Dec 6, 2024
10:45am - 11:00am
Hynes, Level 3, Ballroom C
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 batteries
2, for which cells based on conversion-based cathode materials can provide high specific capacity at the cost of fast capacity fading on cycling
3, 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 lattice
5. This not only led to higher cycling stability but also facilitates the lowering of overpotentials
6. In this respect, different second-generation intercalation-based materials have been derived from initially studied materials
5-7, among which Ruddlesden-Popper type La
2Ni
0.75Co
0.25O
4 have been identified for improved cycling performance
8 and further LaSrMnO
4 / La
1Sr
2Mn
2O
7 are under investigation.
In this study, we explore the structural changes of La
2Ni
0.75Co
0.25O
4 / Pb-PbF
2, LaSrMnO
4 / Pb-PbF
2 and La
1Sr
2Mn
2O
7 / Pb-PbF
2 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 La
2Ni
0.75Co
0.25O
4 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 La
2Ni
0.75Co
0.25O
4 / Pb-PbF
2 cells. Therefore, La
2Ni
0.75Co
0.25O
4 stands out as one of the promising cycling-stable high-energy cathode materials for all-solid-state FIBs, offering improved capacity
8, 9.
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