High-rate electrochemical energy storage through Li+ intercalation pseudocapacitance

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Pseudocapacitance is commonly associated with surface or near-surface reversible redox reactions, as observed with RuO2· xH2O in an acidic electrolyte. However, we recently demonstrated that a pseudocapacitive mechanism occurs when lithium ions are inserted into mesoporous and nanocrystal films of orthorhombic Nb2O5 (T-Nb2O5; refs 1, 2). Here, we quantify the kinetics of charge storage in T-Nb2O5: currents that vary inversely with time, charge-storage capacity that is mostly independent of rate, and redox peaks that exhibit small voltage offsets even at high rates. We also define the structural characteristics necessary for this process, termed intercalation pseudocapacitance, which are a crystalline network that offers two-dimensional transport pathways and little structural change on intercalation. The principal benefit realized from intercalation pseudocapacitance is that high levels of charge storage are achieved within short periods of time because there are no limitations from solid-state diffusion. Thick electrodes (up to 40 μm thick) prepared with T-Nb2O5 offer the promise of exploiting intercalation pseudocapacitance to obtain high-rate charge-storage devices.

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Figure 1: Kinetic analysis of the electrochemical behaviour of T-Nb2O5.
Figure 2: Electrochemical cycling of a 40-μm-thick T-Nb2O5 electrode.
Figure 3: Structural features of lithium intercalation in T-Nb2O5.


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This work was supported by the Molecularly Engineered Energy Materials and the Energy Materials Center at Cornell, Energy Frontiers Research Centers funded by the US DOE Office of Basic Energy Sciences (DE-SC001342 and DE-SC0001086, respectively). XAS was performed at the Cornell High Energy Synchrotron Source, supported by the NSF and NIH/NIGMS (DMR-0936384). M.A.L. acknowledges support from the US DOD National Defense Science and Engineering Fellowship. J.C. was supported by Delegation Generale pour l’Armement (DGA). P.S. and P-L.T. acknowledge the support from the European Research Council (ERC, Advanced Grant, ERC-2011-AdG, Project 291543—IONACES) and the Chair of Excellence ‘Embedded multi-functional nanomaterials’ from the EADS Foundation.

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V.A., J.C., M.A.L. and J.W.K.: experimental work, data analysis. P-L.T., S.H.T., H.D.A., P.S., B.D.: project planning, data analysis.

Correspondence to Bruce Dunn.

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Augustyn, V., Come, J., Lowe, M. et al. High-rate electrochemical energy storage through Li+ intercalation pseudocapacitance. Nature Mater 12, 518–522 (2013) doi:10.1038/nmat3601

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