On the Aggregation of Tin in SnO Composite Glasses Caused by the Reversible Reaction with Lithium

Abstract

We show that the reaction mechanism in Li/[SnO:(B 2 O 3 ) x :(P 2 O 5 ) y glass (0.1 Յ x, y Յ 0.5)], Li/[SnO: B 2 O 3 ) 0.5 :(P 2 O 5 ) 0.5 :(K 2 CO 3 ) 0.04 glass] and Li/SnO cells is common. During the first discharge, the oxygen bonded to tin (as SnO) reacts with lithium to give metallic tin (which can be present as clusters of a few atoms) and lithia. The tin reacts with further lithium to the composition limit of Li 4.4 Sn. During charge the Li is removed from the lithium-tin alloy. The other components of the glass (e.g., B 2 O 3 , P 2 O 5 , Li 2 O, etc.) are inert with respect to lithium, and we call the atoms which make up these phases "spectator atoms." Using X-ray diffraction (XRD) and electrochemical methods, we show that size of the initial tin regions which form is inversely proportional to the spectator:Sn atom ratio. However, during cycling, all of these materials show the subsequent aggregation of the tin atoms into clusters which grow with cycle number until they reach a saturated size. The final cluster size is larger for materials with smaller X:Sn ratio. We propose a speculative model, which predicts the saturated Sn cluster size, as a function of the spectator:Sn ratio.

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