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Title: Co 11Li[(OH) 5O][(PO 3OH)(PO 4) 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, Co 11.0(1)Li 1.0(2)[(OH) 5O][(PO 3OH)(PO 4) 5], corresponding to the simplified composition Co 1.84(2)Li 0.16(3)(OH)PO 4, is prepared by hydrothermal synthesis. Because the pH-dependent formation of other phases such as Co 3(OH) 2(PO 3OH) 2 and olivine-type LiCoPO 4 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) Å 3, Z = 1). The three-dimensional network structure is characterized by partially Li-substituted, octahedral [M 2O 8(OH)] (M = Co, Li) dimer units which form double chains that run along the [001] direction and are connected by [PO 4] and [PO 3(OH)] tetrahedra. Because no Li-free P31$m$-type Co 2(OH)PO 4 phase could be prepared, it can be assumed that the Li ions are crucial for the stabilization of the framework. Co L-edge X-raymore » 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, Co 3(PO 4) 2, and olivine-type LiCoPO 4 with release of water and oxygen.« less

Authors:
ORCiD logo [1];  [2];  [3];  [4]; ORCiD logo [1]
  1. Technical Univ. of Munich, Garching (Germany)
  2. Bavarian Academy of Sciences and Humanities, Garching (Germany). Walther Meissner Inst.
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1532262
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article: 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

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. doi: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. doi: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},
issn = {0020-1669},
number = 18,
volume = 56,
place = {United States},
year = {2017},
month = {8}
}

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