While 3D printing of rechargeable batteries has received immense interest in advancing the next generation of 3D energy storage devices, challenges with the 3D printing of electrolytes still remain. Additional processing steps such as solvent evaporation were required for earlier studies of electrolyte fabrication, which hindered the simultaneous production of electrode and electrolyte in an all-3D-printed battery. Here, a novel method is demonstrated to fabricate hybrid solid-state electrolytes using an elevated-temperature direct ink writing technique without any additional processing steps. The hybrid solid-state electrolyte consists of solid poly(vinylidene fluoride-hexafluoropropylene) matrices and a Li -conducting ionic-liquid electrolyte. The ink is modified by adding nanosized ceramic fillers to achieve the desired rheological properties. The ionic conductivity of the inks is 0.78  × 10 S cm . Interestingly, a continuous, thin, and dense layer is discovered to form between the porous electrolyte layer and the electrode, which effectively reduces the interfacial resistance of the solid-state battery. Compared to the traditional methods of solid-state battery assembly, the directly printed electrolyte helps to achieve higher capacities and a better rate performance. The direct fabrication of electrolyte from printable inks at an elevated temperature will shed new light on the design of all-3D-printed batteries for next-generation electronic devices.

Rechargeable zinc (Zn) batteries suffer from poor cycling performance that can be attributed to dendrite growth and surface-originated side reactions. Herein, we report that cycling performance of Zn metal anode can be improved significantly by utilizing monolayer graphene (Gr) as the electrodeposition substrate. Utilizing microscopy and X-ray diffraction techniques, we demonstrate that electrodeposited Zn on Gr substrate has a compact, uniform, and nondendritic character. The Gr layer, due to its high lattice compatibility with Zn, provides low nucleation overpotential sites for Zn electrodeposition. Atomistic calculations indicate that Gr has strong affinity to Zn (binding energy of 4.41 eV for Gr with four defect sites), leading to uniform distribution of Zinc adatoms all over the Gr surface. This synergistic compatibility between Gr and Zn promotes subsequent homogeneous and planar Zn deposits with low interfacial energy (0.212 J/m2) conformal with the current collector surface.

Despite the ever-growing demand in safe and high power/energy density of Li+ ion and Li metal rechargeable batteries (LIBs), materials-related challenges are responsible for the majority of performance degradation in such batteries. These challenges include electrochemically induced phase transformations, repeated volume expansion and stress concentrations at interfaces, poor electrical and mechanical properties, low ionic conductivity, dendritic growth of Li, oxygen release and transition metal dissolution of cathodes, polysulfide shuttling in Li–sulfur batteries, and poor reversibility of lithium peroxide/superoxide products in Li–O2 batteries. Owing to compelling physicochemical and structural properties, in recent years two-dimensional (2D) materials have emerged as promising candidates to address the challenges in LIBs. This Review highlights the cutting-edge advances of LIBs by using 2D materials as cathodes, anodes, separators, catalysts, current collectors, and electrolytes. It is shown that 2D materials can protect the electrode materials from pulverization, improve the synergy of Li+ ion deposition, facilitate Li+ ion flux through electrolyte and electrode/electrolyte interfaces, enhance thermal stability, block the lithium polysulfide species, and facilitate the formation/decomposition of Li–O2 discharge products. This work facilitates the design of safe Li batteries with high energy and power density by using 2D materials.

Dendritic growth of lithium (Li) has severely impeded the practical application of Li-metal batteries. Herein, a 3D conformal graphene oxide nanosheet (GOn) coating, confined into the woven structure of a glass fiber separator, is reported, which permits facile transport of Li-ions thought its structure, meanwhile regulating the Li deposition. Electrochemical measurements illustrate a remarkably enhanced cycle life and stability of the Li-metal anode, which is explained by various microscopy and modeling results. Utilizing scanning electron microscopy, focused ion beam, and optical imaging, the formation of an uniform Li film on the electrode surface in the case of GO-modified samples is revealed. Ab initio molecular dynamics (AIMD) simulations suggest that Li-ions initially get adsorbed to the lithiophilic GOn and then diffuse through defect sites. This delayed Li transfer eliminates the "tip effect" leading to a more homogeneous Li nucleation. Meanwhile, CC bonds rupture observed in the GO during AIMD simulations creates more pathways for faster Li-ions transport. In addition, phase-field modeling demonstrates that mechanically rigid GOn coating with proper defect size (smaller than 25 nm) can physically block the anisotropic growth of Li. This new understanding is a significant step toward the employment of 2D materials for regulating the Li deposition.

In spite of significant interest toward solid-state electrolytes owing to their superior safety in comparison to liquid-based electrolytes, sluggish ion diffusion and high interfacial resistance