Nanostructured birnessite exhibits high specific capacitance and nearly ideal capacitive behaviour in aqueous electrolytes, rendering it an important electrode material for low-cost, high-power energy storage devices. The mechanism of electrochemical capacitance in birnessite has been described as both Faradaic (involving redox) and non-Faradaic (involving only electrostatic interactions). To clarify the capacitive mechanism, we characterized birnessite’s response to applied potential using ex situ X-ray diffraction, electrochemical quartz crystal microbalance, in situ Raman spectroscopy and operando atomic force microscope dilatometry to provide a holistic understanding of its structural, gravimetric and mechanical responses. These observations are supported by atomic-scale simulations using density functional theory for the cation-intercalated structure of birnessite, ReaxFF reactive force field-based molecular dynamics and ReaxFF-based grand canonical Monte Carlo simulations on the dynamics at the birnessite–water–electrolyte interface. We show that capacitive charge storage in birnessite is governed by interlayer cation intercalation. We conclude that the intercalation appears capacitive due to the presence of nanoconfined interlayer structural water, which mediates the interaction between the intercalated cation and the birnessite host and leads to minimal structural changes.
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Critical role of water structure around interlayer ions for ion storage in layered double hydroxides
Nature Communications Open Access 28 October 2022
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Experimental data (electrochemistry, Raman, XRD, EQCM and AFM) and simulation data (ReaxFF and DFT) are available in this repository: Boyd, S., Ganeshan, K., Tsai, W.-Y., Tao Wu, Saeed, S., Jiang, D., Balke, N., van Duin, A. & Augustyn, V. Effects of interlayer confinement and hydration on capacitive charge storage in birnessite. (Materials Cloud Archive 2021.X, 2021); https://doi.org/10.24435/materialscloud:kh-y2.
The DFT simulations were performed using VASP, which is available under license from VASP (https://www.vasp.at/). The ReaxFF simulations were performed using the ReaxFF module within the ADF code. ADF is available under license from SCM Amsterdam (https://www.scm.com/). Force fields and input files associated with this work can be obtained by a request through the Penn State Materials Computation Center website: https://www.mri.psu.edu/materials-computation-center/connect-mcc.
Gileadi, E. Electrode Kinetics for Chemists, Chemical Engineers, and Materials Scientists (VCH, 1993).
Conway, B. E. Electrochemical Supercapacitors: Scientific Fundamentals and Technological Applications (Kluwer-Academic, 1999).
Srimuk, P., Su, X., Yoon, J., Aurbach, D. & Presser, V. Charge-transfer materials for electrochemical water desalination, ion separation and the recovery of elements. Nat. Rev. Mater. 5, 517–538 (2020).
Waegele, M. M., Gunathunge, C. M., Li, J. & Li, X. How cations affect the electric double layer and the rates and selectivity of electrocatalytic processes. J. Chem. Phys. 151, 160902 (2019).
Fleischmann, S. et al. Pseudocapacitance: from fundamental understanding to high power energy storage materials. Chem. Rev. 120, 6738–6782 (2020).
Brousse, T., Belanger, D., Long, J. W., Bélanger, D. & Long, J. W. To be or not to be pseudocapacitive? J. Electrochem. Soc. 162, A5185–A5189 (2015).
Costentin, C., Porter, T. R., Save, J. & Savéant, J. M. How do pseudocapacitors store energy? Theoretical analysis and experimental illustration. ACS Appl. Mater. Interfaces 9, 8649–8658 (2017).
Mateos, M., Makivic, N., Kim, Y., Limoges, B. & Balland, V. Accessing the two-electron charge storage capacity of MnO2 in mild aqueous electrolytes. Adv. Energy Mater. 10, 2000332 (2020).
Chang, J.-K., Lee, M.-T. & Tsai, W.-T. In situ Mn K-edge X-ray absorption spectroscopic studies of anodically deposited manganese oxide with relevance to supercapacitor applications. J. Power Sources 166, 590–594 (2007).
Liu, L. et al. The origin of electrochemical actuation of MnO2/Ni bilayer film derived by redox pseudocapacitive process. Adv. Funct. Mater. 29, 1806778 (2019).
Chen, D. et al. Probing the charge storage mechanism of a pseudocapacitive MnO2 electrode using in operando Raman spectroscopy. Chem. Mater. 27, 6608–6619 (2015).
Athouël, L. et al. Variation of the MnO2 birnessite structure upon charge/discharge in an electrochemical supercapacitor electrode in aqueous Na2SO4 electrolyte. J. Phys. Chem. C 112, 7270–7277 (2008).
Yang, L. et al. Investigation into the origin of high stability of δ-MnO2 pseudo-capacitive electrode using operando Raman spectroscopy. Nano Energy 30, 293–302 (2016).
