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Addition/Correction pubs.acs.org/cm
Cite This: Chem. Mater. 2018, 30, 5516−5517
Correction to Structure Prediction of Li−Sn and Li−Sb Intermetallics for Lithium-Ion Batteries Anodes Martin Mayo, James P. Darby, Matthew L. Evans, Joseph R. Nelson, and Andrew J. Morris*,† Chemistry of Materials 2017, 29 (14), 5787−5795. DOI: 10.1021/acs.chemmater.6b04914 S Supporting Information *
Chem. Mater. 2018.30:5516-5517. Downloaded from pubs.acs.org by 5.62.154.79 on 10/07/18. For personal use only.
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Table 1. Description of the Experimental and Predicted LixSn Phases Found within 20 meV/atom from the Convex Hulla
e have recently become aware of some errors in the reporting of the Li−Sn structures in our paper:1 (1) The space groups (SG) of certain Li−Sn structures are reported incorrectly in the following cases: (i) The SG of the Li2Sn3 structure is given as P1̅ in six instances: in the Abstract, in the “Low Li-Content Structures” section, in the Discussion, in Table 1, in the image of Figure 2b, and in the caption of Figure 6. It should read P4/mmm. The structure’s ball-and-stick depiction is correct in Figure 2b. (ii) The SG of the Li5Sn3 structure is given as P4̅3m in the “Structures between 1 ≤ x ≤ 4.4 in LixSn” section and in the caption of Figure 2. It should read Im3̅m. (iii) The SG of the Li8Sn3 structure is given as C2/m in the caption of Figure 4. It should read R3̅m. (iv) The SG of the Li5Sn1 structure is given as Pmma in Table 1. It should read P6/mmm. (v) The SG of the Li7Sn1 structure is given as Fmmm in the Abstract; it should read C2. (vi) In the “Lithium Antimonides” Results section, Li1Sb1 is described as being “similar to Li1Sn1−P4/mmm”; this should read “similar to Li1Sn1−Pmm2”. (2) The CIFs provided in the Supporting Information for the Li7Sn9, Li5Sn3, Li3Sn1, Li7Sn2, Li4Sn1, and Li7Sn1 structures are incorrect. This was a result of an invalid final-step conversion of the structures into the CIF format. (3) The Li15Sn4 structure is described in Table 1 as being a “known phase”, citing ref 37; this should read “swap from Na15Sn4”, citing that same work. For completeness, we provide a corrected Table 1 and Figure 2 here. The corrected CIFs of all Li−Sn structures are given as Supporting Information. We would like to emphasize that the conclusions of the work are unchanged by these errors. The reporting of the Li−Sn convex hull (Figure 1), the energetics of different Li−Sn structures relative to the convex hull (Tables 1 and 2), the depictions of these structures (Figures 2, 3, 4, and 5), and our calculated Li−Sn voltage curve (Figure 6) are all correct. All Li−Sb structures are reported correctly. Since the original publication J. P. Darby, M. L. Evans, and J. R. Nelson have been added to the author list due to their contribution in preparing this correction. Their affiliation is the first listed in the original paper, Theory of Condensed Matter Group, Cavendish Laboratory, University of Cambridge, J. J. Thomson Avenue, Cambridge CB3 0HE, United Kingdom. The authors thank the authors of ref 2, R. Sen and P. Johari, for bringing these errors to our attention and A. F. Harper and C. P. Kocer for helpful discussions. © 2018 American Chemical Society
stoichiometry
x in LixSn
distance from the hull [meV/atom]
space group
Sn* Li2Sn*5
0.0 0.4
0 0
I41/amd P4/mbm
LiSn2 Li2Sn3 Li7Sn9 LiSn*
0.5 0.6 0.8 1.0
8 6 19 0
P4/mmm P4/mmm P42/n P2/m
Li3Sn2 Li5Sn3 Li2Sn Li7Sn3
1.5 1.7 2.0 2.3
12 5 1 2
P21/m Im3̅m Cmcm P21/m
Li5Sn2
2.5
2
R3̅m
Li13Sn5*
2.6
0
P3̅m1
Li8Sn*3
2.7
0
R3̅m
Li3Sn Li7Sn2*
3.0 3.5
6 0 6
P32 P1̅ Cmmm
Li15Sn4
3.8
6
I4̅3d
Li4Sn Li17Sn4*
4.0 4.25
13 0
P21 F4̅3m
Li22Sn5
4.4
11
F4̅3m
Li5Sn Li7Sn Li*
5.0 7.0
19 18 0
P6/mmm C2 Im3̅m
structure origin known phase30 AIRSS AIRSS AIRSS known phase31 AIRSS AIRSS AIRSS known phase32 known phase33 known phase34 swap from Li8Pb35 3 AIRSS AIRSS known phase36 swap from Na15Sn37 4 AIRSS known phase3 known phase38 AIRSS AIRSS
a We indicate with a star (*) the most energetically favorable phases which are found on the convex hull. The CIF files of the structures obtained by AIRSS, and the swapping method can be found in the Supporting Information.
