High gravimetric and volumetric energy densities enabled by 3D-printed thick anode

Developing advanced Li-ion batteries with high areal capacity, and gravimetric and volumetric energy densities remains a challenge. This study uses additive manufacturing technology to prepare thick Li 4 Ti 5 O 12 -Li 4 SiO 4 (LTO-LSO) composite electrodes for Li-ion batteries with high area capacity and energy density. The 3D-printed electrodes are made of grid-patterned and closely stacked LTO-LSO composite, carbon black super p, and PVDF. The LSO nanoparticles are uniformly wrapped on the surface of LTO as a protective layer, resulting in increased ionic/electronic conductivity and abundant open and hierarchical macropores in the planned grid-lined 3D-printed LTO-LSO electrodes. The composite electrode has excellent conductivity (up to 4.13 × 10 2 μS cm −1 ) and low charge-transfer resistance, making it suitable for 3D-printed thick electrodes. The 3D-printed thick LTO-LSO composite electrodes (12 layers) have a high areal capacity of 6.56 mAh cm −2 , areal and volumetric energy densities of 388.04 mWh cm −2 and 241.46 mWh cm −3 , as well as excellent cycling performance at 10C after 450 cycles. Moreover, the full cell with a 3D-printed thick LTO-LSO anode and 3D-printed LiCoO 2 (LCO) cathode exhibits exceptional cycle stability, gravimetric and volumetric energy densities of 723.40 Wh kg −1 and 1200 Wh L −1 , respectively. Our strategies show that growing a highly conductive protective layer on the surface of electrodes and designing ultrathick electrodes are promising approaches to the fabrication of multidimensional structures with high area capacity, gravimetric and volumetric Li-ion batteries. • Lithium Orthosilicate (Li 4 SiO 4 ) protective layer high Li + mobility is wrapped on the outer surface of Li 4 Ti 5 O 12 particle through in-situ liquid phase method to improve the outside transfer paths of ions/electrons to the Li 4 Ti 5 O 12 -Li 4 SiO 4 composite. • Highly conductive 3D-printed thick electrode using mixed functional inks employing Li 4 Ti 5 O 12 -Li 4 SiO 4 composite, PVDF as binder, Super P and NMP ( N -methly-2-pyrrolidone was designed to realize high areal and energy density 3D-printed batteries. • The 3D-printed thick LTO-LSO composite electrodes (12 layers) have a high areal capacity, gravimetric and volumetric energy densities of (6.56 mAh cm -2 ), areal and volumetric energy densities of 388.04 mWh cm -2 and 241.46 mWh cm - 3, respectively, as well as excellent cycling performance at 10 C after 450 cycles.