Aiming at the electrical safety problem of a high-voltage lithium-ion battery system caused by an arc, and based on the establishment of a battery arc fault experimental platform, the evolution law of safety caused by an arc in the negative terminal of a battery system under different working conditions is discussed. On this basis, a battery arc evolution model based on magnetohydrodynamics is established to analyze the arc’s electro-thermal coupling characteristics to further obtain the distribution of the arc’s multi-physical field. The results show that the arc generated by the high-voltage grade battery pack will break down the cell’s shell and form a hole, resulting in electrolyte leakage. When the loop current is 10 A, the evolution law of arc voltage and current is basically the same under different supply voltages, charges, and discharges. The accuracy of the battery arc simulation model is verified by comparing the simulation with the experimental results. The research in this paper provides a theoretical basis for the electrical safety design of lithium-ion batteries caused by the arc, fills the gaps in the field of battery system arc simulation, and is of great significance for improving the safety performance of arc protection.