highest lithium concentration; Sn, Li2Sn,, LiSn,
Li7Sn,, Li,Sn,, Li135n,, Li,Sn2, and Li22Sn,, where the crys-

SiSnO3 and Li2SnO,, the presence of substantial amounts

of other "spectator" elements, apparently hinders the for-

tal structures for each of these are known.'4" On each of

Fig. 4 through 8 there are also calculated peak positions
and relative intensities (normalized to 100) for selected
crystal structures so as to ease the identification of the
respective phases. We have only plotted those peaks with
an intensity greater than 10 units (on a scale of 100). In
Fig. 4c we show the three systematic peaks which appear
throughout the experiment, that is, peaks marked "Cell
Part," "BeO," and "Be". The intensity axis for each of the

shown for the charge in Fig. 3a, b, and c are not observed
in Fig. 3d-e. However, it should be emphasized that if cells

scale.

it appears that tin atoms have aggregated to such an

extent that peaks in the differential capacity due to coex-

istence between bulk Li-Sn phases are observed. For

mation of the bulk Li-Sn phases, and hence the peaks

experimental scans is plotted on a logarithmic scale,

whereas the calculated patterns are plotted on a linear

Table I. Experimentally observed and calculated capacities (mAh/g active) for first and second discharges (less than 1.0 V, for observed
quantities) for materials studied.

Material

Sn
SnO
SnO,
SiSnO3

Li,SnO,

Observed first
discharge capacity
(mAh/g)

Observed second
discharge capacity
less than 1.0 V

Calculated first
discharge capacity based
on formation of Li,O

Calculated second
discharge capacity based

and subsequent alloying

on alloying only

(mAh/g)

(mAh/g)

(mAh/g)

800
1200
1450
950

N/A

991
1270
1491

N/A

1200

550

825

650
550

880

873
781
605

1244

652

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2048

SCATTERING ANGLE (deg.)

20

30

100 (a)Scanl2

SCATTERING ANGLE (deg.)

50

40

20

---Sn

O.66V

10 ______

c)

ijjJ

J. Electrochem. Soc., Vol. 144, No.6, June 1997 The Electrochemical Society, Inc.

30

100 (b)Scan 8

C)

O.94V

10 _______
j.... 100 (c) Scan 4

BeO

I-

Cl)

lo:an1jj
Sf0

>-

40

50

ii II lilt II

zu-I
I- 4 I
z

>
0)

a0-

(
20

>0

40

SCAN NUMBER

Fig. 4. In situ XRD results for SnO; (a) scan 12 0.66 V, (b) scan
8 0.94 V, (c) scan 4 1.05 V, (ci) scan 1 1.04 V, and (e) voltaae
profile (scan number vs. voltage) for constant current cycling of cell.
Logarithmic intensities are Dlolted for the scans in reference to the
left-hand vertical axis and )inear intensities are plotted for the calculated patterns (normalized to 100) in reference to the right-hand

vertical axis.

From Fig. 4d (scan 1, 1.04 V) to Fig. 4b (scan 8, 0.94 V)

we can observe the decline of the SnO peaks and an

increase in the background. At Fig. 4a (scan 12, 0.66 V) we

observe broad tin peaks, which confirms that the SnO

loses its oxygen leaving regions of tin metal.

Figure 5c (scan 14, 0.55 V) shows the disappearance of
Sn followed by the emergence of Li2Sn5, whose calculated

SCAN NUMBER
Fig. 5. In situ XRD results for SnO; (a) scan 17 0.41 V, (b) scan
15 0.50 V, (c) scan 14 0.55 V, (ci) scan 12 0.66 V. and (e) voltage profile (scan number vs. voltage) for constant current cycling of
cell. Logarithmic intensities are plotted for the scans in reference to

the left-hand vertical axis and linear intensities are plotted for the
calculated patterns (normalized to 100) in reference to the right.
hand vertical axis. Note the change of intensity scale from Fig. 4.

ken lines in Fig. 8d. It is important to note that crystalline

SnO does not reform. Figure 8a (scan 1, 1.04 V) shows the
first scan on the same scale as Fig. 8b (scan 55, 2.50 V). An

increase in x-ray background has occurred during the

SCATTERING ANGLE (deg.)

peak positions and intensities are shown by the broken

20

lines in Fig. Sc. The Li2Sn5 peaks are gone by Fig. Sa (scan

17, 0.41 V) and we see the emergence on the next Li-Sn

30

(a) Scan 27

phase, LiSn, as shown by the broken lines in Fig. 5a.

