journal article·2023-09Open access

Li iontronics in single-crystalline T-Nb2O5 thin films with vertical ionic transport channels

Hyeon Han, Quentin Jacquet, Zhen Jiang, Farheen N. Sayed, Jae-Chun Jeon, Arpit Sharma, Aaron M. Schankler, Arvin Kakekhani, Holger L. Meyerheim, Jucheol Park, Sang Yeol Nam, Kent J. Griffith, Laura Simonelli, Andrew M. Rappe, Clare P. Grey, Stuart S. P. Parkin

Nature Materials· Volume 22· Issue 9

Abstract

Abstract The niobium oxide polymorph T-Nb2O5 has been extensively investigated in its bulk form especially for applications in fast-charging batteries and electrochemical (pseudo)capacitors. Its crystal structure, which has two-dimensional (2D) layers with very low steric hindrance, allows for fast Li-ion migration. However, since its discovery in 1941, the growth of single-crystalline thin films and its electronic applications have not yet been realized, probably due to its large orthorhombic unit cell along with the existence of many polymorphs. Here we demonstrate the epitaxial growth of single-crystalline T-Nb2O5 thin films, critically with the ionic transport channels oriented perpendicular to the film’s surface. These vertical 2D channels enable fast Li-ion migration, which we show gives rise to a colossal insulator–metal transition, where the resistivity drops by 11 orders of magnitude due to the population of the initially empty Nb 4d0 states by electrons. Moreover, we reveal multiple unexplored phase transitions with distinct crystal and electronic structures over a wide range of Li-ion concentrations by comprehensive in situ experiments and theoretical calculations, which allow for the reversible and repeatable manipulation of these phases and their distinct electronic properties. This work paves the way for the exploration of novel thin films with ionic channels and their potential applications.
Source: crossref · Quality: baseline

Research context

OpenAlex topics: Semiconductor materials and devices · Ga2O3 and related materials · Electronic and Structural Properties of Oxides

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

References (46)

