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We describe for the first time molecular rearrangements in a highly stable and porous Ni-rich layered oxide cathode material (LiNi0.80Co0.15Mn0.05O2, Ni-rich NCM) using a thermally reactive, Co-embedded metal–organic framework (MOF). The thermal decomposition of the MOF on the surface of the active material forms a molecular-level thin layer of CoOx species, which are thought to act as seeds for the dramatic transformation of the surface of the Ni-rich NCM from a layered oxide (Rm) to a more stable spinel-like phase (Fdm) before cycling and the formation of multi-scale (nano-to-micro) pores in the active particles. These phase transformations and morphology changes are associated with a galvanic replacement reaction between Co ions from the MOF and Ni ions near the surface of Ni-rich NCM, where some of the Ni ions migrate to the neighboring vacant Li sites by the diffusion of Co ions through melted residual lithium. Therefore, the resultant Co-/Ni-rich surface domains with a more stable spinel-like phase as well as a porous microstructure improve the cyclability and thermal stability of the MOF-inspired Ni-rich NCM.

The formation of lithium residuals in Ni-rich nickel cobalt manganese oxide is inevitable, due to of the cation mixing by Ni2+ and excess Li required for high energy density. The purpose of this study is to examine the role of Li content in such materials after the washing process, which could reduce Li residuals and enhance the electrochemical performance of lithium ion batteries containing Li1.0Ni0.91Co0.06Mn0.03O2 (NCM) as the cathode. The washing process reduced the Li residuals on the surface as well as the Li in the NCM structure. When a low Li content is used in the NCM, the Li content remaining in its structure after washing is lower than 1 mol. This removal of Li residues from the surface after washing leads to a capacity drop in spite of the improved cycle retention. Therefore, a high Li content is required in order to obtain enhanced electrochemical performance of high-Ni NCM. This trend regarding the Li content is also shown for NCM with small particle size.

Optimizing synthesis parameters is the key to successfully design ideal Ni-rich cathode materials that satisfy principal electrochemical specifications. We herein implement machine learning algorithms using 330 experimental datasets, obtained from a controlled environment for reliability, to construct a predictive model. First, correlation values showed that the calcination temperature and the size of the particles are determining factors for achieving a long cycle life. Then, we compared the accuracy of seven different machine learning algorithms for predicting the initial capacity, capacity retention rate, and amount of residual Li. Remarkable predictive capability was obtained with the average value of coefficient of determinant, R2 = 0.833, from the extremely randomized tree with adaptive boosting algorithm. Furthermore, we propose a reverse engineering framework to search for experimental parameters that satisfy the target electrochemical specification. The proposed results were validated by experiments. The current results demonstrate that machine learning has great potential to accelerate the optimization process for the commercialization of cathode materials.

The growing popularity of Li-ion batteries in the field of energy storage necessitates the constant development of methods for improving their performance. To address this task, this study describes the effect of transition metal (TM = Al, Co, Fe) phosphate coatings on the electrochemical performance of Li1.0Ni0.8Co0.15Mn0.05O2 positive electrode materials, highlighting the importance of the TM/P mole ratio, and reveals that decreased amounts of Li residuals were observed for all coated samples. Considering Li residual removal as well as capacity and capacity retention upon cycling, the most effective surface modification was achieved in the case of a 1:1 Co/P coating, which increased initial capacity and capacity retention by 10 mAh g−1 and 3%, respectively, as compared to the uncoated sample. Moreover, the beneficial effect of the above Co/P coating is also confirmed for the more Ni-rich Li1.0Ni0.91Co0.06Mn0.03O2.

Spinel-embedded lithium-rich oxides are synthesized and their structural phases are analyzed. The type of spinel LiM0.5Mn1.5O4 (M = Ni, Co, Mn) embedded is varied by controlling the spinel composition and content. Of the various composites fabricated with different spinel phases, the LiCo0.5Mn1.5O4-embedded over-lithiated layered oxide (OLO) shows the best electrochemical performance as a cathode because of the absence of a parasitic phase and its high structural stability. The formation energy of the LiCo0.5Mn1.5O4-embedded oxide is determined through first-principles calculations and is found to be lower than that of the pristine oxide as well as other spinel-phase-embedded oxides. It is also observed that use of OLO with optimal embedded spinel LiCo0.5Mn1.5O4 in a cylindrical 18650-type cell results in improvement in the full-cell electrochemical performance.

Ni-rich layered oxides are attractive materials owing to their potentially high capacity for cathode applications. However, when used as cathodes in Li-ion batteries, they contain a large amount of Li residues, which degrade the electrochemical properties because they are the source of gas generation inside the battery. Here, we propose a computational approach to designing optimal coating materials that prevent gas evolution by removing residual Li from the surface of the battery cathode. To discover promising coating materials, the reactions of 16 metal phosphates (MPs) and 45 metal oxides (MOs) with the Li residues, LiOH, and Li2CO3 are examined within a thermodynamic framework. A materials database is constructed according to density functional theory using a hybrid functional, and the reaction products are obtained according to the phases in thermodynamic equilibrium in the phase diagram. In addition, the gravimetric efficiency is calculated to identify coating materials that can eliminate Li residue...

