During the conventional continuous casting process of high-aluminum steels(w([Al])>0.5 wt.%),some components of slag,such as SiO2,B2O3,and TiO2,could be reduced by aluminum in molten steel.Therefore,the CaO-BaO-Al2O3-CaF2-Li2O non-reactive mold fluxes were designed using the simplex grid method and molecular dynamics to mitigate the slag-metal interface reaction and stabilize the performance of mold fluxes.The results show that the components of non-reactive quinary system are 20-40 wt.%CaO,14-34 wt.%BaO,14-34 wt.%Al2O3,4-12 wt.%F,and 4-8 wt.%Li2O.Molecular dynamics simulation results show that[AlO4]-tetrahedron acts as network formers and melt network structure is mainly chain and lamellar in the low-viscosity area.The cross sections of w(F)=8 wt.%,w(Li2O)=8 wt.%and w(F)=12 wt.%,w(Li2O)=8 wt.%are important reference sections for the design of mold flux,with the compositions of 22-40 wt.%CaO,14-34 wt.%BaO,20-34 wt.%Al2O3 and 23-40 wt.%CaO,14-34 wt.%BaO,20-28 wt.%Al2O3,respectively.