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Designing ultrathick and hierarchical electrodes is effective to deal with the challenge of high areal capacity and high power density for lithium-ion batteries (LIBs) manufacturing. Here, a thick electrode with hierarchical porous and multidimensional conductive network is fabricated by 3D printing technology, in which both the conducting polymer of poly(3,4-ethylene dioxythiophene):polystyrene sulfonate (PEDOT:PSS) and graphene oxide (GO) play the dual roles as binders and conductive agents. As a consequence, the 3D-printed thick electrode (∼900 μm) with a mass loading of ∼47 mg/cm2 exhibits a good rate capability of 122 mA·h/g at 2 C, a high areal capacity of up to 5.8 mA·h/cm2, and stable cycling performance of ∼95% capacity retention after 100 cycles. Moreover, the C-O-S bond is further confirmed by the spectral analysis and the DFT calculation, which not only hinders the stack of nanosheets but enhances the mechanical stability and electronic conductivity of electrodes.
Fast charging and high volumetric capacity are two of the critical demands for sodium-ion batteries (SIBs). Although nanostructured materials achieve outstanding rate performance, they suffer from low tap density and small volumetric capacity. Therefore, how to realize large volumetric capacity and high tap density simultaneously is very challenging. Here, N/F co-doped TiO2/carbon microspheres (NF-TiO2/C) are synthesized to achieve both of them. Theoretical calculations reveal that N and F co-doping increases the contents of oxygen vacancies and narrows the bandgaps of TiO2 and C, improving the electronic conductivity of NF-TiO2/C. Furthermore, NF-TiO2/C exhibits the high binding energy and low diffusion energy barrier of Na+, significantly facilitating Na+ storage and Na+ diffusion. Therefore, NF-TiO2/C offers a high tap density (1.51 g cm−3), an outstanding rate performance (∼125.9 mAh g−1 at 100 C), a large volumetric capacity (∼190 mAh cm−3 at 100 C), a high areal capacit