Material strategies for high energy layered cathodes with improved stability for Li-ion batteries: investigation of doping strategies and solid-state concepts using a combined in- situ/operando approach
Physical Chemistry of Solids and Surfaces, Material Characterisation
Final Report Abstract
The main objective of this cooperative project on high energy cathodes is understanding the systematic correlation of redox processes induced by Li ion and electron removal and induced degradation (involving the electrolyte), occurring in the bulk and at surfaces, and to develop strategies to avoid/reduce these unwanted side reactions (in the second phase). As cathodes Ni-rich NCMs (lithium nickel cobalt manganese oxides) are compared to Li/Mn-rich HE-NCM layered oxides to elucidate the central relevance of oxide to transition metal redox reactions. The complimentary expertise of the project consortium in synthesis and structural studies (BIU), analysis of chemical and electronic structure (OF TUDa), and of chemical variation during polarisation (PC TUDa) allows a rather full characterisation of differently prepared electrodes also in their electrochemical behaviour. As materials we investigated commercial NMC powders and thin films as well as BIU prepared and SO2/NH3 gas treated and modified HE- NCMs with improved stability. Using our analytical approach we developed and established essential and reliable methods to discriminate bulk from surface effects. For XPS a mechanical surface scratching procedure allows a so far impossible analysis of bulk properties. XPS and XANES measurements at synchrotrons allow to use changes of excitation energy to vary surface sensitivity. For Raman spectroscopy we evaluated the potential of resonance effects and developed an in-situ/ operando cell with optionally increased sensitivity exploiting SERS effects. One central insight comparing different measurements is the participation of O 2- in the involved redox reactions of all high-energy cathodes. XPS and XANES indicate that the formal oxidations states of 4+ of the metals are not reached and that the oxide ions are oxidized. The relative changes in the oxidation states and their origin (formation of different phases, changes of hybridisation, non-rigid bond effects) cannot be assigned yet (work in progress). A further central insight is the degradation involving surface reactions induced by oxidized oxide ions and high valent transition metal ions. Surprisingly, the surface vs. bulk composition after electrochemical oxidation indicates surface oxide phases with reduced metal ions. Reduced surfaces are also formed on HE-NCMs after SO2/NH3 gas phase treatment. Also, first oxide ALD layers show improved stability. These results are supported by CV and impedance measurements, indicating a degradation by reaction of the cathodes with electrolyte components at high potentials; preferentially are then formed Li-ion permeable layers with reduced reactivity. Summarizing, based on the so far gained insights from this project it is evident that the properties of the CEI phase boundary are critical for the properties of Li-ion batteries and that they must be specifically adjusted. The presented approach promises interesting insights and perspectives but involves a high level of effort because of the inherent complexity in synthesis and characterisation.
Publications
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High‐Temperature Treatment of Li‐Rich Cathode Materials with Ammonia: Improved Capacity and Mean Voltage Stability during Cycling. Advanced Energy Materials, 7(18).
Erickson, Evan M.; Sclar, Hadar; Schipper, Florian; Liu, Jing; Tian, Ruiyuan; Ghanty, Chandan; Burstein, Larisa; Leifer, Nicole; Grinblat, Judith; Talianker, Michael; Shin, Ji‐Yong; Lampert, Jordan K.; Markovsky, Boris; Frenkel, Anatoly I. & Aurbach, Doron
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Enhancement of Electrochemical Performance of Lithium and Manganese-Rich Cathode Materials via Thermal Treatment with SO 2. Journal of The Electrochemical Society, 167(11), 110563.
Sclar, Hadar; Sicklinger, Johannes; Erickson, Evan M.; Maiti, Sandipan; Grinblat, Judith; Talianker, Michael; Amalraj, Susai Francis; Burstein, Larisa; Beyer, Hans; Hartmann, Louis; Avruschenko, Gregory; Gasteiger, Hubert A.; Markovsky, Boris & Aurbach, Doron
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Coupling Long‐Range Raman with X‐Ray Photoelectron Spectroscopy for Complementary Bulk and Surface Characterization of Battery Materials. Chemistry–Methods, 2(1).
Radtke, Mariusz; Kopp, Karl & Hess, Christian
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Operando Raman Shift Replaces Current in Electrochemical Analysis of Li-ion Batteries: A Comparative Study. Molecules, 26(15), 4667.
