journal article·2015-12-22Open access

Interfacial Effects in ε-LixVOPO4 and Evolution of the Electronic Structure

N. F. Quackenbush, L. Wangoh, D. O. Scanlon, R. Zhang, Y. Chung, Z. Chen, B. Wen, Y. Lin, J. C. Woicik, N. A. Chernova, S. P. Ong, M.S. Whittingham, L. F. J. Piper

Chemistry of Materials· Volume 27· Issue 24

Abstract

The epsilon polymorph of vanadyl phosphate ε-VOPO 4 is a promising cathode material for high-capacity Li ion batteries, owing to its demonstrated ability to reversibly incorporate two lithium ions per redox center. As lithium is inserted into the nanosized particles within the cathode, the electrochemical reaction can be largely affected by the interfacial chemistry at the nanoparticle surface. We performed X-ray photoelectron spectroscopy using both soft (XPS) and hard (HAXPES) X-rays to chemically distinguish and depth-resolve the interfacial phase transitions in ε-VOPO 4 electrodes as a function of electrochemical discharge. Our analysis shows that the second lithium reaction begins before the full incorporation of the first lithium. This results in a pronounced lithium gradient within the nanoparticles, with the ε-Li 2 VOPO 4 phase only forming near the surface. These results indicate that a disruption of the kinetics are limiting the realized capacity in our hydrothermally synthesized ε-VOPO 4 . Moreover, from inspection of the valence band region, we were able to monitor the evolution of ε-VOPO 4 to ε-Li 2 VOPO 4 at the surface of our nanoparticles. These assignments are confirmed by hybrid density functional theory of the three end phases.
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Research context

OpenAlex topics: Transition Metal Oxide Nanomaterials · Advancements in Battery Materials · Catalysis and Oxidation Reactions

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Department of Physics, Applied Physics and Astronomy, Binghamton University, Binghamton, New York 13902, United States

University College London, Kathleen Lonsdale Materials Chemistry, Department of Chemistry, 20 Gordon Street, London WC1H 0AJ, United Kingdom

Diamond Light Source Ltd., Diamond House, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0DE, United Kingdom

The Northeast Center for Chemical Energy Storage (NECCES), State University of New York at Binghamton, Binghamton, New York 13902, United States

College of Chemistry & Chemical Engineering, Central South University, Changsha 410083, China

Chemistry and Materials, State University of New York at Binghamton, Binghamton, New York 13902, United States

Department of NanoEngineering, University of California, San Diego, 9500 Gilman Drive, Mail Code 0448, La Jolla, California 92093, United States

Materials Science and Engineering Laboratory, National Institute of Standards and Technology, Gaithersburg, Maryland 20899, United States

Materials Science & Engineering, Binghamton University, Binghamton, New York 13902, United States

Funding

Basic Energy Sciences · Engineering and Physical Sciences Research Council

References (61)

