Virtual screening of borate derivatives as high-performance additives in lithium-ion batteries

Tris(trimethylsilyl) borate as an electrolyte additive for high-voltage lithium-ion batteries using LiNi 1/3 Mn 1/3 Co 1/3 O 2 cathode

“…As a consequence of the electrochemical oxidation behavior, the CEI film originated from the TMSB oxidation may effectively suppress electrolyte decomposition on the cathode and decrease the impedance value under high voltage condition. The Kohn-Sham density functional theory (DFT) equation indicates that the HOMO energy of the TMSB additive ( −7.77 eV) is higher than that of the EC solvent ( −8.25 eV) (higher HOMO energies imply greater oxidation active) [23] , this is in an agreement with the LSV…”

Modeling Electrochemical Decomposition of Fluoroethylene Carbonate on Silicon Anode Surfaces in Lithium Ion Batteries

“…The DFT/PBE functional is chosen to complement AIMD/PBE simulations in this work, and the MP2 method is picked to be consistent with MP2 calculations in one of the authors' previous work 28 and other modeling effort in the literature. 34,35 Both (EC) 2 FEC − :Li + and FEC − :Li + clusters are considered. The larger cluster is chosen to reflect a previous AIMD prediction that Li + is coordinated to slightly more than 3 EC molecules in EC liquid if one EC contains an excess electron.…”

“…A similar discrepancy has been documented for the gas phase Li + :EC − complex. 34 Compared to highly accurate CCSD(T) calculations, the barrier for breaking the C E -O bond in EC − is overestimated by ∼ 0.15 eV when using MP2 and underestimated by BLYP by ∼ 0.33 eV. 34 The hybrid B3LYP DFT functional, which gives predictions closer to the CCSD(T) method for EC − , predicts a more modest 0.392eV barrier for breaking this bond in FEC.…”

“…20 Electronic structure modeling is an excellent complement to experimental analysis. 28,[31][32][33][34][35][36][37][38][39][40][41][42][43] While unlikely to yield the entire sequence of reactions and precise product branching ratios, modeling is useful for interrogating whether each proposed bond-breaking/making step is exothermic, has a sufficiently low free energy barrier, or whether it will be superceded by other reaction pathways. Concerns about theoretical accuracy can be alleviated by using multiple density functional theory (DFT) and quantum chemistry methods to crosscheck predictions.…”

S-containing and Si-containing compounds as highly effective electrolyte additives for SiOx -based anodes/NCM 811 cathodes in lithium ion cells

“…However, the reduction of PS leads to a large impedance of the solid-electrolyte-interphase (SEI) film. Recently, phosphites (P(OR) 3 ), phosphates (OP(OR) 3 ), borates (B(OR) 3 ), and boroxane ( c -B 3 O 3 (OR) 3 ) derivatives, such as tris(trimethylsilyl) phosphite (TTSPi or TMSPi) 11–13 , tris(trimethylsilyl) phosphate (TTSP or TMSP) 14–16 , and tris(trimethylsilyl) borate (TMSB) 17–22 , have been developed as cathode-protective agents, especially for application with nickel-rich layered materials. However, there is a controversy over whether the protective function arises from the scavenging of HF from LiPF 6 hydrolysis through the O-Si bond-breaking pathway 11,12 or from binding of the reaction centres of the layered material to inhibit oxygen removal from the surface by the reaction products 13 .…”