Early state of Li7La3Zr2O12/Li heterointerface in all-solid-state battery: causality dilemma between crack formation and Li-rich nanodendrites

It has been argued that the Li 7 La 3 Zr 2 O 12 /Li hetero-interface in all-solid-state batteries is prone to decomposition and degradation during synthesis and cycling, leading to the formation of Li dendrites and their propagation inside the Li 7 La 3 Zr 2 O 12 bulk. However, the exact formation mechanism of these dendrites, as well as their chemical composition, remains not fully understood until now due to the difficulty of quantifying the Li concentration within the battery materials. Therefore, in this work, we employed atom probe tomography in conjunction with advanced transmission electron microscopy to investigate the Li 7 La 3 Zr 2 O 12 bulk in the vicinity of the Li 7 La 3 Zr 2 O 12 /Li heterointerface, a region prone to crack formation and propagation. We discovered that numerous Li-nanodendrites are present inside the LLZO bulk close to the Li/LLZO interface and that these nanodendrites appear similar to cracks being filled by Li. Therefore, this study raises a possible dilemma of causality between the crack formation and Li segregation in LLZO grains. Interestingly, advanced microscopy investigations prove the existence of a high density of dislocations within LLZO for some grains. Moreover, the finite element modeling suggests that the dislocations’ cores can act as nucleation sites for strong Li segregation, leading to an increase in hydrostatic stress. This implies that this strong Li segregation at the dislocation cores and the resultant high hydrostatic stress might be the cause for the crack formation. Subsequently, Li can be further accumulated at the cracks, forming the Li-nanodendrites. It is without doubt that the presence of such microscopic Li-rich nanodendrites in the as-deposited state will lead to the growth and propagation of the well-known macroscopic Li dendrites during cycling. • Presence of Li-nanodendrites in LLZO bulk close to the Li/LLZO heterointerface. • Existence of a high density of dislocations in LLZO bulk proved by TEM. • The strong Li segregation at the dislocations' cores leads to crack formation. • No secondary phases are formed at the abrupt interface between Li and LLZO.