Understanding the characteristics of high-voltage additives in Li-ion batteries: Solvent effects

Electrolytes and Interphases in Li-Ion Batteries and Beyond

“…Besides the successful example of BDB, whose synthesis was guided by molecular orbital calculation, 273 other computational means such as quantum chemistry and density function theory have enabled the screening and evaluation of a large number of chemicals, and many parameters such as ionization potential and binding energy were developed to correlate to their redox potentials as well as radical stabilities. 275,276 Finally, there is another class of overcharge protection additives that do not form redox shuttle but instead sacrificially decompose, and therefore terminate the cell operation before catastrophic results ensure. These so-called "shutdown overcharge additives" included the pyrocarbonates, cyclohexyl benzene (CHB), and biphenyl (BP).…”

Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries

“…In 2009, Han et al 145 calculated the ionization potential and oxidation potential for 108 organic molecules to search for electrolytes with high oxidation voltage. For the reduction reaction, 7381 EC-based structures have been screened by Halls and Tasaki 146 in 2010.…”

Molecular Modeling of Electrolytes

“…A number of QC studies have focused on understanding the oxidation stability of electrolyte nonionic and ionic solvents [7,8,[17][18][19][20][21][22][23][24], redox shuttles [25][26][27], and anions [28][29][30][31]. The majority of the studies considered isolated solvents or anions that do not explicitly interact with the electrode; in situations where there is no specific interaction such as hydrogen bonding with other electrolyte components; and where the solvent effect is included via the PCM.…”

“…A few studies went beyond to include the condensed-phase interactions present in ionic liquids [32], cation-anion interactions [33], or solvent-anion interactions [16,[34][35][36][37]. The most successful were DFT predictions of shuttle redox potentials [26,38], which reported a close agreement with the experimental data showing a root mean square deviation of 0.08 V. Similarly, Wang, Buhrmester, and Dahn [38] reported excellent agreement between the calculated values for 17 redox shuttle additives, with a root mean square deviation between the calculated and measured oxidation potentials of 0.15 V and a maximum deviation of 0.25 V, indicating that DFT calculations at B3LYP/6-31G(d,p) could be effectively used for screening redox additives. Fu et al [18] have shown that DFT calculations can predict redox potentials for a diverse set of hundreds of organic molecules and free radicals in acetonitrile when 0.25 eV was added to the DFT values, indicating that computational electrochemistry could become a powerful tool for the organic chemistry community.…”