Abstract
Mn dissolution has been a long-standing, ubiquitous issue that negatively impacts the performance of Mn-based battery materials. Mn dissolution involves complex chemical and structural transformations at the electrode–electrolyte interface. The continuously evolving electrode–electrolyte interface has posed great challenges for characterizing the dynamic interfacial process and quantitatively establishing the correlation with battery performance. In this study, we visualize and quantify the temporally and spatially resolved Mn dissolution/redeposition (D/R) dynamics of electrochemically operating Mn-containing cathodes. The particle-level and electrode-level analyses reveal that the D/R dynamics is associated with distinct interfacial degradation mechanisms at different states of charge. Our results statistically differentiate the contributions of surface reconstruction and Jahn–Teller distortion to the Mn dissolution at different operating voltages. Introducing sulfonated polymers (Nafion) into composite electrodes can modulate the D/R dynamics by trapping the dissolved Mn species and rapidly establishing local Mn D/R equilibrium. This work represents an inaugural effort to pinpoint the chemical and structural transformations responsible for Mn dissolution via an operando synchrotron study and develops an effective method to regulate Mn interfacial dynamics for improving battery performance.
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Data availability
The data that support the findings of this study are available within this Article and its Supplementary Information. Any other data are available from the corresponding authors on request.
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Acknowledgements
The work was supported by the National Science Foundation under CBET 1912885 (F.L.). This research used resources of the Advanced Photon Source, US Department of Energy (DOE), Office of Science User Facility, operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. The use of the Stanford Synchrotron Radiation Lightsource (SSRL), SLAC National Accelerator Laboratory, was supported by the US DOE, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-76SF00515. This research used the electron microscopy resources of the Center for Functional Nanomaterials (CFN), US DOE, Office of Science User Facility, at Brookhaven National Laboratory under contract no. DE-SC0012704. Y.Z. and F.L. thank the beamline scientist R. Davis at SSRL for help with the hard XAS measurements.
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F.L. conceived and led the project. F.L. and Y.Z. designed the experiments. Y.Z. performed the materials synthesis, electrochemical tests, synchrotron measurements and data analysis. A.H. and D.X. assisted with the XFM measurements. D.X. assisted with the hard XAS measurements. S.S. and D.N. performed the soft XAS measurements. S.H. performed the TEM measurements and data analysis. F.M.M. participated in the data discussion. R.B.M. participated in the experimental design and data discussion. L.L. assisted with the XFM measurements and participated in the discussion and data analysis. Y.Z. and F.L. wrote the manuscript with inputs from all the co-authors. All the authors approved the final draft of the manuscript.
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Extended data
Extended Data Fig. 1 Cell configuration for the in-situ X-ray fluorescence microscopy (XFM) experiment.
The three-electrode cell used for the in situ and operando X-ray fluorescence microscopy (XFM) experiment. The X-rays hit the electrode from the side of the current collector (carbon paper).
Extended Data Fig. 2 XFM images of LMO particles at different states of charge.
The XFM images at the single-particle level of LMO electrodes at different states of charge during the first cycle, showing a heterogeneous Mn D/R behaviours.
Extended Data Fig. 3 Mn deposition on the counter electrode.
(a) The photo of a graphite paper used as the counter electrode during electrochemical cycling, where the arrows indicate the original and cycled regions; (b) XFM image of the region labelled by blue frame in (a), showing a much higher Mn concentration in the cycled region and confirming that the dissolved Mn species can deposit on the counter electrode surface. Note that XFM is extremely elementally sensitive, the minor Mn concentration in the pristine graphite originates from the impurity.
Extended Data Fig. 4 Mn D/R dynamics of Mn3O4 held at 1.2 V.
The Mn D/R dynamics of Mn3O4 held at 1.2 V. The CA protocol is applied for 21 minutes to keep the voltage at 1.2 V and monitor the Mn concentration variation. Each XFM image takes 7 minutes.
Extended Data Fig. 5 Mn D/R dynamics of MnO2 held at 1.2 V.
The Mn D/R dynamics of MnO2 held at 1.2 V. The CA protocol is applied for 21 minutes to keep the voltage at 1.2 V and monitor the Mn concentration variation. Each XFM image takes 7 minutes.
Extended Data Fig. 6 Mn D/R dynamics of LMO cycled in 2 M LiTFSI-TEGDME electrolyte.
(a) The XFM images of Mn concentration in the LMO electrode during electrochemical cycling in 2 M LiTFSI in tetraethylene glycol dimethyl ether (TEG-DME) solvents; (b) the corresponding Mn D/R behaviours during the first cycle.
Extended Data Fig. 7 Trapped Mn ions in the Nafion membrane.
(a) The photos of casted Nafion membrane; (b) the EDS mapping of Mn element for pristine and soaked Nafion membranes. The Mn signal in pristine membranes is caused by the uncertainty from the instrument, the actual Mn atomic ratio is zero.
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Supplementary Figs. 1–18 and Tables 1–5.
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Zhang, Y., Hu, A., Xia, D. et al. Operando characterization and regulation of metal dissolution and redeposition dynamics near battery electrode surface. Nat. Nanotechnol. 18, 790–797 (2023). https://doi.org/10.1038/s41565-023-01367-6
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DOI: https://doi.org/10.1038/s41565-023-01367-6
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