widely used in consumer electronics due to the advantages of rechargeability and high energy density. [4][5][6] Commercial LIBs are usually fabricated in fixed geometry such as cylinder, coin, and pouch with scrolled or layered planar sheets for each component. [7] Nevertheless, LIBs with customizable geometry are desired for specialized applications such as wearable electronics [8,9] and on-device power systems [10,11] for automobile and aerospace vehicles, For example, LIBs can be made into a watchband to power an electronic watch, [12] which eliminates the installation and replacement of coin cell. To meet such demands, irregular, customizable LIBs in arbitrary geometry on 3D structures along with the packaging, integrating, and manufacturing approaches need to be developed. So far, the most effective solution to fabricate freeform LIBs is additive manufacturing (AM, popularly known as 3D printing). [13][14][15][16] The on-demand and layer-by-layer manufacturing method has provided the flexibility to accommodate customizable designs of 3D LIBs.Electrodes are the most essential components of LIBs. Currently reported AM processes for electrodes are mostly based on extrusion printing, [17][18][19][20][21][22][23][24] with a few reports on other ink-based printing methods including inkjet printing [25] and aerosol printing. [10] In extrusion printing, active material laden inks are directly deposited and powered by ultra-high air pressure. The materials are extruded into semi-solidified and self-supportive filaments owing to the shear-thinning characteristics of the highly viscous inks. Main advantage of AM processes is the capability of printing electrodes in arbitrary geometry. For example, Lacey et al. and Wang et al. demonstrated 3D printing of mesh and lattice structured electrodes, which effectively introduced macroporosity and facilitated the transportation of lithium-ions under high charging/discharging rate. [18,23] The flexibility in printed geometry also enables the fabrication of electrodes with high aspect ratio and high areal capacity, which are usually not processable by conventional slurry-casting method. Sun et al. first printed high aspect ratio, multilayer, interdigitated electrodes for micro-LIBs with high energy density and power density. [21] Despite these advantages, in extrusion-printing, composition and rheological behaviors of inks are demanding due to the requirements in clogging prevention, substrate bonding and shape maintenance. [19,20] Alternatively, aerosol printing Lithium-ion batteries (LIBs) are widely used in consumer electronics due to their rechargeability and high energy density. Commercial LIBs are fabricated in fixed geometries such as cylinder, coin, and pouch. However, for specialized applications such as wearable electronics and on-device power systems, customizable LIBs with arbitrary geometry on threedimensional (3D) structures need to be developed. For this purpose, aerosol printing is uniquely suitable due to its flexible working distance, allowing deposition on nonp...