High-Throughput Evaluation of Discharge Profiles of Nickel Substitution in LiNiO₂ by Ab Initio Calculations

Abstract

Substitution of a Ni cation in a LiNiO2 cathode is a common strategy for improving the lifetime and thermal stability of lithium-ion batteries. However, this strategy does not improve the discharging capacity more than that of pristine LiNiO2. We investigated whether the capacity of a cation-substituted battery can be improved by an exhaustive search based on ab initio calculations. To ensure a feasible search at a practical computational cost, many data points obtained by expensive ab initio calculations were bridged by interpolation using the cluster expansion method. Then, the candidates screened by the search were analyzed by more reliable calculations based on density functional theory with the strongly constrained and appropriately normed (SCAN) exchange–correlation functional, which determines the discharging voltage profiles. The screening predicted that partial substitution of Ni with Pt and Pd can improve the discharging capacity of a lithium-ion battery.

Computational Design to Suppress Thermal Runaway of Li-Ion Batteries via Atomic Substitutions to Cathode Materials

“…To this end, we discuss the effect of W on capacity. In the literature, where the effect on the charge–discharge profile was calculated from first-principles, the voltage drops due to the addition of W were comparable to that of Co . This means that additional thermal stability can be expected at the same capacity as that with Co addition.…”

“…The cathode material is one of the primary LIB components that affects durability, capacity, safety, and price. There have been cumulative efforts to improve its operating characteristics since the LIB was first commercialized. − In particular, LiNiO 2 -based cathode materials (LNOs) have been investigated thoroughly because of their cost effectiveness as well as the potentially better battery capacity compared to LiCoO 2 (LCO) . For the same voltage, LNO can provide more Li ions than LCO, leading to the higher battery capacity.…”

Effect of the oxygen vacancy electronic state on Ni migration in Li0.5(Ni0.8Mn0.1Co0.1)O2 cathode material

“…13,14 Doping or substitution of transition metals has been shown to reduce this defect and promote phase stability. [15][16][17][18][19] Another cation disordering is known to occur upon delithiation of the layered NMC cathode, wherein the Ni ions would migrate and occupy the Li site upon prolonged charge/discharge cycles. This then leads to the irreversible phase transformation of a layered structure into a disordered spinel/rock-salt structure.…”

Shry: Application of Canonical Augmentation to the Atomic Substitution Problem

“…If the thermodynamical properties are in focus, the cluster expansion method with Monte Carlo sampling 13 is another very effective technique for studying disordered crystals. 14 Several schemes have been developed 15 − 18 to correct spurious interactions between supercell images for studying charged defects in crystals more quantitatively. These methods ensure that the supercell approach is effective and reliable.…”

“…One such successful method is the method of quasi-random structures (SQS), , which finds the closest periodic supercell to a genuine disordered state based on correlation functions. If the thermodynamical properties are in focus, the cluster expansion method with Monte Carlo sampling is another very effective technique for studying disordered crystals . Several schemes have been developed − to correct spurious interactions between supercell images for studying charged defects in crystals more quantitatively.…”