Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Effects of interlayer confinement and hydration on capacitive charge storage in birnessite

Abstract

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.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Fig. 1: Conceptual comparison of cation adsorption at a planar electrochemical interface and into a nanoconfined interlayer of an electrode material.
Fig. 2: Structure and morphology of electrodeposited birnessite thin films.
Fig. 3: Electrochemical and structural behaviour of birnessite in 0.5 M K2SO4.
Fig. 4: Cation-dominated capacitive charge storage in birnessite.
Fig. 5: Changes in the local and electronic structures of birnessite during K+ and H2O (de)intercalation.
Fig. 6: Effect of charge stratification on the K+–OMn distance.

Data availability

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.

Code availability

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.

References

  1. 1.

    Gileadi, E. Electrode Kinetics for Chemists, Chemical Engineers, and Materials Scientists (VCH, 1993).

  2. 2.

    Conway, B. E. Electrochemical Supercapacitors: Scientific Fundamentals and Technological Applications (Kluwer-Academic, 1999).

  3. 3.

    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).

    CAS  Article  Google Scholar 

  4. 4.

    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).

    Article  CAS  Google Scholar 

  5. 5.

    Fleischmann, S. et al. Pseudocapacitance: from fundamental understanding to high power energy storage materials. Chem. Rev. 120, 6738–6782 (2020).

    CAS  Article  Google Scholar 

  6. 6.

    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).

    CAS  Article  Google Scholar 

  7. 7.

    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).

    CAS  Article  Google Scholar 

  8. 8.

    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).

    CAS  Article  Google Scholar 

  9. 9.

    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).

    CAS  Article  Google Scholar 

  10. 10.

    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).

    Article  CAS  Google Scholar 

  11. 11.

    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).

    CAS  Article  Google Scholar 

  12. 12.

    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).

    Article  CAS  Google Scholar 

  13. 13.

    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).

    CAS  Article  Google Scholar 

  14. 14.

    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).

    CAS  Article  Google Scholar 

  15. 15.

    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).

    CAS  Article  Google Scholar 

  16. 16.

    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).

    CAS  Article  Google Scholar 

  17. 17.

    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).

    CAS  Article  Google Scholar 

  18. 18.

    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).

    CAS  Article  Google Scholar 

  19. 19.

    Dong, W., Rolison, D. R. & Dunn, B. Electrochemical properties of high surface area vanadium oxide aerogels. Electrochem. Solid State Lett. 3, 457–459 (2000).

    CAS  Article  Google Scholar 

  20. 20.

    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).

    CAS  Article  Google Scholar 

  21. 21.

    Shan, X. et al. Structural water and disordered structure promote aqueous sodium-ion energy storage in sodium-birnessite. Nat. Commun. 10, 4975 (2019).

    Article  CAS  Google Scholar 

  22. 22.

    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).

    CAS  Article  Google Scholar 

  23. 23.

    Shan, X. et al. Framework doping of Ni enhances pseudocapacitive Na-ion storage of (Ni)MnO2 layered birnessite. Chem. Mater. 31, 8774–8786 (2019).

    CAS  Article  Google Scholar 

  24. 24.

    Julien, C. et al. Raman spectra of birnessite manganese dioxides. Solid State Ion. 159, 345–356 (2003).

    CAS  Article  Google Scholar 

  25. 25.

    Kanke, Y., Kato, K., Takayama-muromachi, E., Isobe, M. & Kosuda, K. Structure of K0.5V2O5. Acta Cryst. C 46, 1590–1592 (1990).

    Article  Google Scholar 

  26. 26.

    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).

    CAS  Article  Google Scholar 

  27. 27.

    Zhang, Q. et al. The charge storage mechanisms of 2D cation-intercalated manganese oxide in different electrolytes. Adv. Energy Mater. 9, 1802707 (2019).

    Article  CAS  Google Scholar 

  28. 28.

    Sparks, D. L. Environmental Soil Chemistry 2nd edn (Elsevier Science, 2003).

  29. 29.

    Ward, M. D. in Physical Electrochemistry: Principles, Methods, and Applications (ed. Rubinstein, I.) 293–338 (MarcelDekker, 1995).

  30. 30.

    Gao, Q. et al. Tracking ion intercalation into layered Ti3C2 MXene films across length scales. Energy Environ. Sci. 13, 2549–2558 (2020).

    CAS  Article  Google Scholar 

  31. 31.

    Zhang, Q. et al. The charge storage mechanisms of 2D cation-intercalated manganese oxide in different electrolytes. Adv. Energy Mater. 9, 1802707 (2018).

