(190f) Nanostructured Layered Oxide Cathodes for Lithium Ion Batteries

Nanostructured Layered Oxide
Cathodes for Lithium Ion Batteries

Krista L. Hawthorne,^a Ryan Franck,^a Siu
on Tung,^c James Mainero,^b Yi Ding,^b Levi T.
Thompson^a

^aDepartment of Chemical Engineering,
University of Michigan, Ann Arbor, MI 48109

^bUnited States Army Tank Automotive Research, Development,
and Engineering Center, Warren, MI 48092

^aDepartment of Macromolecular Engineering,
University of Michigan, Ann Arbor, MI 48109

Lithium ion batteries typically operate by reversibly
intercalating lithium ions in layered oxide cathodes, such as LiCoO₂;
consequently the capacity is directly correlated to the amount of lithium ions
that can be inserted and extracted.¹ This repeated insertion of
lithium ions causes strain on the crystal structure, leading to fracture and
capacity fade.^2-4 Additionally, diffusion of the lithium ions
through the crystal is relatively slow, limiting the rate capabilities of the
battery. Several efforts reported in the literature have focused on engineering
the structure of the cathode materials. We propose a nanostructuring of layered
oxides by the chemical insertion of pillars between the layers.^5,6
These pillars act as scaffolds, providing structural support and increasing the
interlayer spacing, which in turn increases the battery capacity and lifetime.

Our efforts focused on vanadium pentoxide xerogels (V₂O₅)⁷
and manganese oxide (MnO₂). Typical manganese oxide cathodes are in
a spinel structure; however, the birnessite phase of manganese oxide is a
layered structure, with potassium ions between the layers.⁸ Both
materials were pillared with Al₁₃ Keggin ions. The pillared vanadium
oxide xerogels exhibit an increase in the (001) interlayer spacing from 11 to
13 Å, as observed by XRD and an increase in thermal stability over the
unpillared xerogel. During cycling, pillared V₂O₅ shows
an increase in capacity at high rates as well as an increase in capacity
retention, when returning to cycling at low rates after the high rate
experiments (Figure 1). We will report thermal stability of coin cells with
pillared V₂O₅ cathodes, through the use of an Accelerating
Rate Calorimeter, and mechanical and electrochemical properties of pillared
birnessite materials. Pillared manganese oxide structures may exhibit similar
increases in capacity. Additionally, other pillars such as SiO₂ and
TiO₂ can be used in birnessite.

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