Kanoh, H., Tang, W., Makita, Y. & Ooi, K. Electrochemical intercalation of alkali-metal ions into birnessite-type manganese oxide in aqueous solution. Langmuir 13, 6845–6849 (1997).
Arias, C. R. et al. New insights into pseudocapacitive charge-storage mechanisms in Li-birnessite type MnO2 monitored by fast quartz crystal microbalance methods. J. Phys. Chem. C 118, 26551–26559 (2014).
Toupin, M., Brousse, T. & Bélanger, D. Influence of microstructure on the charge storage properties of chemically synthesized manganese dioxide. Chem. Mater. 14, 3946–3952 (2002).
Leong, Z. Y. & Yang, H. Y. A study of MnO2 with different crystalline forms for pseudocapacitive desalination. ACS Appl. Mater. Interfaces 11, 13176–13184 (2019).
Lanson, B., Drits, V. A., Feng, Q. & Manceau, A. Structure of synthetic Na-rich birnessite: evidence for a triclinic one-layer cell. Am. Mineral. 87, 1662–1671 (2002).
Dong, W., Rolison, D. R. & Dunn, B. Electrochemical properties of high surface area vanadium oxide aerogels. Electrochem. Solid State Lett. 3, 457–459 (2000).
Ghodbane, O., Ataherian, F., Wu, N.-L. L. & Favier, F. In situ crystallographic investigations of charge storage mechanisms in MnO2-based electrochemical capacitors. J. Power Sources 206, 454–462 (2012).
Shan, X. et al. Structural water and disordered structure promote aqueous sodium-ion energy storage in sodium-birnessite. Nat. Commun. 10, 4975 (2019).
Xiong, P. et al. Redox active cation intercalation/deintercalation in two-dimensional layered MnO2 nanostructures for high-rate electrochemical energy storage. ACS Appl. Mater. Interfaces 9, 6282–6291 (2017).
Shan, X. et al. Framework doping of Ni enhances pseudocapacitive Na-ion storage of (Ni)MnO2 layered birnessite. Chem. Mater. 31, 8774–8786 (2019).
Julien, C. et al. Raman spectra of birnessite manganese dioxides. Solid State Ion. 159, 345–356 (2003).
Kanke, Y., Kato, K., Takayama-muromachi, E., Isobe, M. & Kosuda, K. Structure of K0.5V2O5. Acta Cryst. C 46, 1590–1592 (1990).
Beasley, C. A., Sassin, M. B. & Long, J. W. Extending electrochemical quartz crystal microbalance techniques to macroscale electrodes: insights on pseudocapacitance mechanisms in MnOx-coated carbon nanofoams. J. Electrochem. Soc. 162, A5060–A5064 (2015).
Zhang, Q. et al. The charge storage mechanisms of 2D cation-intercalated manganese oxide in different electrolytes. Adv. Energy Mater. 9, 1802707 (2019).
Sparks, D. L. Environmental Soil Chemistry 2nd edn (Elsevier Science, 2003).
Ward, M. D. in Physical Electrochemistry: Principles, Methods, and Applications (ed. Rubinstein, I.) 293–338 (MarcelDekker, 1995).
Gao, Q. et al. Tracking ion intercalation into layered Ti3C2 MXene films across length scales. Energy Environ. Sci. 13, 2549–2558 (2020).
Zhang, Q. et al. The charge storage mechanisms of 2D cation-intercalated manganese oxide in different electrolytes. Adv. Energy Mater. 9, 1802707 (2018).
Hsu, Y. K., Chen, Y. C., Lin, Y. G., Chen, L. C. & Chen, K. H. Reversible phase transformation of MnO2 nanosheets in an electrochemical capacitor investigated by in situ Raman spectroscopy. Chem. Commun. 47, 1252–1254 (2011).
Costentin, C., Porter, T. R. & Savéant, J. M. Nature of electronic conduction in ‘pseudocapacitive’ films: transition from the insulator state to band-conduction. ACS Appl. Mater. Interfaces 11, 28769–28773 (2019).
Fung, V., Wu, Z. & Jiang, D. E. New bonding model of radical adsorbate on lattice oxygen of perovskites. J. Phys. Chem. Lett. 9, 6321–6325 (2018).
Tsai, W., Wang, R., Boyd, S., Augustyn, V. & Balke, N. Probing local electrochemistry via mechanical cyclic voltammetry curves. Nano Energy 81, 105592 (2020).
Ma, Z. et al. Construction of hierarchical α-MnO2 nanowires@ultrathin δ-MnO2 nanosheets core-shell nanostructure with excellent cycling stability for high-power asymmetric supercapacitor electrodes. ACS Appl. Mater. Interfaces 8, 9050–9058 (2016).