Radtke, Mariusz & Hess, Christian
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Operando Surface Enhanced Raman Spectroelectrochemistry for Mechanistic Understanding of Energy Storage in Lithium/Sodium/Potassium Ion-Batteries. Oral presentation at MRS, Boston, USA.
Radtke, M. & Hess, C.
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Surface Enhanced Raman spectroelectrochemistry as a tool in operando studies of energy storage systems. Oral presentation at European Congress and Exhibition on Advanced Materials and Processes, Graz, Austria.
Radtke, M. & Hess, C.
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Double gas treatment: A successful approach for stabilizing the Li and Mn-rich NCM cathode materials’ electrochemical behavior. Energy Storage Materials, 45, 74-91.
Maiti, Sandipan; Sclar, Hadar; Rosy, NA; Grinblat, Judith; Talianker, Michael; Tkachev, Maria; Tsubery, Merav; Wu, Xiaohan; Noked, Malachi; Markovsky, Boris & Aurbach, Doron
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Exploring Impact of Thermal Gas Treatment of High-Energy Materials on Stability of the Cathode/Electrolyte Interface upon Electrochemical Cycling to 4.8 V. Poster presentation at IMLB, Sydney, Australia.
Mellin, M.; Maiti, S.; Jaegermann, W.; Radtke, M.; Hess, C.; Hausbrand, R.; Markovsky, B.; Aurbach, D.; Hofmann J. P. & Cherkashinin, G.
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Mapping of the RedOx intercalation activity in 2D TMD flakes within Li-Ion-Batteries by 4-dimensional Raman Potentioelectrochemical impedance spectroscopy. Oral presentation at International Workshop on Impedance Spectroscopy (IWIS), Chemnitz, Germany.
Radtke, M. & Hess, C.
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Monitoring electrode/electrolyte interfaces of Li‐ion batteries under working conditions: A surface‐enhanced Raman spectroscopic study on LiCoO 2 composite cathodes. Surface and Interface Analysis, 54(8), 847-854.
Heber, Marcel & Hess, Christian
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Raman Diagnostics of Cathode Materials for Li-Ion Batteries Using Multi-Wavelength Excitation. Batteries, 8(2), 10.
Heber, Marcel; Hofmann, Kathrin & Hess, Christian
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Exploring an Impact of Thermal Gas on the Surface Modification and Stability of Li-, Mn-, and Ni- Rich Cathode Materials: Electron Spectroscopy Study. Oral presentation at the Li-ion battery discussion (LIBD-10), Arcachon, France
Mellin, M.; Liang, Z.; Maheu, C.; Maiti, S.; Sclar, H.; Píš, I.; Nappini, S.; Magnano, E.; Bondino, F.; Napal, I.; Hausbrand, R., Hofmann, J. P.; Alff, L.; Markovsky, B.; Aurbach, D.; Jaegermann, W. & Cherkashinin, G.
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Impact of thermal gas treatment on the surface modification of Li-rich Mn-based cathode materials for Li-ion batteries. Materials Advances, 4(17), 3746-3758.
Mellin, Maximilian; Liang, Zhili; Sclar, Hadar; Maiti, Sandipan; Píš, Igor; Nappini, Silvia; Magnano, Elena; Bondino, Federica; Napal, Ilargi; Winkler, Robert; Hausbrand, Réne; Hofmann, Jan P.; Alff, Lambert; Markovsky, Boris; Aurbach, Doron; Jaegermann, Wolfram & Cherkashinin, Gennady
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Fundamental understanding of working batteries by in situ and operando Raman spectroelectrochemistry. Encyclopedia of Solid-Liquid Interfaces, 399-411. Elsevier.
Radtke, M.; Heber, M. & Hess, C.
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Voltage-dependent charge compensation mechanism and cathode electrolyte interface stability of the lithium-ion battery cathode materials LiCoO2 and LiNi1/3Mn1/3Co1/3O2 studied by photoelectron spectroscopy. Journal of Materials Chemistry A, 12(6), 3644-3658.
Mellin, Maximilian; Cherkashinin, Gennady; Mohseni, Elham; Phillips, Robert; Jaegermann, Wolfram & Hofmann, Jan P.