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ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.chemmater.8b02803. CIF files of the Li−Sn structures obtained by AIRSS and species-swapping methods (ZIP) Published: July 26, 2018 5516
DOI: 10.1021/acs.chemmater.8b02803 Chem. Mater. 2018, 30, 5516−5517
Chemistry of Materials
Addition/Correction
Figure 2. Structures found by AIRSS within 0 < x ≤ 1.7 in LixSn which exhibit layer-like Sn structures. (a) LiSn2−P4/mmm is found 8 meV/atom from the convex hull. It features double layers of Sn ions with cubic angles and intercalated Li in between. (b) The Li2Sn3−P4/mmm phase found by AIRSS is predicted to lie 6 meV/atom above the convex hull. The structure shows alternate double- and single-layers of four-membered rings of Sn atoms arranged in a cubic geometry. (c) Li7Sn9−P42/n showing distorted two-dimensional sheets of Sn atoms linked by an Sn atom between the layers at the edge of the primitive cells. Flat sheets of Li are intercalated between the Sn layers. (d) Li1Sn1−Pmm2 structure discovered by AIRSS showing layers of Sn atoms arranged in a cubic fashion with intercalated sheets of Li in-between. (e) Li3Sn2−P21/m structure obtained by AIRSS formed of intercalated zigzag-like Sn ions and almost flat Sn sheets. (f) Li5Sn3−Im3̅m is an AIRSS structure found 1.7 meV/atom from the convex hull. Sn ions form a three-dimensional cubic arrangement and a Li bcc-like sublattice. Green and purple spheres denote Li and Sn atoms, respectively, with the purple lines indicating Sn−Sn bonds.
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AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. Present Address †
(A.J.M.) School of Metallurgy and Materials, University of Birmingham, Edgbaston, Birmingham, B15 2TT, United Kingdom.
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ACKNOWLEDGMENTS M.M., J.R.N., and A.J.M. acknowledge the Winton Programme for the Physics of Sustainability. J.P.D. acknowledges the Sims Fund for a scholarship. M.L.E. acknowledges the EPSRC Centre for Doctoral Training in Computational Methods for Materials Science for funding under Grant Number EP/ L015552/1. Calculations were carried out using Athena (HPC Midlands Plus) using Tier-2 funding from the EPSRC (Grant Number EP/P020232/1).
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REFERENCES
(1) Mayo, M.; Morris, A. J. Structure Prediction of Li-Sn and Li-Sb Intermetallics for Lithium-Ion Batteries Anodes. Chem. Mater. 2017, 29, 5787−5795. (2) Sen, R.; Johari, P. Understanding the Lithiation of the Sn Anode for High-Performance Li-Ion Batteries with Exploration of Novel LiSn Compounds at Ambient and Moderately High Pressure. ACS Appl. Mater. Interfaces 2017, 9, 40197−40206.
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DOI: 10.1021/acs.chemmater.8b02803 Chem. Mater. 2018, 30, 5516−5517
