A high-capacity lithium-storage material in metal-oxide form has been synthesized that can replace the carbon-based lithium intercalation materials currently in extensive use as the negative electrode (anode) of lithium-ion rechargeable batteries. This tin-based amorphous composite oxide (TCO) contains Sn(II)-O as the active center for lithium insertion and other glass-forming elements, which make up an oxide network. The TCO anode yields a specific capacity for reversible lithium adsorption more than 50 percent higher than those of the carbon families that persists after charge-discharge cycling when coupled with a lithium cobalt oxide cathode. Lithium-7 nuclear magnetic resonance measurements evidenced the high ionic state of lithium retained in the charged state, in which TCO accepted 8 moles of lithium ions per unit mole.
The lithium insertion reactions with tin (II) oxide (SnO) and
tin-based composite oxide (abbreviated as TBCO) are studied by solid
7Li-NMR Knight shift, T1 and T1ρ relaxation rate, TEM and in situ XRD methods. By the insertion reaction for SnO, the lithium oxide and
β-tin are produced first at Li/Sn = 2; at Li/Sn = 3 to 6
the products are not simple and a mixture of LiSn2, LiSn,
Li5Sn2 and Li7Sn2 alloys is detected during
the insertion. For the
TBCO, which is revealed as amorphous, mainly constituted by randomly
distributed very short-range (order of 10-9 m) regions by TEM
observation, it is found that electrochemically inserted lithium forms Li2O
and produces metallic tin (Sn) in the first step (Li/Sn <2), then
the highly ionic lithium-tin alloys, Li7Sn2 (and Li7Si2), are
produced in the second step (Li/Sn >2). During the second step, the
Li/Sn ratio of formed lithium-tin alloy is kept at almost 4. By the analyses
of 7Li NMR Knight shifts, line shape and in situ XRD, the
lithium-inserted TBCOs are characterized as almost amorphous and mixtures of
highly ionic components.
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