The composite material Li x Ni 0.25 Co 0.10 Mn 0.65 O (3.4 + x) / 2 (x = 1.6, 1.4, 1.2, 1.0, 0.8) were synthesized and characterized for their structural, morphological, and performance as cathode materials in Li-ion batteries. The Rietveld refinement results indicate the presence of two phases at high lithium levels (x = 1.6 and 1.4): Li 2 MnO 3 ( C 2/ m ) and Li M O 2 ( M Ni, Co, Mn) ( R 3¯ m ); the latter contains Ni 2 + and Ni 3 + . At low lithium levels (x = 1.2, 1.0, and 0.8) an additional spinel phase Li M 2 O 4 ( Fd 3¯ m ) emerges, which is known to affect the electrochemical performance of the oxide. Structural analysis reveals that the spinel phase contains mixed transition metals Ni, Co, and Mn as [Li + ,Co 2 + ][Ni 2 + ,Co 3 + ,Mn 4 + ] 2 O 4 . A low lithium level is found to induce primary particle growth, as well as Co and Ni segregation within the secondary particles. These results are expected to contribute to material optimization and commercialization of lithium-rich oxide cathodes.

The effect of bi-functional coatings consisting of Zr and phosphate (P) on the electrochemical performance of Li1.0Ni0.8Co0.15Mn0.05O2 (NCM) has been investigated. The presence of various types of Zr and P compounds such as oxides (ZrO2 and Li2ZrO3) and phosphates (Zr2P2O9, ZrP2O7 and LiZr2(PO4)3) in the coating was confirmed by experiments as well as density functional theory (DFT) calculations. When the NCM samples were coated with the Zr/P hybrid material, the cycle retention and the amount of removed Li residuals (LiOH, Li2CO3) were enhanced by the synergistic effect from Zr and P. The NCM sample coated with a Zr/P layer with a Zr/P ratio of 1 : 1 exhibited an increase in the initial capacity (209.3 mA h g−1) compared to the pristine sample (207.4 mA h g−1) at 0.1C, owing to the formation of the coating layer. The capacity retention of the Zr/P coated sample (92.4% at the 50th cycle) was also improved compared to that of the pristine NCM sample (90.6% at the 50th cycle). Moreover, the amount of Li residuals in the Zr/P coated NCM sample was greatly reduced from 3693 ppm (pristine NCM) to 2525 ppm (Zr/P = 5 : 5).

Ni-rich layered oxides are promising cathode materials due to their high capacities. However, their synthesis process retains a large amount of Li residue on the surface, which is a main source of gas generation during operation of the battery. In this study, combined with simulation and experiment, we propose the optimal metal phosphate coating materials for removing residual Li from the surface of the Ni-rich layered oxide cathode material LiNi0.91Co0.06Mn0.03O2. First-principles-based screening process for 16 metal phosphates is performed to identify an ideal coating material that is highly reactive to Li2O. By constructing the phase diagram, we obtain the equilibrium phases from the reaction of coating materials and Li2O, based on a database using a DFT hybrid functional. Experimental verification for this approach is accomplished with Mn3(PO4)2, Co3(PO4)2, Fe3(PO4)2, and TiPO4. The Li-removing capabilities of these materials are comparable to the calculated results. In addition, electrochemical performances up to 50 charge/discharge cycles show that Mn-, Co-, Fe-phosphate materials are superior to an uncoated sample in terms of preventing capacity fading behavior, while TiPO4 shows poor initial capacity and rapid reduction of capacity during cycling. Finally, Li-containing equilibrium phases examined from XRD analysis are in agreement with the simulation results.

The solvent evaporation method on the structural changes and surface chemistry of the cathode and the effect of electrochemical performance of Li1.0Ni0.8Co0.15Mn0.05O2 (NCM) has been investigated. After dissolving of Li residuals using minimum content of solvent in order to minimize the damage of pristine material and the evaporation time, the solvent was evaporated without filtering and remaining powder was re-heated at 700 °C in oxygen environment. Two kinds of solvent, de-ionized water and diluted nitric acid, were used as a solvent. The almost 40% of Li residuals were removed using solvent evaporation method. The NCM sample after solvent evaporation process exhibited an increase in the initial capacity (214.3 mAh/g) compared to the pristine sample (207.4 mAh/g) at 0.1C because of enhancement of electric conductivity caused by decline of Li residuals. The capacity retention of NCM sample after solvent evaporation process (96.0% at the 50th cycle) was also improved compared to that of the pristine NCM sample (90.6% at the 50th cycle). The uniform Li residual layer after solvent treated and heat treatment acted like a coating layer, leading to enhance the cycle performance. The NCM sample using diluted nitric acid showed better performance than that using de-ionized water.