Figure 6d shows the calculated intensities for Li7Sn3,

which has strong features at approximately 22 and 38.

One could imagine that we have Li7Sn3 as at Fig. 6c (scan
21, 0.31 V). However, it turns out that all of the remaining

(b) Scan 22

III

Li-Sn phases, that is Li5Sn2, Li13Sn5, Li7Sn2, and Li22Sn5

are structurally similar to each other and to Li7Sn3 as

shown by the calculated peaks in Fig. 7d, again with

strong features at approximately 22 and 38. Throughout

Fig. 6b, a, 7c, and b (scan 22, 0.23 V, scan 27, 0.10 V, scan
31, 0.23 V charge, and scan 43, 0.43 V charge, respectively)
we observe these broad features at 22 and 38. These Li-

zu-j
I.

0.78 V charge) shows the re-emergence of LiSn. From

Fig. 8d-c and b (scan 47, 1.00 V, Scan 50, 1.44 V; and scan

55, 2.50 V respectively) we observe the reformation of

metallic tin whose calculated peaks are shown by the bro-

(d)

- - - U7Sn3

,.

the patterns of Fig. 6a, b, c, 7b, and c arise from these

atom mobility at room temperature.

Further charging the cell to 0.78 V by Fig. 7a (scan 45,

(c) Scan 21

based on the BCC unit cell of lithium14 and differ primarily in the arrangement of Li and Sn on the lattice sites. The
phases also exhibit structural distortions and appropriate
superstructures. It is our opinion that the broad peaks in

the Li-Sn phase diagram which shows that the Li-rich

phases have the highest melting point, and hence lowest

ihIhu

4
6

rich alloy phases Li5Sn2, Li13Sn5, Li7Sn2, and Li22Sn5 are all

phases or mixtures of these phases with poorly developed

long-range order. Apparently the Li and Sn atoms cannot
move effectively in these phases at room temperature to
form long-range ordered structures. This is suggested by

50

40

>

...I.
20

40

SCAN NUMBER
Fig. 6. In situ XRD results for SnO; (a) scan 27 0.10 V, (b) scan
22 023 V, (c) scan 21 0.31 V, (d) valculated peak positions for
Li7Sn3, and (e) voltage profile (scan number vs. voltage) for constant
current cycling of cell. Logarithmic intensities are Dlotted for the
scans in reference to the left-hand vertical axis and linear intensities are plotted for the calculated patterns (normalized to 100) in
reference to the right-hand vertical axis.

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2049

J. Electrochem. Soc., Vol. 144, No. 6, June 1997 The Bectrochemical Society, Inc.

SCATTERING ANGLE (deg.)

SCATTERING ANGLE (deg.)

20

(Y)

30

40

20

50

30

40

50

IU)

LU

F-

>

>

4)

C)

a)
C)
(5

(5

>

20

4-.

40

SCAN NUMBER
Fig. 7. In situ XRD results for SnO; (a) scan 45 0.78 V, (b) Scan
43 0.64 V. (c) scan 31 0.23 V, (d) calculated peak positions for
Li5Sn2, 1i13Sn5, Li7Sn2, and 1i22Sn5 (The majority of peaks for all of

these structures are around 22 and 38), and (e) voltage profile
(scan number vs. voltage) for constant current cycling of cell.
Logarithmic intensities are plotted for the scans in reference to the
left-hand vertical axis and linear intensities are plotted for the calculated patterns (normalized to 100) in reference to the right-hand
vertical axis.