    Article  CAS  Google Scholar 

  32. 32.

    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).

    CAS  Article  Google Scholar 

  33. 33.

    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).

    CAS  Article  Google Scholar 

  34. 34.

    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).

    CAS  Article  Google Scholar 

  35. 35.

    Tsai, W., Wang, R., Boyd, S., Augustyn, V. & Balke, N. Probing local electrochemistry via mechanical cyclic voltammetry curves. Nano Energy 81, 105592 (2020).

    Article  CAS  Google Scholar 

  36. 36.

    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).

    CAS  Article  Google Scholar 

  37. 37.

    Banerjee, R. et al. Strain modulated superlattices in graphene. Nano Lett. 20, 3113–3121 (2020).

    CAS  Article  Google Scholar 

  38. 38.

    Ando, Y., Okubo, M., Yamada, A. & Otani, M. Capacitive versus pseudocapacitive storage in MXene. Adv. Funct. Mater. 30, 2000820 (2020).

    CAS  Article  Google Scholar 

  39. 39.

    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).

    CAS  Article  Google Scholar 

  40. 40.

    Merlet, C. et al. On the molecular origin of supercapacitance in nanoporous carbon electrodes. Nat. Mater. 11, 306–310 (2012).

    CAS  Article  Google Scholar 

  41. 41.

    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).

    CAS  Article  Google Scholar 

  42. 42.

    Nakayama, M. et al. Cathodic synthesis of birnessite-type layered manganese oxides for electrocapacitive catalysis. J. Electrochem. Soc. 159, A1176–A1182 (2012).

    CAS  Article  Google Scholar 

  43. 43.

    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).

    CAS  Article  Google Scholar 

  44. 44.

    Wang, R. et al. Operando atomic force microscopy reveals mechanics of structural water driven battery-to-pseudocapacitor transition. ACS Nano 12, 6032–6039 (2018).

    CAS  Article  Google Scholar 

  45. 45.

    Operation and Service Manual QCM200 Quartz Crystal Microbalance Digital Controller QCM25 5 MHz Crystal Oscillator (Stanford Research Systems, 2016).

  46. 46.

    Gabrielli, C., Keddam, M. & Torresi, R. Calibration of the electrochemical quartz crystal microbalance. J. Electrochem. Soc. 138, 2657–2660 (1991).

    CAS  Article  Google Scholar 

  47. 47.

    Kresse, G. & Hafner, J. Ab initio molecular-dynamics simulation of the liquid–metalamorphous–semiconductor transition in germanium. Phys. Rev. B 49, 14251–14269 (1994).

    CAS  Article  Google Scholar 

  48. 48.

    Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558–561 (1993).

    CAS  Article  Google Scholar 

  49. 49.

    Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).

    Article  Google Scholar 

  50. 50.

    Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).

    CAS  Article  Google Scholar 

  51. 51.

    Kresse, G. & Hafner, J. Ab initio molecular dynamics for open-shell transition metals. Phys. Rev. B 48, 13115–13118 (1993).

    CAS  Article  Google Scholar 

  52. 52.

    Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

    CAS  Article  Google Scholar 

  53. 53.

    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).

    CAS  Article  Google Scholar 

  54. 54.

    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).

    Article  CAS  Google Scholar 

  55. 55.

    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).

    CAS  Article  Google Scholar 

  56. 56.

    Senftle, T. P. et al. The ReaxFF reactive force-field: development, applications and future directions. NPJ Comput. Mater. 2, 15011 (2016).

    CAS  Article  Google Scholar 

  57. 57.

    Rappé, A. K., & Goddard, W. A. Charge equilibration for molecular dynamics simulations. J. Phys. Chem. 95, 3358–3363 (1991).

    Article  Google Scholar 

Download references

Acknowledgements

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.

Author information

Affiliations

Authors

Contributions

S.B. and V.A. developed the experimental study. S.B. performed materials synthesis, aqueous electrochemistry, Raman, XRD and EQCM. S.S. performed non-aqueous electrochemistry. S.B., W.-Y.T. and N.B. performed AFM. K.G. performed ReaxFF simulations. T.W. performed DFT simulations. N.B., D.-E.J., A.C.T.v.D. and V.A. supervised the project. All authors contributed to the discussion of the results and writing the paper.

Corresponding author

Correspondence to Veronica Augustyn.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

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.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

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).

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Boyd, S., Ganeshan, K., Tsai, WY. et al. Effects of interlayer confinement and hydration on capacitive charge storage in birnessite. Nat. Mater. (2021). https://doi.org/10.1038/s41563-021-01066-4

Download citation

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing