Abstract
Intercalation-type metal oxides are promising negative electrode materials for safe rechargeable lithium-ion batteries due to the reduced risk of Li plating at low voltages. Nevertheless, their lower energy and power density along with cycling instability remain bottlenecks for their implementation, especially for fast-charging applications. Here, we report a nanostructured rock-salt Nb2O5 electrode formed through an amorphous-to-crystalline transformation during repeated electrochemical cycling with Li+. This electrode can reversibly cycle three lithiums per Nb2O5, corresponding to a capacity of 269 mAh g−1 at 20 mA g−1, and retains a capacity of 191 mAh g−1 at a high rate of 1 A g−1. It exhibits superb cycling stability with a capacity of 225 mAh g−1 at 200 mA g−1 for 400 cycles, and a Coulombic efficiency of 99.93%. We attribute the enhanced performance to the cubic rock-salt framework, which promotes low-energy migration paths. Our work suggests that inducing crystallization of amorphous nanomaterials through electrochemical cycling is a promising avenue for creating unconventional high-performance metal oxide electrode materials.
This is a preview of subscription content, access via your institution
Access options
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
Data availability
The data that support the findings of this study are available from the corresponding authors on reasonable request.
References
Melot, B. C. & Tarascon, J. M. Design and preparation of materials for advanced electrochemical storage. Acc. Chem. Res. 46, 1226–1238 (2013).
Ohzuku, T., Sawai, K. & Hirai, T. Electrochemistry of L-niobium pentoxide in a lithium/non-aqueous cell. J. Power Sources 19, 287–299 (1987).
Reichman, B. & Bard, A. J. The application of Nb2O5 as a cathode in non-aqueous lithium cells. J. Electrochem. Soc. 128, 344–346 (1981).
Nowak, I. & Ziolek, M. Niobium compounds: preparation, characterization, and application in heterogeneous catalysis. Chem. Rev. 99, 3603–3624 (1999).
Aegerter, M. A. Sol–gel niobium pentoxide: a promising material for electrochromic coatings, batteries, nanocrystalline solar cells and catalysis. Sol. Energy Mater. Sol. Cells 68, 401–422 (2001).
Le Viet, A., Reddy, M. V., Jose, R., Chowdari, B. V. R. & Ramakrishna, S. Nanostructured Nb2O5 polymorphs by electrospinning for rechargeable lithium batteries. J. Phys. Chem. C 114, 664–671 (2010).
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).
Yan, L. T. et al. Recent advances in nanostructured Nb-based oxides for electrochemical energy storage. Nanoscale 8, 8443–8465 (2016).
Brezesinski, K. et al. Pseudocapacitive contributions to charge storage in highly ordered mesoporous group V transition metal oxides with iso-oriented layered nanocrystalline domains. J. Am. Chem. Soc. 132, 6982–6990 (2010).
Augustyn, V. et al. High-rate electrochemical energy storage through Li+ intercalation pseudocapacitance. Nat. Mater. 12, 518–522 (2013).
Wang, X. L. et al. High-performance supercapacitors based on nanocomposites of Nb2O5 nanocrystals and carbon nanotubes. Adv. Energy Mater. 1, 1089–1093 (2011).
Mukherjee, R., Krishnan, R., Lu, T. M. & Koratkar, N. Nanostructured electrodes for high-power lithium ion batteries. Nano Energy 1, 518–533 (2012).
Wei, M. D., Qi, Z. M., Ichihara, M. & Zhou, H. S. Synthesis of single-crystal niobium pentoxide nanobelts. Acta Materialia 56, 2488–2494 (2008).
Brauer, G. Die oxyde des niobs. Z. Anorg. Allg. Chem. 248, 1–31 (1941).
Schäfer, H., Gruehn, R. & Schulte, F. The modifications of niobium pentoxide. Angew. Chem. Int. Ed. 5, 40–52 (1966).
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).
Pralong, V. Lithium intercalation into transition metal oxides: a route to generate new ordered rock salt type structure. Prog. Solid State Chem. 37, 262–277 (2009).
Xiong, H. et al. Self-improving anode for lithium-ion batteries based on amorphous to cubic phase transition in TiO2 nanotubes. J. Phys. Chem. C 116, 3181–3187 (2012).
Yildirim, H., Greeley, J. P. & Sankaranarayanan, S. K. R. S. Concentration-dependent ordering of lithiated amorphous TiO2. J. Phys. Chem. C 117, 3834–3845 (2013).