Show source-provided references
1. Guan, Y., Han, H., Li, F., Li, G. & Parkin, S. S. P. Ionic gating for tuning electronic and magnetic properties. Ann. Rev. Mater. Res. 53, 25–51 (2023).10.1146/annurev-matsci-080619-012219 ↗
2. Jeong, J. et al. Suppression of metal-insulator transition in VO2 by electric field-induced oxygen vacancy formation. Science 339, 1402–1405 (2013).10.1126/science.1230512 ↗
3. Jeong, J. et al. Giant reversible, facet-dependent, structural changes in a correlated-electron insulator induced by ionic liquid gating. Proc. Natl Acad. Sci. USA 112, 1013–1018 (2015).10.1073/pnas.1419051112 ↗
4. Lu, N. et al. Electric-field control of tri-state phase transformation with a selective dual-ion switch. Nature 546, 124–128 (2017).10.1038/nature22389 ↗
5. Leng, X. et al. Insulator to metal transition in WO3 induced by electrolyte gating. npj Quant. Mater. 2, 35 (2017).10.1038/s41535-017-0039-2 ↗
6. Hope, M. A. et al. The role of ionic liquid breakdown in the electrochemical metallization of VO2: an NMR study of gating mechanisms and VO2 reduction. J. Am. Chem. Soc. 140, 16685–16696 (2018).10.1021/jacs.8b09513 ↗
7. Han, H. et al. Control of oxygen vacancy ordering in brownmillerite thin films via ionic liquid gating. ACS Nano 16, 6206–6214 (2022).10.1021/acsnano.2c00012 ↗
8. Han, H. et al. Strain-driven formation of epitaxial nanostructures in brownmillerite strontium cobaltite thin films. Proc. Natl Acad. Sci. USA 120, e2221651120 (2023).10.1073/pnas.2221651120 ↗
9. Altendorf, S. G. et al. Facet-independent electric-field-induced volume metallization of tungsten trioxide films. Adv. Mater. 28, 5284–5292 (2016).10.1002/adma.201505631 ↗
10. Wang, M. et al. Electric-field-controlled phase transformation in WO3 thin films through hydrogen evolution. Adv. Mater. 29, 1703628 (2017).10.1002/adma.201703628 ↗
11. Perez-Muñoz, A. M. et al. In-situ evidence of deoxygenation in ionic liquid gating of YBa2Cu3O7-X. Proc. Natl Acad. Sci. USA 114, 215–220 (2017).10.1073/pnas.1613006114 ↗
12. Passarello, D. et al. Evidence for ionic liquid gate-induced metallization of vanadium dioxide bars over micron length scales. Nano Lett. 17, 2796–2801 (2017).10.1021/acs.nanolett.6b05029 ↗
13. Cui, B. et al. Direct imaging of structural changes induced by ionic liquid gating leading to engineered three-dimensional meso-structures. Nat. Commun. 9, 3055 (2018).
14. Tarascon, J. M. & Armand, M. Issues and challenges facing rechargeable lithium batteries. Nature 414, 359–367 (2001).10.1038/35104644 ↗
15. Xu, K. Electrolytes and interphases in Li-ion batteries and beyond. Chem. Rev. 114, 11503–11618 (2014).10.1021/cr500003w ↗
16. Griffith, K. J., Wiaderek, K. M., Cibin, G., Marbella, L. E. & Grey, C. P. Niobium tungsten oxides for high-rate lithium-ion energy storage. Nature 559, 556–563 (2018).10.1038/s41586-018-0347-0 ↗
17. Kang, B. & Ceder, G. Battery materials for ultrafast charging and discharging. Nature 458, 190–193 (2009).10.1038/nature07853 ↗
18. Liu, C., Neale, Z. G. & Cao, G. Understanding electrochemical potentials of cathode materials in rechargeable batteries. Mater. Today 19, 109–123 (2016).10.1016/j.mattod.2015.10.009 ↗
19. Sood, A. et al. Electrochemical ion insertion from the atomic to the device scale. Nat. Rev. Mater. 6, 847–867 (2021).10.1038/s41578-021-00314-y ↗
20. Dahlman, C. J. et al. Dynamics of lithium insertion in electrochromic titanium dioxide nanocrystal ensembles. J. Am. Chem. Soc. 143, 8278–8294 (2021).10.1021/jacs.0c10628 ↗
21. Lu, H. C. et al. Synthesis and dual-mode electrochromism of anisotropic monoclinic Nb12O29 colloidal nanoplatelets. ACS Nano 14, 10068–10082 (2020).10.1021/acsnano.0c03283 ↗
22. Granqvist, C. G. Electrochromic oxides: a bandstructure approach. Sol. Energy Mater. Sol. Cells 32, 369–382 (1994).10.1016/0927-0248(94)90100-7 ↗
