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2048 J. Electrochem. Soc., Vol. 144, No.6, June 1997 The Electrochemical Society, Inc.

SCATTERING ANGLE (deg.) SCATTERING ANGLE (deg.)

20 30 40 50 20 30 40 50
100 (a)Scanl2 ---Sn
O.66V

10 ______
4 I I I I
100 (b)Scan 8
c) O.94V
10 _______
C)
0
4 I I I I I
>- I I
j.... 100 (c) Scan 4 BeO
I-
Cl)
zu-I
ii II lilt II
lo:an1jj Sf0 I- 4 I
z
>
0)
1 _
(
a0- 20 40 >0
0
SCAN NUMBER SCAN NUMBER
Fig. 4. In situ XRD results for SnO; (a) scan 12 —0.66 V, (b) scan Fig. 5. In situ XRD results for SnO; (a) scan 17 —0.41 V, (b) scan
8 —0.94 V, (c) scan 4 —1.05 V, (ci) scan 1 —1.04 V, and (e) voltaae 15 —0.50 V, (c) scan 14 —0.55 V, (ci) scan 12 —0.66 V. and (e) volt-
profile (scan number vs. voltage) for constant current cycling of cell. age profile (scan number vs. voltage) for constant current cycling of
Logarithmic intensities are Dlolted for the scans in reference to the cell. Logarithmic intensities are plotted for the scans in reference to
left-hand vertical axis and )inear intensities are plotted for the cal- the left-hand vertical axis and linear intensities are plotted for the
culated patterns (normalized to 100) in reference to the right-hand calculated patterns (normalized to 100) in reference to the right.
vertical axis. hand vertical axis. Note the change of intensity scale from Fig. 4.

From Fig. 4d (scan 1, 1.04 V) to Fig. 4b (scan 8, 0.94 V) ken lines in Fig. 8d. It is important to note that crystalline
we can observe the decline of the SnO peaks and an SnO does not reform. Figure 8a (scan 1, 1.04 V) shows the
increase in the background. At Fig. 4a (scan 12, 0.66 V) we first scan on the same scale as Fig. 8b (scan 55, 2.50 V). An
observe broad tin peaks, which confirms that the SnO increase in x-ray background has occurred during the
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
peak positions and intensities are shown by the broken SCATTERING ANGLE (deg.)
lines in Fig. Sc. The Li2Sn5 peaks are gone by Fig. Sa (scan 20 30 40 50
17, 0.41 V) and we see the emergence on the next Li-Sn
phase, LiSn, as shown by the broken lines in Fig. 5a. (a) Scan 27
Figure 6d shows the calculated intensities for Li7Sn3,
which has strong features at approximately 22° and 38°.
1
One could imagine that we have Li7Sn3 as at Fig. 6c (scan 4 I I
21, 0.31 V). However, it turns out that all of the remaining (b) Scan 22
Li-Sn phases, that is Li5Sn2, Li13Sn5, Li7Sn2, and Li22Sn5
are structurally similar to each other and to Li7Sn3 as
III
ihIhu
shown by the calculated peaks in Fig. 7d, again with 4
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
zu-j 1
(c) Scan 21

31, 0.23 V charge, and scan 43, 0.43 V charge, respectively) I.

6
we observe these broad features at 22° and 38°. These Li- 4 1

rich alloy phases Li5Sn2, Li13Sn5, Li7Sn2, and Li22Sn5 are all (d)
based on the BCC unit cell of lithium14 and differ primar- - - - U7Sn3
ily 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 patterns of Fig. 6a, b, c, 7b, and c arise from these
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
—
>
2

0
...I. 20
SCAN NUMBER
40

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

phases have the highest melting point, and hence lowest
atom mobility at room temperature.
Further charging the cell to 0.78 V by Fig. 7a (scan 45,
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-
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 intensi-
ties are plotted for the calculated patterns (normalized to 100) in
reference to the right-hand vertical axis.