Jung, H. et al. Redox cycling driven transformation of layered manganese oxides to tunnel structures. J. Am. Chem. Soc. 142, 2506–2513 (2020).
Liu, H. D. et al. A disordered rock salt anode for fast-charging lithium-ion batteries. Nature 585, 63–67 (2020).
Schmuki, P. & Virtanen, S. (eds) Electrochemistry at the Nanoscale (Springer, 2009).
Liu, C. F., Neale, Z. G. & Cao, G. Z. Understanding electrochemical potentials of cathode materials in rechargeable batteries. Mater. Today 19, 109–123 (2016).
Sasaki, T., Ukyo, Y. & Novak, P. Memory effect in a lithium-ion battery. Nat. Mater. 12, 569–575 (2013).
Madej, E., La Mantia, F., Schuhmann, W. & Ventosa, E. Impact of the specific surface area on the memory effect in Li-ion batteries: the case of anatase TiO2. Adv. Energy Mater. https://doi.org/10.1002/aenm.201400829 (2014).
Ventosa, E., Loffler, T., La Mantia, F. & Schuhmann, W. Understanding memory effects in Li-ion batteries: evidence of a kinetic origin in TiO2 upon hydrogen annealing. Chem. Commun. 52, 11524–11526 (2016).
Ovejas, V. J. & Cuadras, A. Effects of cycling on lithium-ion battery hysteresis and overvoltage. Sci. Rep. https://doi.org/10.1038/s41598-019-51474-5 (2019).
Dahlman, C. J. et al. Dynamics of lithium insertion in electrochromic titanium dioxide nanocrystal ensembles. J. Am. Chem. Soc. 143, 8278–8294 (2021).
Scherrer, P. The space grid of aluminium. Phys. Z. 19, 23–27 (1918).
Garbassi, F., Bart, J. C. J. & Petrini, G. XPS study of tellurium—niobium and tellurium—tantalum oxide systems. J. Electron Spectrosc. Relat. Phenom. 22, 95–107 (1981).
Ozer, N., Rubin, M. D. & Lampert, C. M. Optical and electrochemical characteristics of niobium oxide films prepared by sol-gel process and magnetron sputtering. A comparison. Sol. Energy Mater. Sol. Cells 40, 285–296 (1996).
Bahl, M. K. ESCA studies of some niobium compounds. J. Phys. Chem. Solids 36, 485–491 (1975).
Simon, D., Perrin, C. & Baillif, P. Electron spectrometry study (ESCA) of niobium and its oxides. Application to the oxidation at high temperature and low oxygen pressure. C. R. Hebd. Acad. Sci. Ser. C 283, 241–244 (1976).
Jouve, J., Belkacem, Y. & Severac, C. X-ray photoelectron-spectroscopy study of phosphorus incorporation in anodic oxide-films on niobium. Thin Solid Films 139, 67–75 (1986).
Verma, P., Maire, P. & Novak, P. A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries. Electrochim. Acta 55, 6332–6341 (2010).
Monfort, Y., Maisseu, A., Allais, G., Deschanv, A. & Delavign, P. Structure and morphology of niobium suboxides. Phys. Status Solidi A Appl. Res. 15, 129–142 (1973).
Yabuuchi, N. et al. High-capacity electrode materials for rechargeable lithium batteries: Li3NbO4-based system with cation-disordered rocksalt structure. Proc. Natl Acad. Sci. USA 112, 7650–7655 (2015).
Preefer, M. B. et al. Multielectron redox and insulator-to-metal transition upon lithium insertion in the fast-charging, Wadsley-Roth phase PNb9O25. Chem. Mater. 32, 4553–4563 (2020).
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).
Van der Ven, A., Ceder, G., Asta, M. & Tepesch, P. D. First-principles theory of ionic diffusion with nondilute carriers. Phys. Rev. B https://doi.org/10.1103/PhysRevB.64.184307 (2001).
Lee, J. et al. Unlocking the potential of cation-disordered oxides for rechargeable lithium batteries. Science 343, 519–522 (2014).
Thinius, S., Islam, M. M., Heitjans, P. & Bredow, T. Theoretical study of Li migration in lithium-graphite intercalation compounds with dispersion-corrected DFT methods. J. Phys. Chem. C 118, 2273–2280 (2014).
