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Electrochemically induced amorphous-to-rock-salt phase transformation in niobium oxide electrode for Li-ion batteries

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.

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Fig. 1: Characterization of the as-prepared NCNO.
Fig. 2: Voltage profiles and differential capacity plots of the NCNO subjected to electrochemical cycling.
Fig. 3: SAED and high-resolution TEM images of the NCNO samples at different stages of electrochemical cycling; grazing-incidence X-ray diffraction of a cycled NCNO sample; and Nb K-edge EXAFS of samples at different states of discharge.
Fig. 4: Characterization of the oxidation state of Nb in RS-Nb2O5; compound phase diagram computed by Perdew–Burke–Ernzerhof; and voltage profiles of LixNb2O5.
Fig. 5: Electrochemical performance of RS-Nb2O5 and a-Nb2O5 samples with calculated migration barrier for RS-Li3Nb2O5.
Fig. 6: Characterization of the electrical conductivity of RS-Nb2O5 and a-Nb2O5 samples.

Data availability

The data that support the findings of this study are available from the corresponding authors on reasonable request.

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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.

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Authors and Affiliations

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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.

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Correspondence to Shyue Ping Ong or Hui Xiong.

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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 = b, 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.

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Supplementary Figs. 1–22, Tables 1–3 and text.

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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

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