Direct synthesis and characterization of mixed-valent Li0.5$-$δCoPO4, a Li-deficient derivative of the Cmcm polymorph of LiCoPO4

Ludwig, Jennifer; Alarcon-Suesca, Carlos; Geprags, Stephan; Nordlund, Dennis; Doeff, Marca M.; Orench, Ines Puente; Nilges, Tom

doi:10.1039/c7ra04043a

Title: Direct synthesis and characterization of mixed-valent Li_0.5$$-$$δCoPO₄, a Li-deficient derivative of the Cmcm polymorph of LiCoPO₄

Journal Article · Fri May 26 00:00:00 EDT 2017 · RSC Advances

DOI:https://doi.org/10.1039/c7ra04043a· OSTI ID:1369476

Ludwig, Jennifer ^[1]; Alarcon-Suesca, Carlos ^[1]; Geprags, Stephan ^[2]; Nordlund, Dennis ^[3]; Doeff, Marca M. ^[4]; Orench, Ines Puente ^[5];

^[1]

Technical Univ. of Munich, Garching (Germany)
Bavarian Academy of Sciences and Humanities, Garching (Germany)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Instituto de Ciencia de Materiales de Aragon, Zaragoza (Spain); Institut Laue-Langevin, Grenoble Cedex (France)

While the majority of research activities on LiCoPO₄ is focussed on the thermodynamically stable olivine-type Pnma polymorph, the metastable Pna2₁ and Cmcm modifications have recently attracted considerable attention due to their interesting material properties. In this study, we present the first Li-deficient structural derivative of the Cmcm modification with the nominal composition Li_0.5–δCoPO₄. As opposed to the substoichiometric olivine (Pnma) phases Li_xCoPO₄ (x = 0; 2/3), which are exclusively accessible by electrochemical or chemical Li extraction techniques, this is also the first time that a direct soft-chemical synthesis route towards a Li_xCoPO₄-type material is accomplished. X-ray and neutron diffraction studies indicate that Cmcm-type Li_0.5–δCoPO₄ shows vacancies on both the Li and Co sites, whereas X-ray absorption spectra demonstrate that the structure features heterovalent Co ions (+2/+3) to compensate for the Li deficit. Magnetic measurements reveal a long-range antiferromagnetic order below 10.5 K. A thorough investigation of the thermal stability using thermogravimetric analysis, differential scanning calorimetry, and temperature-dependent in situ X-ray powder diffraction demonstrates that Li_0.5–δCoPO₄ is metastable and exhibits a complex, multi-step thermal decomposition mechanism. In the first step at 394 °C, it decomposes to α-Co₂P₂O₇ (P2₁/c) and LiCoPO₄ (Cmcm) upon O₂ release. The LiCoPO₄ (Cmcm) intermediate is then irreversibly transformed to olivine-type LiCoPO₄ (Pnma) at 686 °C. Furthermore, the material properties of Li_0.5–δCoPO₄ are further compared to the fully lithiated, isostructural LiCoPO₄ (Cmcm) phase, for which an improved structure solution as well as Co L_2,3-edge X-ray absorption spectra are reported for the first time.

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Research Organization:: SLAC National Accelerator Lab., Menlo Park, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1369476

Journal Information:: RSC Advances, Vol. 7, Issue 45; ISSN 2046-2069

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 4 works

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Title: Direct synthesis and characterization of mixed-valent Li0.5$$-$$δCoPO4, a Li-deficient derivative of the Cmcm polymorph of LiCoPO4

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Title: Direct synthesis and characterization of mixed-valent Li_0.5$$-$$δCoPO₄, a Li-deficient derivative of the Cmcm polymorph of LiCoPO₄