December 1 - 6, 2024
Boston, Massachusetts
Symposium Supporters
2024 MRS Fall Meeting & Exhibit
EN08.12.07

Investigation of Ruddlesden Popper-Type Oxide as an Intercalation Based Cathode Material for All-Solid-State Fluoride-Ion Batteries

When and Where

Dec 6, 2024
10:45am - 11:00am
Hynes, Level 3, Ballroom C

Presenter(s)

Co-Author(s)

Vanita Vanita1,Aamir Waidha1,Sami Vasala2,Pascal Puphal3,Roland Schoch4,Pieter Glatzel2,Matthias Bauer4,Oliver Clemens1

Universität Stuttgart1,European Synchrotron Radiation Facility2,Max Planck Institute for Solid State Research3,Universität Paderborn4

Abstract

Vanita Vanita1,Aamir Waidha1,Sami Vasala2,Pascal Puphal3,Roland Schoch4,Pieter Glatzel2,Matthias Bauer4,Oliver Clemens1

Universität Stuttgart1,European Synchrotron Radiation Facility2,Max Planck Institute for Solid State Research3,Universität Paderborn4
Increasing use of Lithium-ion batteries (LIBs) has led to and will further lead to the depletion of lithium reserves. In response, investigations are being done on other cations (Na+) and anions (F-, Cl-)1 as shuttling ions for battery systems. Recently, fluoride ion batteries (FIBs) are considered to as an alternative for all-solid-state batteries2, for which cells based on conversion-based cathode materials can provide high specific capacity at the cost of fast capacity fading on cycling3, 4. This can be understood from the fact that the conversion mechanism involves large degree of atom organisation, changes in chemical bonds and massive volume changes upon cycling. This has been shown to be prevented by using intercalation-based cathode materials, which drastically reduce the volume changes due to the possible intercalation and de-intercalation of ions from the host lattice5. This not only led to higher cycling stability but also facilitates the lowering of overpotentials6. In this respect, different second-generation intercalation-based materials have been derived from initially studied materials5-7, among which Ruddlesden-Popper type La2Ni0.75Co0.25O4 have been identified for improved cycling performance8 and further LaSrMnO4 / La1Sr2Mn2O7 are under investigation.
In this study, we explore the structural changes of La2Ni0.75Co0.25O4 / Pb-PbF2, LaSrMnO4 / Pb-PbF2 and La1Sr2Mn2O7 / Pb-PbF2 cells during fluoride intercalation and de-intercalation by using X-ray diffraction (XRD) and electrochemical characterization methods. By X-ray diffraction analysis of cells cycled to different cut-off conditions, reveal an increase of the unit cell along the c-axis and contraction in the ab-plane. The detailed complex reaction behaviour of the phase, focusing on changes in the oxidation states and co-ordination environments of Ni and Co in La2Ni0.75Co0.25O4 was studied via X-ray absorption spectroscopy (XAS). Under optimized operating conditions, we achieved a cycle life of 120-cycles at a critical cut-off capacity of 40 mAh.g-1 and over 400-cycles under a pressure of 452 MPa. The average Coulombic efficiencies ranged from 85% to 90% for the cell operated without pressure and 95 % to 99 % for the cell operated under pressure for La2Ni0.75Co0.25O4 / Pb-PbF2 cells. Therefore, La2Ni0.75Co0.25O4 stands out as one of the promising cycling-stable high-energy cathode materials for all-solid-state FIBs, offering improved capacity 8, 9.

References
1.Gao, P.; Reddy, M. A.; Mu, X.; Diemant, T.; Zhang, L.; Zhao-Karger, Z.; Chakravadhanula, V. S.; Clemens, O.; Behm, R. J.; Fichtner, M., Angew Chem Int Ed Engl 2016, 55 (13), 4285-90.
2. Nowroozi, M. A.; Mohammad, I.; Molaiyan, P.; Wissel, K.; Munnangi, A. R.; Clemens, O., Journal of Materials Chemistry A 2021, 9 (10), 5980-6012.
3. Nitta, N.; Wu, F. X.; Lee, J. T.; Yushin, G., Materials Today 2015, 18 (5), 252-264.
4. Anji Reddy, M.; Fichtner, M., Journal of Materials Chemistry 2011, 21 (43), 17059-17062.
5. Nowroozi, M. A.; Ivlev, S.; Rohrer, J.; Clemens, O., Journal of Materials Chemistry A 2018, 6 (11), 4658-4669.
6. Nowroozi, M. A.; Wissel, K.; Rohrer, J.; Munnangi, A. R.; Clemens, O., Chemistry of Materials 2017, 29 (8), 3441-3453.
7. Wissel, K.; Schoch, R.; Vogel, T.; Donzelli, M.; Matveeva, G.; Kolb, U.; Bauer, M.; Slater, P. R.; Clemens, O., Chemistry of Materials 2021, 33 (2), 499-512.
8. Vanita, V.; Waidha, A. I.; Vasala, S.; Puphal, P.; Schoch, R.; Glatzel, P.; Bauer, M.; Clemens, O., Journal of Materials Chemistry A 2024, 12 (15), 8769-8784.
9. Chen, H.; Aalto, T.; Vanita, V.; Clemens, O., Small Structures 2024, 2300570

Keywords

intercalation | reactive ball milling

Symposium Organizers

Kelsey Hatzell, Vanderbilt University
Ying Shirley Meng, The University of Chicago
Daniel Steingart, Columbia University
Kang Xu, SES AI Corp

Session Chairs

Rafael Gomez-Bombarelli
Kang Xu

In this Session