Highly Loaded Graphite Composite PLA-Based Filaments for Lithium-Ion Battery 3D-Printing
Authors: Maurel Alexis , Courty Matthieu , Fleutot Benoit , Tortajada Hugues , Prashantha Kalappa , Armand Michel , Grugeon Sylvie , Panier Stéphane , Dupont Loic 
Published: February 2020

Actual parallel-plate architecture of lithium-ion batteries consists in lithium ion diffusion in one dimension between the electrodes. To achieve higher performances in terms of specific capacity and power, configurations enabling lithium ion diffusion in two or three dimensions have been considered (1-5). With a view to build these complex 3D battery architectures avoiding the electrodes interpenetration issues, this work was focused on the Fused Deposition Modeling (FDM). In this presentation, the formulation and characterization of a 3D-printing graphite/polylactic-acid (PLA) filament, specially designed to be used as negative electrode in a lithium-ion battery, and to feed a conventional FDM 3D-printer will be described (6).
Graphite loading into the produced filament was increased as high as possible (up to 62.5%wt) to enhance the electrochemical performances while maintaining sufficient mechanical strength to be printed. Formulation process is displayed in Fig. 1a. With such a high ratio of active material, the graphite/PLA filament was found to be very brittle. To overcome this problem, a plasticizer has been added to the PLA matrix to improve its ductility and decrease its stiffness. Influence of the amount of various plasticizers such as propylene carbonate (PC), poly(ethylene glycol) dimethyl ether average Mn~2000 (PEGDME2000), poly(ethylene glycol) dimethyl ether average Mn~500 (PEGDME500) and acetyl tributyl citrate (ATBC) was investigated by performing both differential scanning calorimetry and tensile mechanical tests. On the other hand, printability behavior of the extruded composite filaments was tested by using a commercially available 3D printer. From the optimized plasticizer composition, two-dimensional discs but also high resolution complex three-dimensional structures, such as a semi-cube lattice and a “3Dbenchy” boat, were successfully 3D-printed.
Finally, considering this optimized composite, an in-depth study was carried out to identify the electronic percolation (Fig. 1b) and electrochemical impact of carbon black SuperP and carbon nanofibers as conductive additives; electrical conductivities were determined from impedance measurements performed at various stabilized temperatures ranging from 20ºC to 50°C and, in parallel, capacity retention was investigated in detail at different current densities after the different elaboration steps (film before extrusion and disc after printing).
Significant progress has been achieved regarding the capacity retention as compared to Foster et al. (7) who was the first group to use FDM technology to 3D-print a negative electrode disc. They were aware that the low specific capacity values reported (15.8 mAh.g-1 at current density of 10 mA.g-1) were unfortunately caused by the use of a filament containing only 8%wt of graphene as active material and 92%wt of PLA. In this work, by increasing the graphite loading up to 62.5%wt, a reversible capacity of 201 mAh.g- 1 at current density of 4 mA.g-1 was achieved for the 3D-printed negative electrode disc by using the most printable filament (Fig. 1c).

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Figure 1