Banerjee, R. et al. Strain modulated superlattices in graphene. Nano Lett. 20, 3113–3121 (2020).
Ando, Y., Okubo, M., Yamada, A. & Otani, M. Capacitive versus pseudocapacitive storage in MXene. Adv. Funct. Mater. 30, 2000820 (2020).
Rowley, C. N. & Roux, B. The solvation structure of Na+ and K+ in liquid water determined from high level ab initio molecular dynamics simulations. J. Chem. Theory Comput. 8, 3526–3535 (2012).
Merlet, C. et al. On the molecular origin of supercapacitance in nanoporous carbon electrodes. Nat. Mater. 11, 306–310 (2012).
Boyd, S., Geise, N. R., Toney, M. F. & Augustyn, V. High power energy storage via electrochemically expanded and hydrated manganese-rich oxides. Front. Chem. 8, 715 (2020).
Nakayama, M. et al. Cathodic synthesis of birnessite-type layered manganese oxides for electrocapacitive catalysis. J. Electrochem. Soc. 159, A1176–A1182 (2012).
Yoon, Y., Yan, B. & Surendranath, Y. Suppressing ion transfer enables versatile measurements of electrochemical surface area for intrinsic activity comparisons. J. Am. Chem. Soc. 140, 2397–2400 (2018).
Wang, R. et al. Operando atomic force microscopy reveals mechanics of structural water driven battery-to-pseudocapacitor transition. ACS Nano 12, 6032–6039 (2018).
Operation and Service Manual QCM200 Quartz Crystal Microbalance Digital Controller QCM25 5 MHz Crystal Oscillator (Stanford Research Systems, 2016).
Gabrielli, C., Keddam, M. & Torresi, R. Calibration of the electrochemical quartz crystal microbalance. J. Electrochem. Soc. 138, 2657–2660 (1991).
Kresse, G. & Hafner, J. Ab initio molecular-dynamics simulation of the liquid–metalamorphous–semiconductor transition in germanium. Phys. Rev. B 49, 14251–14269 (1994).
Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558–561 (1993).
Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).
Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).
Kresse, G. & Hafner, J. Ab initio molecular dynamics for open-shell transition metals. Phys. Rev. B 48, 13115–13118 (1993).
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
Anisimov, V. I., Aryasetiawan, F. & Lichtenstein, A. I. First-principles calculations of the electronic structure and spectra of strongly correlated systems: the LDA+U Method. J. Phys. Condens. Matter 9, 767–808 (1997).
Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A. Consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H–Pu. J. Chem. Phys. 132, 154104 (2010).
Chenoweth, K., Van Duin, A. C. T. & Goddard, W. A. ReaxFF reactive force field for molecular dynamics simulations of hydrocarbon oxidation. J. Phys. Chem. A 112, 1040–1053 (2008).
Senftle, T. P. et al. The ReaxFF reactive force-field: development, applications and future directions. NPJ Comput. Mater. 2, 15011 (2016).
Rappé, A. K., & Goddard, W. A. Charge equilibration for molecular dynamics simulations. J. Phys. Chem. 95, 3358–3363 (1991).
This work was supported as part of the Fluid Interface Reactions, Structures and Transport, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences at Oak Ridge National Laboratory under contract no. DE-AC0500OR22725 with UT Battelle, LLC (V.A., N.B., D.-E.J. and A.C.T.v.D.). S.B. acknowledges a graduate fellowship through the National Science Foundation Graduate Research Fellowship Program under grant no. 571800. This work was performed in part at the Analytical Instrumentation Facility (AIF) at North Carolina State University, which is supported by the State of North Carolina and the National Science Foundation (award no. ECCS-1542015). The AIF is a member of the North Carolina Research Triangle Nanotechnology Network (RTNN), a site in the National Nanotechnology Coordinated Infrastructure (NNCI). Operando AFM was conducted at the Center for Nanophase Materials Sciences, which is a US Department of Energy Office of Science User Facility.
The authors declare no competing interests.
Peer review information Nature Materials thanks Thierry Brousse, Patrice Simon and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
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Supplementary Figs. 1–17, Tables 1 and 2, and Methods.
Supplementary Video 1
ReaxFF GCMC simulation intercalating K+ cations and H2O molecules in dry MnO2. The local inhomogeneity of species intercalation causes wrinkling of the MnO2 layers.
Supplementary Video 2
ReaxFF GCMC simulation intercalating K+ cations into MnO2·0.25(H2O).
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Boyd, S., Ganeshan, K., Tsai, WY. et al. Effects of interlayer confinement and hydration on capacitive charge storage in birnessite. Nat. Mater. 20, 1689–1694 (2021). https://doi.org/10.1038/s41563-021-01066-4
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