Fabrication and Characterization of 3D-Printed Highly-Porous 3D LiFePO₄ Electrodes by Low Temperature Direct Writing Process.

LiFePO₄ (LFP) is a promising cathode material for lithium-ion batteries. In this study, low temperature direct writing (LTDW)-based 3D printing was used to fabricate three-dimensional (3D) LFP electrodes for the first time. LFP inks were deposited into a low temperature chamber and solidified to maintain the shape and mechanical integrity of the printed features. The printed LFP electrodes were then freeze-dried to remove the solvents so that highly-porous architectures in the electrodes were obtained. LFP inks capable of freezing at low temperature was developed by adding 1,4 dioxane as a freezing agent. The rheological behavior of the prepared LFP inks was measured and appropriate compositions and ratios were selected. A LTDW machine was developed to print the electrodes. The printing parameters were optimized and the printing accuracy was characterized. Results showed that LTDW can effectively maintain the shape and mechanical integrity during the printing process. The microstructure, pore size and distribution of the printed LFP electrodes was characterized. In comparison with conventional room temperature direct ink writing process, improved pore volume and porosity can be obtained using the LTDW process. The electrochemical performance of LTDW-fabricated LFP electrodes and conventional roller-coated electrodes were conducted and compared. Results showed that the porous structure that existed in the printed electrodes can greatly improve the rate performance of LFP electrodes.