20

40

SCAN NUMBER
Fig. 8. In situ XRD results for SnO; (a) scan 1 1.04 V. (bJ scan
55 2.50 V, (c) scan 50 1.44 V, (d) scan 47 1.00 V, and (e} voltage profile (scan number vs. voltage) for constant current cycling of
cell. Logarithmic intensities are plotted for the scans in reference to

left-hand vertical axis and linear intensities are plotted for the Caiculated patterns (normalized to 100) in reference to the right-hand
vertical axis.

cycling of the cell. This is likely due to the amorphous Li20

and 0.8 V during charging) are difficult to observe com-

insertion and now remains after charging of the cell. The

in situ XRD data together with the electrochemical arguments presented previously strongly supports Eq. 2. The

(Fig. 3b). This is because extended regions of Sn, Li2Sn5,

and LiSn do not form. The presence of a-Si02 apparently
prevents it. Nevertheless, the basic reaction mechanism is
still thought to be the same as for SnO and Sn02, only the
size scale of the tin alloy phases differs. The starting mate-

matrix that formed during the early stages of lithium

remaining issue is that of universality to all of the tin
oxides and tin oxide composites that we have studied.

Figure 9 shows the in situ XRD data for the Sn02.

pared to those for SnO cells where metallic tin forms

Starting with the tin oxide [Fig. 9d, first scan 2.5 V) we

form tin metal which subsequently alloys with lithium

through to Li22Sn5. Figure 9c shows the calculated intensities for the last four phases of Li-Sn, and in Fig. 9b (end of
discharge 0.0 V) we can see the formation of these broad
features at around 22 and 38. Figure 9b is very similar to

Fig. 6a, suggesting the same discharge products for the

SnO and Sn02 cells. Figure 9a (end of charge 2.5 V)
shows the re-emergence of metallic tin as indicated by the
broken lines, but more importantly there is no Sn02. The
shift between the measured and calculated tin peak positions is due to a displacement of this particular x-ray cell
with respect to the goniometer axis.

SCATTERING ANGLE (deg.)

20

50

U)

C-)

>F-

(Fig. lOd) and by discharging to 0.0 V (Fig. lOb) the broad

features at 22 and 38, indicative of the lower Li-Sn alloy
phases, form. The calculated patterns of the lower alloys
are shown in Fig. JOe. The diffraction pattern measured at

U)

Crystalline metallic tin does not form to the same degree,

as in Fig. 8b or 9a. There is an increase in the height of the
metallic tin peaks from Fig. lOd to Fig. lOa, and there is a
broad maximum near 31 which forms when the lithium is

40

4-.

Figure 10 shows some of the in situ XRD results for

SiSnO3. This time we start with an amorphous material

2.5 V differs from those of the SnO and Sn02 cells.

30

z
LU

I-

Z 200

broad maximum is due to small regions (1 nm) of metallic tin. The tin atoms cannot migrate sufficiently to form
large regions of tin metal, presumably because of the presence of Si02 and Li20. Figure 3d shows that the features in

Fig. 9. In situ XRD results for 5n02; (a) end of charge 2.5 V. (b)
end of discharge 0.0 V, (c) calculated peak positions for L155n2,
Li135n5, Li7Sn2, and Li22Sn5 (The majority of peaks for all of these
structures are around 22 and 38), and (dl first scan 2.5 V. The
intensity (in counts per second) is plotted for scans in reference to
the right-hand vertical axis (on a linear scale). There is a change of
scale from (b) to (d). Calculated patterns (normalized to 100) are

region between Sn-Li2Sn5 and Li25n5-LiSn (peaks near 0.7

plotted (on a linear scale) in reference to the right-hand vertical

axis.

removed from the material. It is our opinion that this

the differential capacity associated with the two-phase

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2050

J. Electrochem. Soc., Vol. 144, No. 6, June 1997 The Electrochemical Society, Inc.

reacted on discharge, the starting material does not form

SCATTERING ANGLE (deg.)

