Lithium metal has been gained intense research interest because of its high specific capacity and lowest electrochemical potential for next generation battery systems with high energy density. However, the utilization of Li metal as an anode material has been limited due to the uncontrolled Li deposition and side reactions on Li metal surface that induce low coulombic efficiency, poor cycle performance and safety issues. Controlling morphology of electrodeposited Li metal is one major direction to resolve these issues. Identification of Li deposition mechanism governing the morphology evolution is prerequisite for establishing strategy for controlling morphology. Herein, we explore governing deposition mechanism from the morphology evolution at varied current (0.2- 1.8 mA cm^-2) and suggest a strategy for growing low surface area Li fibers.

We found that fibrous Li growth follows the initial spherical Li particle formation when the Li sphere size reaches the critical value. The diameter of the initially formed Li particles decreases with the current density. Initially formed spherical Li particles at a low current density (0.2 mA cm^-2) are sufficiently large to grow with a fibrous morphology. Thus, the spherical particles evolve to fibrous Li during subsequent growth. On the other hand, at a higher current density, the Li particles are initially smaller than the critical size and thus cannot immediately grow into a fibrous morphology. Spherical growth of the existing Li particles and additional nucleation on the current collector surface continue, resulting in multilayer Li particles. After Li particles reach the critical size, Li can grow with a fibrous form. Due to the preferential deposition on the existing fibrous Li, the morphology of spherical Li particles smaller than the critical size does not change. Therefore, only fibrous Li deposits were formed at low current density (0.2 mA cm^-2), but both spherical and fibrous Li deposits were formed at higher current densities.

Based on the morphology evolution mechanism, seeded Li deposition strategy was proposed to minimize the surface area of Li deposits and improve cycling stability of Li metal electrode. The stepwise spherical to fibrous Li growth was achieved by changing the current from low to high (0.2 to 1.8 mA cm^-2). Li deposits morphology was well controlled by this strategy resulting in all fibrous morphology with smooth surface. The Li deposits of seeded growth strategy achieved smaller surface area, suppressed side reactions and improved cycle life more than four times compared to that of constant current deposition with same average current density (1 mA cm^-2).