The superior interfacial properties possessed by some unique LiF phases makes them highly desirable components in a solid electrolyte interface (SEI) of Li-ion batteries and all solid-state lithium metal batteries (LIBs and ASSLMBs). However, rock salt ordered LiF being the most energetically stable under ambient conditions, other phases are highly susceptible to phase transformation, thus hampering their deployment for interfacial stabilization in LIBs. Therefore, the intrinsic role of LiF as protective layer remains uncertain as rock salt structured LiF phase suffers from poor lithium-ion transport properties. Understanding whether some less common LiF phases with superior performance as a flexible interfacial protective layer can be stabilized by impurities and dopants is of critical importance. Uncovering strategies for such material transformation can help us design in situ and ex situ processes for controlled synthesis of LiF-rich interfacial composites. In this study, we explore a host of monoatomic, polyatomic, polyanionic dopants and investigate their bonding and aggregation behaviors within a LiF matrix. We are able to detect tendencies of segregation among some of the dopant choices and link such component agglomeration to derogatory consequences like phase transformation of the host matrix. Furthermore, the limited, yet unique covalent character of LiF is analyzed. Bonding (stabilizing) as well as antibonding (destabilizing) contributions to the electronic band structure are noted; and a case-by-case comparison is drawn between different dopant-infused compositions in order to identify chemical signatures which can act as indicators for phase transformation or stabilization in LiF. The lithium-dopant interactions are found to be critical towards sustaining unique and otherwise unstable phases in LiF network. A favorable/strong interaction of the dopant with surrounding LiF appears to mimic an effect of charge injection into the matrix and is seen to manifest as discernable bonding signatures in our chemical analysis. This seems to have a decisive impact on the LiF structure and its various phases, as is confirmed from ground-state DFT analysis, and the chemical bonding signatures involved can act as a predictor for controlling constituent impurities during in-situ and ex-situ synthesis of LiF.