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

2051

(a) Li2Sn5
S
S S
•S . •S
a S
SI 55 •••
• US
S
SIl S• •SISSS
SS SS • S
S• SSS II II, 51551555
C
S•
.• •5 •• •• I •S
S
I
• •

Li S •
S S
S
S
Fig. 12. Crystal structure dia-
grams for; (a) L125n5 and (b) LiSn.

(b) LiSn a
S S
I • .
a
S
S

I
.5 •
b
•
S• •S• •S S.. S S S
••• SSS US • •SS
•••SS
S•5••IS•••U
•SS •
S
• • S• S

•.U . U• •
C S
.U .
S

crumbling under the large volume changes in the alloying lithium through to LiSn involves the formation of lithium
process. The breakdown of the oxide into Li20 and Sn is layered structures and that these structurally related
for the most part irreversible. The further insertion of 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 re-
versibly with lithium in a similar manner. Lithium first
reacts irreversibly in a manner consistent with the forma-
tion 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 aggrega-
tion of tin atoms into large coherent regions. Once large tin
LU regions form, the large volume differences between coex-
(5 isting bulk Li-Sn phases may induce cracking and crum-
bling of the structure, and capacity loss. This effect is
apparently not as severe when the Li-Sn phases are struc-
turally 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,
graphite.
Further work is warranted on these materials, particu-
larly focusing on ways to capitalize on the factors that
0 400
tend to make the reaction reversible. The materials also
800 1200 show large irreversible capacity which may present tech-
CAPACITY (mAh/g) nical challenges for their implementation as anodes in Li-
ion cells.
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 Manuscript submitted Nov. 12, 1996; revised manuscript
0.4 V. received Feb. 19, 1997.