23. Li, Y. et al. Low-voltage, CMOS-free synaptic memory based on LixTiO2 redox transistors. ACS Appl. Mater. Interfaces 11, 38982–38992 (2019).10.1021/acsami.9b14338 ↗
24. Fuller, E. J. et al. Li-ion synaptic transistor for low power analog computing. Adv. Mater. 29, 1604310 (2017).10.1002/adma.201604310 ↗
25. Zhu, Y. et al. Lithium-film ceramics for solid-state lithionic devices. Nat. Rev. Mater. 6, 313–331 (2020).10.1038/s41578-020-00261-0 ↗
26. Marianetti, C. A., Kotliar, G. & Ceder, G. A first-order Mott transition in LixCoO2. Nat. Mater. 3, 627–631 (2004).10.1038/nmat1178 ↗
27. Sun, Y. et al. Strongly correlated perovskite lithium ion shuttles. Proc. Natl Acad. Sci. USA 115, 9672–9677 (2018).10.1073/pnas.1805029115 ↗
28. Griffith, K. J. et al. Ionic and electronic conduction in TiNb2O7. J. Am. Chem. Soc. 141, 16706–16725 (2019).10.1021/jacs.9b06669 ↗
29. Tang, J. et al. ECRAM as scalable synaptic cell for high-speed, low-power neuromorphic computing. In IEEE International Electron Devices Meeting 13.1.1–13.1.4 (IEEE, 2018).
30. Muscher, P. K. et al. Highly efficient uniaxial in-plane stretching of a 2D material via ion insertion. Adv. Mater. 33, 2101875 (2021).10.1002/adma.202101875 ↗
31. He, Y. et al. Atomistic conversion reaction mechanism of WO3 in secondary ion batteries of Li, Na, and Ca. Angew. Chem. Int. Ed. Engl. 55, 6244–6247 (2016).10.1002/anie.201601542 ↗
32. Griffith, K. J., Forse, A. C., Griffin, J. M. & Grey, C. P. High-rate intercalation without nanostructuring in metastable Nb2O5 bronze phases. J. Am. Chem. Soc. 138, 8888–8899 (2016).10.1021/jacs.6b04345 ↗
33. Chen, D. et al. Unraveling the nature of anomalously fast energy storage in T-Nb2O5. J. Am. Chem. Soc. 139, 7071–7081 (2017).10.1021/jacs.7b03141 ↗
34. Augustyn, V. et al. High-rate electrochemical energy storage through Li+ intercalation pseudocapacitance. Nat. Mater. 12, 518–522 (2013).10.1038/nmat3601 ↗
35. Kim, J. W., Augustyn, V. & Dunn, B. The effect of crystallinity on the rapid pseudocapacitive response of Nb2O5. Adv. Energy Mater. 2, 141–148 (2012).10.1002/aenm.201100494 ↗
36. Lübke, M. et al. High power nano-Nb2O5 negative electrodes for lithium-ion batteries. Electrochim. Acta 192, 363–369 (2016).10.1016/j.electacta.2016.01.226 ↗
37. Brauer, G. Die Oxyde des Niobs. Z. Anorg. Allg. Chem. 248, 1–31 (1941).10.1002/zaac.19412480101 ↗
38. Nico, C., Monteiro, T. & Graça, M. P. F. Niobium oxides and niobates physical properties: review and prospects. Prog. Mater. Sci. 80, 1–37 (2016).10.1016/j.pmatsci.2016.02.001 ↗
39. Kato, K. & Tamura, S. Die Kristallstruktur von T-Nb2O5. Acta Cryst. B31, 673 (1975).10.1107/S0567740875003603 ↗
40. Boschker, J. E., Markurt, T., Albrecht, M. & Schwarzkopf, J. Heteroepitaxial growth of T-Nb2O5 on SrTiO3. Nanomaterials 8, 895 (2018).10.3390/nano8110895 ↗
41. Seo, J. W., Dieker, C., Fompeyrine, J., Siegwart, H. & Locquet, J.-P. Structural domains in antiferromagnetic LaFeO3 thin films. Int. J. Mater. Res. 97, 943–947 (2006).
42. Leriche, J.B. et al. An electrochemical cell for operando study of lithium batteries using synchrotron radiation. J. Electrochem. Soc. 157, A606–A610 (2010).10.1149/1.3355977 ↗
43. Barnes, P. et al. Electrochemically induced amorphous-to-rock-salt phase transformation in niobium oxide electrode for Li-ion batteries. Nat. Mater. 21, 795–803 (2022).10.1038/s41563-022-01242-0 ↗
44. Kowalski, D., Aoki, Y. & Habazaki, H. Characterization of amorphous anodic Nb2O5 nanofilm for gas sensing. ECS Trans. 16, 57–65 (2009).10.1149/1.3149569 ↗
45. Kodama, R., Terada, Y., Nakai, I., Komaba, S. & Kumagai, N. Electrochemical and in situ XAFS-XRD investigation of Nb2O5 for rechargeable lithium batteries. J. Electrochem. Soc. 153, A583–A588 (2006).10.1149/1.2163788 ↗
46. Simonelli, L. et al. CLÆSS: the hard X-ray absorption beamline of the ALBA CELLS synchrotron. Cogent Phys. 3, 1231987 (2016).10.1080/23311940.2016.1231987 ↗