Lithium cobalt(II) pyrophosphate, Li1.86CoP2O7, from synchrotron X-ray powder data

Zhou, H.; Upreti, S.; Chernova, N.A.; Whittingham, M.S.

doi:10.1107/S1600536811038451

Volume 67
Part 10
Pages i58-i59
October 2011

Received 30 August 2011
Accepted 19 September 2011
Online 30 September 2011

Key indicators
Powder Synchrotron study
T = 297 K
Mean (O-Li) = 0.020 Å
Disorder in main residue
R = 0.057
wR = 0.080
Data-to-parameter ratio = 91.1
Details

Lithium cobalt(II) pyrophosphate, Li_1.86CoP₂O₇, from synchrotron X-ray powder data

Hui Zhou,^a Shailesh Upreti,^a Natasha A. Chernova ^a and M. Stanley Whittingham ^a ^*

^aChemistry and Materials, SUNY Binghamton, Binghamton, NY, USA
Correspondence e-mail: stanwhit@gmail.com

Structure refinement of high-resolution X-ray powder diffraction data of the title compound gave the composition Li_1.865CoP₂O₇, which is also verified by the ICP measurement. Two Co sites exist in the structure: one is a CoO₅ square pyramid and the other is a CoO₆ octahedron. They share edges and are further interconnected through P₂O₇ groups, forming a three-dimensional framework, which exhibits different kinds of intersecting tunnels containing Li cations and could be of great interest in Li ion battery chemistry. The structure also exhibits cation disorder with 13.5% Co residing at the lithium (Li1) site. Co seems to have an average oxidation state of 2.135, as obtained from the strutural stochiometry that closely supports the magnetic susceptibility findings.

Related literature

For related structures, see: Adam et al. (2008); Nishimura et al. (2010); Zhou et al. (2011). For related materials with Na⁺ and K⁺ cations, see: Erragh et al. (1991); Sanz et al. (1999); Beaury et al. (2004); Gopalakrishna et al. (2005); Bih et al. (2006); Guesmi et al. (2007). For related structural frameworks, see: Beaury et al. (2004); Fagginani & Calvo (1976); Sandström et al. (2003); Etheredge & Hwu (1995); El Maadi et al. (1995); Huang & Hwa (1998); Sanz et al. (1999); Erragh et al. (1998). Pseudovoigt profile coefficients as parameterized in Thompson et al. (1987) and Finger et al. (1994).

Experimental

Crystal data

CoLi_1.865O₇P₂
M_r = 245.82
Monoclinic, P 2₁ /a
a = 9.76453 (4) Å
b = 9.69622 (4) Å
c = 10.95952 (4) Å
= 101.7664 (2)°
V = 1015.83 (1) Å³
Z = 8
Synchrotron radiation, = 0.413988 Å
= 0.89 mm^-1
T = 297 K
irregular shape, 15 × 13 mm

Data collection

Advanced Photon Source diffractometer
Specimen mounting: kapton capillary
Data collection mode: transmission
Scan method: continuous

Refinement

R_p = 0.057
R_wp = 0.080
R_exp = 0.049
R(F²) = 0.04534
² = 2.624
24500 data points
269 parameters

Data collection: Advance Photon Source Argonne National Laboratory; cell refinement: GSAS (Larson & Von Dreele, 2000); data reduction: Powder4 (Dragoe, 2001); program(s) used to solve structure: GSAS; program(s) used to refine structure: GSAS; molecular graphics: CrystalMaker (Palmer, 2005); software used to prepare material for publication: publCIF (Westrip, 2010).

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BR2175 ).

Acknowledgements

Use of the Advanced Photon Source at the Argonne National Laboratory was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. The research at Binghamton was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy under Contract No. DE-AC02-05CH11231, under the Batteries for Advanced Transportation Technologies (BATT) Program subcontract # 6807148.

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inorganic compounds