Show source-provided references
1. 10.1021/cr500300310.1021/cr5003003 ↗
2. 10.3390/ma601015610.3390/ma6010156 ↗
3. 10.1021/cm901452z10.1021/cm901452z ↗
4. 10.1021/ar300088q10.1021/ar300088q ↗
5. 10.1039/b501961c10.1039/b501961c ↗
6. 10.1149/1.186226510.1149/1.1862265 ↗
7. 10.1021/cm200753g10.1021/cm200753g ↗
8. 10.1021/cm300399610.1021/cm3003996 ↗
9. 10.1107/S002188980801201610.1107/S0021889808012016 ↗
10. 10.1039/c4ta01518e10.1039/c4ta01518e ↗
11. Lavrov A. V. · Doklady Akademii Nauk Sssr · 1982 · 266 · 343
12. 10.1016/j.solidstatesciences.2006.04.00810.1016/j.solidstatesciences.2006.04.008 ↗
13. 10.1149/1.243353910.1149/1.2433539 ↗
14. 10.1021/cm801995p10.1021/cm801995p ↗
15. 10.1021/cm301569m10.1021/cm301569m ↗
16. 10.1016/j.electacta.2013.03.01010.1016/j.electacta.2013.03.010 ↗
17. 10.1021/nn506495x10.1021/nn506495x ↗
18. 10.1021/cm400227j10.1021/cm400227j ↗
19. 10.1039/C4CP03628J10.1039/C4CP03628J ↗
20. 10.1149/2.064310jes10.1149/2.064310jes ↗
21. 10.1021/cm900862v10.1021/cm900862v ↗
22. 10.1103/PhysRevB.54.1116910.1103/PhysRevB.54.11169 ↗
23. 10.1103/PhysRevB.49.1425110.1103/PhysRevB.49.14251 ↗
24. 10.1103/PhysRevLett.77.386510.1103/PhysRevLett.77.3865 ↗
25. 10.1103/PhysRevB.50.1795310.1103/PhysRevB.50.17953 ↗
26. 10.1103/PhysRevB.59.175810.1103/PhysRevB.59.1758 ↗
27. 10.1063/1.156406010.1063/1.1564060 ↗
28. 10.1063/1.240466310.1063/1.2404663 ↗
29. 10.1063/1.218700610.1063/1.2187006 ↗
30. 10.1063/1.176007410.1063/1.1760074 ↗
31. 10.1063/1.208517010.1063/1.2085170 ↗
32. 10.1103/PhysRevB.75.04512110.1103/PhysRevB.75.045121 ↗
33. 10.1103/PhysRevB.79.07310510.1103/PhysRevB.79.073105 ↗
34. 10.1063/1.307449910.1063/1.3074499 ↗
35. 10.1103/PhysRevB.81.16110310.1103/PhysRevB.81.161103 ↗
36. 10.1021/jz101172510.1021/jz1011725 ↗
37. 10.1039/B812838C10.1039/B812838C ↗
38. 10.1021/jz100962n10.1021/jz100962n ↗
39. 10.1103/PhysRevB.74.07310110.1103/PhysRevB.74.073101 ↗
40. 10.1103/PhysRevLett.103.09640510.1103/PhysRevLett.103.096405 ↗
41. 10.1103/PhysRevB.79.20120110.1103/PhysRevB.79.201201 ↗
42. 10.1039/b927508h10.1039/b927508h ↗
43. 10.1103/PhysRevLett.106.18640310.1103/PhysRevLett.106.186403 ↗
44. 10.1103/PhysRevB.83.07511210.1103/PhysRevB.83.075112 ↗
45. 10.1039/C4TA00434E10.1039/C4TA00434E ↗
46. 10.1039/C4TA00673A10.1039/C4TA00673A ↗
47. 10.1073/pnas.30.9.24410.1073/pnas.30.9.244 ↗
48. 10.1038/3364710.1038/33647 ↗
49. 10.1016/j.apsusc.2009.06.00910.1016/j.apsusc.2009.06.009 ↗
50. 10.1149/2.069306jes10.1149/2.069306jes ↗
51. 10.1021/cm203419510.1021/cm2034195 ↗
52. 10.1039/C3TA12728A10.1039/C3TA12728A ↗
53. 10.1016/S0378-7753(03)00240-410.1016/S0378-7753(03)00240-4 ↗
54. 10.1007/s10008-011-1484-710.1007/s10008-011-1484-7 ↗
55. 10.1016/j.elspec.2004.03.00410.1016/j.elspec.2004.03.004 ↗
56. 10.1103/PhysRevB.85.11510610.1103/PhysRevB.85.115106 ↗
57. 10.1021/jp312237410.1021/jp3122374 ↗
58. Scofield, J. H.Theoretical Photoionization Cross Sections from 1 to 1500 keV.Lawrence Livermore National Laboratory Rep. UCRL-51326, Lawrence Livermore National Laboratory: Livermore, CA, 1973.
59. 10.1103/PhysRevB.54.223610.1103/PhysRevB.54.2236 ↗
60. 10.1016/j.apsusc.2008.07.19610.1016/j.apsusc.2008.07.196 ↗
61. 10.1016/j.jssc.2009.08.00510.1016/j.jssc.2009.08.005 ↗