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Science 14 June 2002:
Vol. 296. no. 5575, pp. 2012 - 2015
DOI: 10.1126/science.1071079
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Reports

A Reversible Solid-State Crystalline Transformation in a Metal Phosphide Induced by Redox Chemistry

D. C. S. Souza,1 V. Pralong,1 A. J. Jacobson,2 L. F. Nazar1*

We demonstrate low-potential intercalation of lithium in a solid-state metal phosphide. A topotactic first-order transition between different but related crystal structures at room temperature takes place by an electrochemical redox process: MnP4 <-> Li7MnP4. The P-P bonds in the MnP4 structure are cleaved at the time of Li insertion (reduction) to produce crystalline Li7MnP4 and are reformed after reoxidation to MnP4, thereby acting as an electron storage reservoir. This is an unusual example of facile covalent bond breaking within the crystalline solid state that can be reversed by the input of electrochemical energy.

1 Department of Chemistry and the Waterloo Centre for Materials Research, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada.
2 Department of Chemistry, University of Houston, Houston, TX 77204, USA.
*   To whom correspondence should be addressed. E-mail: lfnazar{at}uwaterloo.ca

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Science. ISSN 0036-8075 (print), 1095-9203 (online)