30

20

again. Sn peaks do not form after the first charge as

40

50

0
1

04

observed for SnO, Sn02, and SiSnO3. This could be due to

the fact that for Li2SnO3 3 mol of Li20 per mole of Li2 Sn03
form during the discharge (Eq. 5). This higher concentration of lithia could prevent large regions of tin metal from
forming and as a result we do not observe well defined tin
peaks in our XRD scan.

We believe that the lithia matrix that is formed during

the initial stages of lithium insertion in these materials
acts as a 'glue," which helps to hold the Li-Sn regions
together through the large volume changes in the alloy-

zw
Iz
Cl)

ing/dealloying process. This is based on the reversibility of

the processes as demonstrated electrochemically when

compared to metallic tin (Fig. 2). Table II shows the calculated volume per mole of Sn atoms in each of the respec-

tive Li-Sn phases. Notice the relatively small volume

increase factor to LiSn, 1.53, and the large volume increase factor to the alloying limit of Li22Sn5, 3.59.
Fig. 10. In situ XRD results for SiSnO3; (a) end of charge 2.5 V,
(b) end of discharge 0.0 V, (c) calculated peak positions for Li5Sn2,
Li135n5, Li75n2, and U225n5 (the majority of peaks for all of these

structures are around 22 and 381, and (d) first scan 2.5 V.
Logarithmic intensities are plotted for scans in reference to the lefthand vertical axis and linear intensifies are plotted for the calculated patterns (normalized to 100) in reference to the right-hand vertical axis.

An investigation of the crystal structures of each of the

various phases shows that both Li2Sn, and LiSn are layered structures, whereas higher concentrations of lithium
lead to more complicated structures where layers or tunnels of Li atoms are not formed. Figure 12 is a diagram of
the crystal structures of Li2Sn5 and LiSn. The crystal
structure of Li2Sn5 has some prominent features which are
outlined by the solid lines in the right-hand diagram of
Fig. 12a. The lithium resides within pentagonal structures
between the layers of Sn atoms. There are also square and

triangular sites which exist. If all the triangular and

rial does not reappear during the charge as can be determined by comparing Fig. iOa and d.

Figure ii shows some of the in situ XED scans for

Li2SnO3. Figure lid shows the first scan (2.5 V) and the
corresponding calculated peaks for Li2SnO3 are shown by
the broken lines in that figure. When the cell is fully dis-

charged, the broad features at 22 and 38, which are

indicative of the lower Li-Sn alloy phases, appear

(Fig. lib 0.0 V). The original peaks of Li2SnO3 do not
entirely disappear for this cell. The first discharge capacity for this cell was approximately 1000 mAh/g instead of

approximately 1200 mAh/g for other cells (Fig. 2e).

Therefore we believe that not all of the starting material

has reacted in this in situ cell. By the end of charge

(Fig. ha 2,5 V) the lower Li-Sn phases are no longer pre-

sent and, with the exception of the Li2SnO3 that has not

SCATTERING ANGLE (deg.)

20
100
3

0r

P1

10
100
3

10
>.

U)

zLu

30

50

40

TT
(a) End ot Charge

II iIll .(!l ii
{b) End of Discharge - 0.0 V

Ii

I I.i' IS Jill iiii 4....

(C)

Jll

Li5Sn2, Li13Sn5,

square sites were filled with Li, a stoichiometry of LiSn

would result. However there would be three inequivalent
types of Li atoms. A slight skewing to create an overall
coordination of 8 Sn per Li (square sites) and vice versa
results in the crystal structure shown in Fig. i2b, or LiSn.
Over certain ranges the Li-Sn alloy structural transitions
are minimally disruptive and so should be quite reversible.
We cycled cells of SnO over various voltage ranges in
order to confirm that the first two Li-Sn phases should
demonstrate good reversibility. Figure 13 shows the results
of two of these cycling experiments. In Fig. 13a we show a
cell that has been cycled between 1.3 and 0.0 V Over this
voltage range the process is not very reversible. We believe
that this is due to the cracking and crumbling of the material by the large volume increases that are involved in realizing the lower Li-Sn alloy phases. Figure 13b shows the
results for a SnO cell that has been discharged to 0.4 V and
then charged to 1.3 V for ten cycles. We can see that this
process is more reversible, and that the phase definition as
indicated by the plateaus seems to improve with cycling.
Since the first two Li-Sn phases, that is Li25n5 and LiSn,

