Co11Li[(OH)5O][(PO3OH)(PO4)5], a Lithium-Stabilized, Mixed-Valent Cobalt(II,III) Hydroxide Phosphate Framework
Abstract
A new metastable phase, featuring a lithium-stabilized mixed-valence cobalt(II,III) hydroxide phosphate framework, Co11.0(1)Li1.0(2)[(OH)5O][(PO3OH)(PO4)5], corresponding to the simplified composition Co1.84(2)Li0.16(3)(OH)PO4, is prepared by hydrothermal synthesis. Because the pH-dependent formation of other phases such as Co3(OH)2(PO3OH)2 and olivine-type LiCoPO4 competes in the process, a pH value of 5.0 is crucial for obtaining a single-phase material. The crystals with dimensions of 15 μm × 30 μm exhibit a unique elongated triangular pyramid morphology with a lamellar fine structure. Powder X-ray diffraction experiments reveal that the phase is isostructural with the natural phosphate minerals holtedahlite and satterlyite, and crystallizes in the trigonal space group P31$$m$$ ($$a$$ = 11.2533(4) Å, c = 4.9940(2) Å, V = 547.70(3) Å3, Z = 1). The three-dimensional network structure is characterized by partially Li-substituted, octahedral [M2O8(OH)] (M = Co, Li) dimer units which form double chains that run along the [001] direction and are connected by [PO4] and [PO3(OH)] tetrahedra. Because no Li-free P31$$m$$-type Co2(OH)PO4 phase could be prepared, it can be assumed that the Li ions are crucial for the stabilization of the framework. Co L-edge X-ray absorption spectroscopy demonstrates that the cobalt ions adopt the oxidation states +2 and +3 and hence provides further evidence for the incorporation of Li in the charge-balanced framework. The presence of three independent hydroxyl groups is further confirmed by infrared spectroscopy. Magnetization measurements imply a paramagnetic to antiferromagnetic transition at around T = 25 K as well as a second transition at around 9–12 K with a ferromagnetic component below this temperature. The metastable character of the phase is demonstrated by thermogravimetric analysis and differential scanning calorimetry, which above 558 °C reveal a two-step decomposition to CoO, Co3(PO4)2, and olivine-type LiCoPO4 with release of water and oxygen.
- Authors:
-
- Technical Univ. of Munich, Garching (Germany)
- Bavarian Academy of Sciences and Humanities, Garching (Germany). Walther Meissner Inst.
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1532262
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 56; Journal Issue: 18; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Ludwig, Jennifer, Geprägs, Stephan, Nordlund, Dennis, Doeff, Marca M., and Nilges, Tom. Co11Li[(OH)5O][(PO3OH)(PO4)5], a Lithium-Stabilized, Mixed-Valent Cobalt(II,III) Hydroxide Phosphate Framework. United States: N. p., 2017.
Web. doi:10.1021/acs.inorgchem.7b01152.
Ludwig, Jennifer, Geprägs, Stephan, Nordlund, Dennis, Doeff, Marca M., & Nilges, Tom. Co11Li[(OH)5O][(PO3OH)(PO4)5], a Lithium-Stabilized, Mixed-Valent Cobalt(II,III) Hydroxide Phosphate Framework. United States. https://doi.org/10.1021/acs.inorgchem.7b01152
Ludwig, Jennifer, Geprägs, Stephan, Nordlund, Dennis, Doeff, Marca M., and Nilges, Tom. Tue .
"Co11Li[(OH)5O][(PO3OH)(PO4)5], a Lithium-Stabilized, Mixed-Valent Cobalt(II,III) Hydroxide Phosphate Framework". United States. https://doi.org/10.1021/acs.inorgchem.7b01152. https://www.osti.gov/servlets/purl/1532262.
@article{osti_1532262,
title = {Co11Li[(OH)5O][(PO3OH)(PO4)5], a Lithium-Stabilized, Mixed-Valent Cobalt(II,III) Hydroxide Phosphate Framework},
author = {Ludwig, Jennifer and Geprägs, Stephan and Nordlund, Dennis and Doeff, Marca M. and Nilges, Tom},
abstractNote = {A new metastable phase, featuring a lithium-stabilized mixed-valence cobalt(II,III) hydroxide phosphate framework, Co11.0(1)Li1.0(2)[(OH)5O][(PO3OH)(PO4)5], corresponding to the simplified composition Co1.84(2)Li0.16(3)(OH)PO4, is prepared by hydrothermal synthesis. Because the pH-dependent formation of other phases such as Co3(OH)2(PO3OH)2 and olivine-type LiCoPO4 competes in the process, a pH value of 5.0 is crucial for obtaining a single-phase material. The crystals with dimensions of 15 μm × 30 μm exhibit a unique elongated triangular pyramid morphology with a lamellar fine structure. Powder X-ray diffraction experiments reveal that the phase is isostructural with the natural phosphate minerals holtedahlite and satterlyite, and crystallizes in the trigonal space group P31$m$ ($a$ = 11.2533(4) Å, c = 4.9940(2) Å, V = 547.70(3) Å3, Z = 1). The three-dimensional network structure is characterized by partially Li-substituted, octahedral [M2O8(OH)] (M = Co, Li) dimer units which form double chains that run along the [001] direction and are connected by [PO4] and [PO3(OH)] tetrahedra. Because no Li-free P31$m$-type Co2(OH)PO4 phase could be prepared, it can be assumed that the Li ions are crucial for the stabilization of the framework. Co L-edge X-ray absorption spectroscopy demonstrates that the cobalt ions adopt the oxidation states +2 and +3 and hence provides further evidence for the incorporation of Li in the charge-balanced framework. The presence of three independent hydroxyl groups is further confirmed by infrared spectroscopy. Magnetization measurements imply a paramagnetic to antiferromagnetic transition at around T = 25 K as well as a second transition at around 9–12 K with a ferromagnetic component below this temperature. The metastable character of the phase is demonstrated by thermogravimetric analysis and differential scanning calorimetry, which above 558 °C reveal a two-step decomposition to CoO, Co3(PO4)2, and olivine-type LiCoPO4 with release of water and oxygen.},
doi = {10.1021/acs.inorgchem.7b01152},
journal = {Inorganic Chemistry},
number = 18,
volume = 56,
place = {United States},
year = {Tue Aug 29 00:00:00 EDT 2017},
month = {Tue Aug 29 00:00:00 EDT 2017}
}
Web of Science
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