The invention relates to the technical field of lithium secondary battery additives and particularly relates to a lithium secondary battery additive, a preparation method thereof and application thereof. The additive is LibMaXc, M is B, Al, Ga, In, Y, Sc, Sb, Bi, Nb, Ta, Ti, Zr, V, Cr, Mo, W, Mn, Tc, Re, Fe, Co, Ni, Cu, Ag, Zn, Cd, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu, X isF, Cl, Br or I, b is larger than or equal to 0.2 and smaller than or equal to 6, a is larger than or equal to 0.1 and smaller than or equal to 3, and c is larger than or equal to 1 and smaller than or equal to 9. The lithium secondary battery additive has the advantages of high ionic conductivity and air stability, the rapid transmission of electrode ions can be improved, the electrode loading capacity and thickness are improved, and the energy density of the battery is improved.