are layered and related structures, then over this region

the reaction with Li is more reversible than if we were to
react over the full range of Li-Sn alloys.
Figure 14 is a schematic of the reaction mechanism that
occurs in the tin oxides and tin oxide composites that we
have studied. In the diagram we assume SnO as the starting material, but this could he easily replaced by any of
the other starting materials by simply adjusting the stoi-

chiometry of the added lithium. We first introduce lithium

forming a Li2O "matrix-glue" which assists in the reversibility of the subsequent alloying/dealloying by resisting

1i7Sn2 Li229n5

100
3
10

: :;j

j L_.4_,;

i1T5u20L.3

Fig. 11. In situ XRD results for Li25n03; (a) end of charge 2.5 V,
(b) end of discharge 0.0 V, (c) calculated peak positions for Li5Sn2,
Li13Sn5, Li7Sn2, and LiSn5 (the majority of peaks for a11 of these

structures are around 22 and 381, and (d) first scan 2.5 V.
Logarithmic intensities are plotted for scans in reference to the lefthand vertical axis and linear intensities are plotted for the calculated patterns (normalized to 100) in reference to the right-hand ver-

tical axis.

Table Il. Calculated volume per mol Sn (cm3/mol) and volume

increase factor (over Sn metal) for each of U-Sn alloy phases.
Phase

Sn
Li2Sn,
LiSo
Li75n3
Li55n2

Li3Sn,

Li75n2
Li,25n5

Volume per mol Sn (cm/mol) Volume increase factor

16.18
19.88
24.74
36.95
44.64
45.45
48.31
58.14

1.00
1.23
1.53

2.28

2.76
2.81
2.99
3.59

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2051

J. Electrochem. Soc., Vol. 144, No. 6, June 1997 The Electrochemical Society, Inc.

(a) Li2Sn5
a

SI

S SSS II II, 51551555

. 5

. S

SIl S SISSS
55
US
SS
SS

S
I

Li

S
Fig. 12. Crystal structure diagrams for; (a) L125n5 and (b) LiSn.

(b) LiSn

S S S.. S
SSS US SS

S
C

SS
S5ISU
SS

.U

.5
I

S
U
.U .

crumbling under the large volume changes in the alloying

process. The breakdown of the oxide into Li20 and Sn is

for the most part irreversible. The further insertion of

lithium through to LiSn involves the formation of lithium

layered structures and that these structurally related

phases could be considered to be lithium intercalates.
Further lithium insertion through to Li22Sn5 involves the

insertion of lithium into unlayered structures together

with large volume increases.
0

400

800

1200

Conclusion
SnO, Sn02, Li2SnO3, and SiSnO3 glass all react reversibly with lithium in a similar manner. Lithium first
reacts irreversibly in a manner consistent with the formation of amorphous Li20 and Sn, then further Li alloys with
Sn in the manner suggested by the Li-Sn phase diagram.
The reversibility of the alloying process may be influenced
by the Li20 matrix which may act to retard the aggregation of tin atoms into large coherent regions. Once large tin
regions form, the large volume differences between coexisting bulk Li-Sn phases may induce cracking and crum-

>
LU

(5

bling of the structure, and capacity loss. This effect is

apparently not as severe when the Li-Sn phases are structurally related, as they are for the first two Li-Sn phases,
Li2Sn5 and LiSn. Materials of these types have the theo-

retical potential to have a greater capacity for lithium

than the present anode material of choice, namely,

400

800

1200

CAPACITY (mAh/g)
Fig. 13. Cycling of SnO over different voltage ranges; (a) 10
cycles between 1.3 and 0.0 V and (b) 10 cycles between 1.3 and
0.4 V.

graphite.
Further work is warranted on these materials, particularly focusing on ways to capitalize on the factors that
tend to make the reaction reversible. The materials also
show large irreversible capacity which may present technical challenges for their implementation as anodes in Liion cells.
Manuscript submitted Nov. 12, 1996; revised manuscript
received Feb. 19, 1997.

