ORALS

SESSION: SolidStateChemistryMonAM-R6	Alario-Franco international Symposium (2nd Intl Symp on Solid State Chemistry for Applications & Sustainable Development)
Mon. 28 Nov. 2022 / Room: Andaman 1
Session Chairs: Alejandro Varez; Session Monitor: TBA

12:20: [SolidStateChemistryMonAM03] OS
NASICON ceramic electrolytes produced by combination of tape-casting and hot-pressing with high performances at room temperature. Towards sustainable all-solid-state sodium batteries.
Alejandro Varez¹ ; Belén Levenfeld² ; Cynthia Martinez Cisneros³ ; Johanna M Naranjo Balseca¹ ; Bidhan Pandit¹ ; ¹UNIVERSIDAD CARLOS III DE MADRID, LEGANES, Spain; ²Universidad Carlos III de Madrid, Leganés, Spain; ³Universidad Carlos III de Madrid, LEGANES, Spain;
Paper Id: 443 [Abstract]

The abundance of sodium and the physical-chemical similarities with lithium make sodium batteries a technology to the Lithium ones, with the potential to produce disruptive changes in the transition towards cleaner and sustainable energy sources less dependent on fossil fuels. In this experimental work, we propose a new processing methodology, based on the combination of tape-casting and hot-pressing, to develop high performances ceramic NASICON electrolytes with formula Na3.16Zr1.84Y0.16Si2PO12 and high ionic conductivity (from 0.12 mS/cm at 20ºC to 1.29 mS/cm at 100ºC), wide electrochemical window (from 1.5V to 4V), good mechanical properties and (325 HV of hardness) and high thermal stability. In order to study the compatibility of the chemical and electrochemical characteristics the electrolytes with the solid-state battery approach, half-cells (Na0/NASICON/FePO4) were prepared and tested at room temperature. Preliminary results reveal that capacity slightly increases as the number of cycle does, reporting values of up to 85 mAh/g (at a C-rate of C/20), about 50% of the theoretical capacity and 60% of the capacity typically reported for their liquid-based counterparts. Due to these results were obtained for room temperature, the application scope of the proposed electrolytes broadens not only to stationary applications but to transport, where highly efficient and sustainable devices are highly demanded. Therefore, the all-solid-state sodium battery based on Na0/NASICON/FePO4 here proposed demonstrates to be functional and a potential competitor for current all-solid-state batteries based on the electrochemistry of lithium.

SESSION: SolidStateChemistryMonAM-R6	Alario-Franco international Symposium (2nd Intl Symp on Solid State Chemistry for Applications & Sustainable Development)
Mon. 28 Nov. 2022 / Room: Andaman 1
Session Chairs: Alejandro Varez; Session Monitor: TBA

12:45: [SolidStateChemistryMonAM04] OS
3D-printing of easily recyclable all-ceramic thick LiCoO2 electrodes with enhanced areal capacity for Li-ion batteries using a highly filled thermoplastic filament
Belén Levenfeld¹ ; Alejandro Varez² ; Carmen De La Torre¹ ; Daniel Del Rio¹ ; ¹Universidad Carlos III de Madrid, Leganés, Spain; ²UNIVERSIDAD CARLOS III DE MADRID, LEGANES, Spain;
Paper Id: 442 [Abstract]

The final prices of a LIB depend to a large extent on the materials used and the manufacturing process. The reduction of non-active materials (50% of battery weight) (Al and Cu current collectors, separators),, plays a fundamental role in reducing costs for both the production process and the final device [1]. On the other hand, the cathode thickness currently limits the total energy density and power of LIBs. One option to address this limitation is to increase the cathode thickness and consequently balancing with a thicker anode. In this way, the active materials volume ratio in the cell increases (the electrodes areal and volume capacities grow), achieving higher specific energy and specific power per weight and per volume [2]. Commercially available batteries are usually composed by cylindrical, coin, prismatic or pouch cells. Therefore, the development of new processing technologies is needed to design more complex geometries that could fit specific cell designs. In this context, additive manufacturing (AM) technologies have shown their potential for the design of 3D objects with non-conventional geometries and reduce number of produced parts and have been recently applied to different energy devices [3]. Although AM technology has not been used for commercial batteries, its use can contribute to the optimization of the final design of the devices, allowing the use of batteries with more complex shapes. In this work, Fused Filament Fabrication (FFF) is proposed as a cheap, affordable and solvent-free processing method alternative to conventional electrode manufacturing for Li-ion batteries, which allows developing additive-free ceramic electrodes with enhanced energy density. The production of thick ceramic LiCoO2 (LCO) electrodes using a desktop 3D-printing was developed as an alternative to conventional electrode manufacturing for Li-ion batteries. Firstly, the filament formulation based on LCO powders and a sacrificial polymers blend, is optimized in order to achieve the suitable features (viscosity, flexibility and mechanical consistency) to be used in a conventional desktop 3-D printing. Printing parameters were optimized to produce defect-free bodies with coin geometry (12 mm diameter and 230-850 µm thickness). Thermal debinding and sintering were studied in order to obtain all ceramic LCO electrodes with adequate porosity. The additive-free sintered electrodes (850 µm thickness) have enhanced areal and volumetric capacities (up to 28 mA·h·cm-2 and 354 mA·h·cm-3) due to their extremely high mass loading (up to 285 mg·cm-2). Thus, the Li//LCO half-cell delivered an energy density of 1310 W·h·L-1. The ceramic nature of the electrode permits the use of a thin film of paint gold as current collector, reducing considerably the polarization of thick electrodes. Thus, the whole manufacturing process developed in this work is a complete solvent-free method to produce tuneable shape electrodes with enhanced energy density, opening the door for the manufacturing of high-density batteries with complex geometries and easily recyclable.

References:
[1] Y. Kuang, C. Chen, D. Kirsch, L. Hu, Advanced Energy Materials 1901457 (2019) 1–19.
[2] Y. Liu, S. Zheng, J. Ma, Y. Zhu, J. Wang, X. Feng, Z.S. Wu, Journal of Energy Chemistry 63 (2021)
[3] L. Fieber, J.D. Evans, C. Huang, P.S. Grant, Additive Manufacturing 28 (2019) 344–353 514–520.