Effect Mechanism of Phosphorus-Containing Flame Retardants with Different Phosphorus Valence States on the Safety and Electrochemical Performance of Lithium-Ion Batteries

With the widespread application of lithium-ion batteries (LIBs), safety performance has become a critical factor limiting the commercialization of large-scale, high-capacity LIBs. The main reason for the safety problem is that the electrolytes of LIBs are extremely flammable. Adding flame retardants to conventional electrolytes is an effective method to improve battery safety. In this paper, trimethyl phosphate (TMP) and trimethyl phosphite (TMPi) were used as research objects, and the flame-retardant test and differential scanning calorimetry (DSC) of the electrolytes configured by them were first carried out. The self-extinguishing time of the electrolyte with 5% TMP and TMPi is significantly reduced, achieving a flame-retardant effect. Secondly, the electrochemical performance of LiFePO4|Li half-cells after adding different volume ratios of TMP and TMPi was studied. Compared with TMPi5, the peak potential difference between the oxidation peak and the reduction peak of the LiFePO4|Li half-cell with TMP5 added is reduced, the battery polarization is reduced, the discharge specific capacity after 300 cycles is large, the capacity retention rate is as high as 99.6%, the discharge specific capacity is larger at different current rates, and the electrode resistance is smaller. TMPi5 causes the discharge-specific capacity to attenuate, which is more obvious at high current rates. LiFePO4|Li half-cells with 5% volume ratio of flame retardant have the best electrochemical performance. Finally, the influence mechanism of the phosphorus valence state on battery safety and electrochemical performance was compared and studied. After 300 cycles, the surface of the LiFePO4 electrode with 5% TMP added had a smoother and more uniform CEI film and higher phosphorus (P) and fluorine (F) content, which was beneficial to the improvement of electrochemical performance. The cross-section of the LiFePO4 electrode showed slight collapse and cracks, which slowed down the attenuation of battery capacity.