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20b2

J. blectrocflem. Soc., vol. 144, No. 6, June 1997 (c) The Electrochemical Society, Inc.

2. J. R. Dahn, T. Zheng, Y. Liu, and J. S. Xue, Science,

270, 590 (1995).

3. J. 0. Besenhard, P. Komenda, A. Paxinos, E. Wudy, and

M. Josowicz, Solid State lonics, 18, 19, 823 (1986).

4. J. Wang, I. D. Raistrick, and R. A. Huggins, This

Journal, 133, 457 (1986).

I-UKMA lION OF MATRIX

tORMATION OF Sn

Sn REGIONS

5. A. Anani, S. Crouch-Baker, and R. A. Huggins, in

Lithium Batteries, A. N. Dey, editor PV 87-1, p. 365,

The Electrochemical Society Proceedings Series,

Pennington, NJ (1987).

6. J. 0. Besenhard, J. Yang, and M. Winter, in 8th

Extended Abstracts of International Meeting on
Lithium Batteries, pp. 69-72, Nagoya, Japan, June
16-21, 1996.

7. Y. Idota, M. Nishima, Y. Miyaki, T. Kubota, and T.

STRUCTURALLY
RELATED PHASES

Miyasaki, Can. Pat. Appl. 2,1134,053 (1994).

8. A. M. Wilson and J. R. Dahn, This Journal, 142, 326

(1995).

9. M. N. Richard, I. Koetschau, and J. H. Dahn, ibid., 144,

LiSn REGIONS

554 (1997).

LITHIA

10. A. S. Gozdz, C. N. Schmutz, J. M. Tarascon, and P. C.

Warren, Pat. Coop. Treaty Appl., PCT/US94/08772,

MATRIX

11. J. Carb Nver and J. Williamson, Phys. Chem.

(1994).

i NU(.TURALLY
JNRFLATED PHASES

Glasses, 8, 164 (Aug. 1967).

12. R. Kevbeliz and E. J. Kohlmeyer, Metal Erz., 30, 189

(1933).

_- LinSn5
REGIONS

13. W. G. Moffat, The Handbook of Binary Phase Diagrams, Genium Pub. Corp., Schenectady, NY (1990).
14. R. W. G. Wyckoff, Crystal Structures, 2nd ed., Vol 1,
Krieger, Florida (1982).
15. D. A. Hansen and L. J. Chang, Acta Crystallogr., B25,
2392 (1969).

Fig. 14. Reaction mechanism schematic for the reaction of lithium

with tin(ll} oxide.

16. W. Muller and H. Schafer; Z. Naturforsch., 28b, 246

(1973).

17. W. Muller, ibid., 29b, 304 (1974).

Dalhousie University assisted in meeting the publication

costs of this article.

18. U. Frank, W. Muller, and H. Schafer, ibid., 30b,

(1975).

19. U. Frank and W. Muller; ibid., 30b, 316 (1975).

REFERENCES
1. W. R. McKinnon and R. R. Haering, Modern Aspects of

20. U. Frank, W Muller, and H. Schafer, ibid., 30b, 6

Bockris, and B. E. Conway, Editors, Plenum, New

vich, Soviet Physics-Crytstallography, 9(3), 338

Electrochemistry, No. 15, R. E. White, J. O'M.

York (1983).

(1975).

21. E. I. Gladyeshevskii, G. I. Oleksiv, and P. I. Kripyake(1964).

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