Acevedo-Pena, P. & Gonzalez, I. EIS characterization of the barrier layer formed over Ti during its potentiostatic anodization in 0.1 M HClO4/x mM HF (1 mM ≤ x ≤ 500 mM). J. Electrochem. Soc. 159, C101–C108 (2012).
Conway, B. E., Birss, V. & Wojtowicz, J. The role and utilization of pseudocapacitance for energy storage by supercapacitors. J. Power Sources 66, 1–14 (1997).
Wang, J., Polleux, J., Lim, J. & Dunn, B. Pseudocapacitive contributions to electrochemical energy storage in TiO2 (anatase) nanoparticles. J. Phys. Chem. C 111, 14925–14931 (2007).
Savva, A. I. et al. Defect generation in TiO2 nanotube anodes via heat treatment in various atmospheres for lithium- ion batteries. Phys. Chem. Chem. Phys. 20, 22537–22546 (2018).
Rani, R. A., Zoolfakar, A. S., O’Mullane, A. P., Austin, M. W. & Kalantar-Zadeh, K. Thin films and nanostructures of niobium pentoxide: fundamental properties, synthesis methods and applications. J. Mater. Chem. A 2, 15683–15703 (2014).
Islam, S. Z., Reed, A., Wanninayake, N., Kim, D. Y. & Rankin, S. E. Remarkable enhancement of photocatalytic water oxidation in N2/Ar plasma treated, mesoporous TiO2 films. J. Phys. Chem. C 120, 14069–14081 (2016).
Barnes, P. et al. Electropolishing valve metals with a sulfuric acid-methanol electrolyte at low temperature. Surf. Coat. Technol. 347, 150–156 (2018).
Lee, K., Yang, Y., Yang, M. & Schmuki, P. Formation of highly ordered nanochannel Nb oxide by self-organizing anodization. Chem. Eur. J. 18, 9521–9524 (2012).
Roslyakov, I. V. et al. Annealing induced structural and phase transitions in anodic aluminum oxide prepared in oxalic acid electrolyte. Surf. Coat. Technol. https://doi.org/10.1016/j.surfcoat.2019.125159 (2020).
Baram, N. & Ein-Eli, Y. Electrochemical impedance spectroscopy of porous TiO2 for photocatalytic applications. J. Phys. Chem. C 114, 9781–9790 (2010).
Kresse, G. & Furthmuller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).
Blochl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
Jain, A. et al. Commentary: the materials project: a materials genome approach to accelerating materials innovation. Appl. Mater. https://doi.org/10.1063/1.4812323 (2013).
Hart, G. L. W. & Forcade, R. W. Algorithm for generating derivative structures. Phys. Rev. B https://doi.org/10.1103/Physrevb.77.224115 (2008).
Ong, S. P. et al. Python Materials Genomics (pymatgen): a robust, open-source python library for materials analysis. Comput. Mater. Sci. 68, 314–319 (2013).
Aydinol, M. K., Kohan, A. F., Ceder, G., Cho, K. & Joannopoulos, J. Ab initio study of lithium intercalation in metal oxides and metal dichalcogenides. Phys. Rev. B 56, 1354–1365 (1997).
Acknowledgements
This work was supported by the National Science Foundation (grant no. DMR-1454984). Use of the environmental atomic force microscope was supported by the National Science Foundation Major Research Instrumentation Program (grant no. 1727026). We acknowledge B. Dunn from the University of California, Los Angeles for insightful discussion. We also thank W. Xu from Argonne National Laboratory for support of synchrotron X-ray diffraction measurements. We thank P. Boysen from the Boise State University machine shop for his knowledge and expertise in the production of equipment used in this study. Use of the Center for Nanoscale Materials and Advanced Photon Source, both Department of Energy Office of Science User Facilities, was supported by the US Department of Energy, Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357. XPS, time-of-flight secondary-ion mass spectrometry and data analysis were supported by the US Department of Energy Office of Science, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under award no. 10122 and performed using the Environmental Molecular Sciences Laboratory (grid.436923.9), a Department of Energy Office of Science User Facility sponsored by the Biological and Environmental Research programme. This research also used recourses at the Surface Science Laboratory and Boise State Center for Materials Characterization at Boise State University. Y.Z., J.Q., Zhuoying Zhu, C.C. and S.P.O. acknowledge funding from the National Science Foundation Materials Research Science and Engineering Center programme through the University of California, Irvine Center for Complex and Active Materials (DMR-2011967) for the computational portions of this work; the use of data and software resources from the Materials Project, funded by the US Department of Energy Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division under contract no. DE-AC02-05-CH11231 (Materials Project programme KC23MP); and computing resources provided by the Extreme Science and Engineering Discovery Environment under grant ACI-1548562.
Author information
Authors and Affiliations
Contributions
H.X. and P.B. conceived and designed all experiments. S.P.O., Y. Zuo, J.Q., Zhuoying Zhu and C.C. designed all computational modelling work. P.B. and K.D. synthesized the materials. P.B. conducted all electrochemical measurements. S.L., P.B. and C.D. conducted structural characterization by XAS. H. Zhou, Z.M., P.B., C.D. and E.G. conducted structural characterization by synchrotron X-ray diffraction. J.G.C. and Y.D. collected XPS data. D.H., Y.L., K.S. and P.B. collected focused ion beam TEM, high-resolution TEM and SAED data. P.B., H. Zhu, O.O.M. and P.H.D. designed and performed the PF-TUNA experiments. P.B., A. B. and P.J.S. designed and collected the two-point probe measurements. Zihua Zhu, Y. Zhou and Y.D. conducted the time-of-flight secondary-ion mass spectrometry measurements. D.S. and P.B. conducted and analysed the inductively coupled plasma mass spectrometry measurements. P.B., H.X., S.L., J.G.C., D.H., H. Zhou, Z.M., P.H.D., Zihua Zhu, Y.D. and P.J.S. analysed the collected data. P.B., Y. Zuo, H.X. and S.P.O. wrote the manuscript. All authors were involved in editing the manuscript.
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing interests.
Peer review
Peer review information
Nature Materials thanks the anonymous reviewers for their contribution to the peer review of this work.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Extended data
Extended Data Fig. 1 Characterization of lithium ion diffusivity and charge storage of RS-Nb2O5 and a-Nb2O5 sample.
a, GITT measurements of the RS- and a-Nb2O5 electrodes. b, The logarithmic plot of Li ion diffusivity as a function of voltage by GITT measurements. Overall, RS-Nb2O5 exhibited an order of magnitude higher Li ion diffusivity compared to a-Nb2O5 within the potential window during lithiation. During the cathodic scan, both samples experienced a gradual decrease in diffusivity as more Li+ occupied the vacant sites in the host material. It is worth noting that below 1.1 V, Li+ diffusivity in RS-Nb2O5 slightly increased, concurrent with the ongoing phase transformation upon cycling. Li+ diffusivity in RS-Nb2O5 is also higher than that of other polymorphs of Nb2O5 electrodes. c and d, cyclic voltammograms of RS- and a-Nb2O5 electrodes at varying scan rates. Insights in terms of diffusion and capacitive contribution to Li storage can be obtained by analyzing the peak current (i) dependence on scan rate (ν). For a redox reaction limited by semi-infinite diffusion, the peak current is proportional to the square root of the scan rate (ν1/2); while for a capacitive process it varies linearly with ν44,45. A b value can be obtained by analyzing the power law relationship between i and ν via i = aνb, where a and b are adjustable parameters. It was found that the b values for RS-Nb2O5 and a-Nb2O5 sample were ~0.85 and ~0.80, respectively. The results suggest both electrodes have mixed contribution from diffusion and capacitive process with RS-Nb2O5 electrode having a slightly higher capacitive contribution indicative of a faster kinetic in RS-Nb2O5.
Supplementary information
Supplementary Information
Supplementary Figs. 1–22, Tables 1–3 and text.
Rights and permissions
About this article
Cite this article
Barnes, P., Zuo, Y., Dixon, K. et al. Electrochemically induced amorphous-to-rock-salt phase transformation in niobium oxide electrode for Li-ion batteries. Nat. Mater. 21, 795–803 (2022). https://doi.org/10.1038/s41563-022-01242-0
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41563-022-01242-0
This article is cited by
-
Capturing ion trapping and detrapping dynamics in electrochromic thin films
Nature Communications (2024)
-
Amorphous Sb/C composite with isotropic expansion property as an ultra-stable and high-rate anode for lithium-ion batteries
Rare Metals (2024)
-
Control of metal oxides’ electronic conductivity through visual intercalation chemical reactions
Nature Communications (2023)
-
Discovery of fast and stable proton storage in bulk hexagonal molybdenum oxide
Nature Communications (2023)
-
Li iontronics in single-crystalline T-Nb2O5 thin films with vertical ionic transport channels
Nature Materials (2023)