Understanding the influence of Mg doping for the stabilization of capacity and higher discharge voltage of Li- and Mn-rich cathodes for Li-ion batteries.

Although Li- and Mn-rich layered cathodes exhibit high specific capacity, the cathode materials of the general formula Li1+x[NiyMnzCow]O2 (x + y + z + w = 1) suffer from capacity fading and discharge-voltage decay during prolonged cycling, due to the layered-to-spinel transformation upon cycling to potentials higher than 4.5 V vs. Li. In this paper, we study the effect of Mg doping (by partial replacement of Mn ions) on the electrochemical performance of Li- and Mn-rich cathodes in terms of specific capacity, capacity retention and discharge voltage upon cycling. Mg-doped Li- and Mn-rich Li1.2Ni0.16Mn0.54Mg0.02Co0.08O2 and Li1.2Ni0.16Mn0.51Mg0.05Co0.08O2 cathode materials were synthesized by a self-combustion reaction (SCR), and their electrochemical performance in Li-ion batteries was tested. The replacement of a small amount of Mn ions by Mg ions in these materials results in a decrease in their specific capacity. The doping of a small amount of Mg (x = 0.02) resulted only in the stabilization of the capacity, whereas a greater amount (x = 0.05) resulted in improved capacity retention and discharge voltage upon cycling. Li1.2Ni0.16Mn0.51Mg0.05Co0.08O2 exhibits a low specific capacity of about 160 mA h g-1, which increases and then stabilizes at about 230 mA h g-1, and finally decreases to 210 mA h g-1 during 100 cycles. The substitution of Mg for Mn (x = 0.05) results in a higher discharge voltage than the other two cathode materials examined in this study. Structural analysis of the cycled electrodes suggests that Mg suppresses the activation of Li2MnO3 during the initial cycling, and hence, partially prevents layered-to-spinel transformation, resulting in a better electrochemical performance of the Mg-doped cathode material as compared to the undoped material.

Thermodynamic and kinetic studies of LiNi0.5Co0.2Mn0.3O2 as a positive electrode material for Li-ion batteries using first principles.

Ni-rich Li-based layered Ni, Co, and Mn (NCM) materials have shown tremendous promise in recent years as positive electrode materials for Li-ion batteries. This is evident as companies developing batteries for electrical vehicles are currently commercializing these materials. Despite the considerable research performed on LiNiαCoßMnγO2 systems, we do not yet have a complete atomic level understanding of these materials. In this work we study the cationic ordering, thermodynamics, and diffusion kinetics of LiNi0.5Co0.2Mn0.3O2 (NCM-523). Initially, we show that cationic ordering can be predicted employing cheap atomistic simulations, instead of using expensive first-principles methods. Subsequently, we investigate the electrochemical, thermodynamic and kinetic properties of NCM-523 using density functional theory (DFT). Our results demonstrate the importance of including dispersion corrections to standard first principles functionals in order to correctly predict the lattice parameters of layered cathode materials. We also demonstrate that a careful choice of computational protocol is essential to reproduce the experimental intercalation potential trends observed in the LiNi0.5Co0.2Mn0.3O2 electrodes. Analysis of the electronic structure confirms an active role of Ni in the electrochemical redox process. Moreover, we confirm the experimental finding that on complete delithiation, this material remains in an O3 phase, unlike LiCoO2 and NCM-333. Finally, we study various pathways for the Li-ion diffusion in NCM-523, and pinpoint the preferred diffusion channel based on first principles simulations. Interestingly, we observe that the Li diffusion barrier in NCM-523 is lower than that in LiCoO2.

Studies of Nickel-Rich LiNi0.85Co0.10Mn0.05O2 Cathode Materials Doped with Molybdenum Ions for Lithium-Ion Batteries.

In this work, we continued our systematic investigations on synthesis, structural studies, and electrochemical behavior of Ni-rich materials Li[NixCoyMnz]O2 (x + y + z = 1; x ≥ 0.8) for advanced lithium-ion batteries (LIBs). We focused, herein, on LiNi0.85Co0.10Mn0.05O2 (NCM85) and demonstrated that doping this material with high-charge cation Mo6+ (1 at. %, by a minor nickel substitution) results in substantially stable cycling performance, increased rate capability, lowering of the voltage hysteresis, and impedance in Li-cells with EC-EMC/LiPF6 solutions. Incorporation of Mo-dopant into the NCM85 structure was carried out by in-situ approach, upon the synthesis using ammonium molybdate as the precursor. From X-ray diffraction studies and based on our previous investigation of Mo-doped NCM523 and Ni-rich NCM811 materials, it was revealed that Mo6+ preferably substitutes Ni residing either in 3a or 3b sites. We correlated the improved behavior of the doped NCM85 electrode materials in Li-cells with a partial Mo segregation at the surface and at the grain boundaries, a tendency established previously in our lab for the other members of the Li[NixCoyMnz]O2 family.

Modification of Li- and Mn-Rich Cathode Materials via Formation of the Rock-Salt and Spinel Surface Layers for Steady and High-Rate Electrochemical Performances.

We demonstrate a novel surface modification of Li- and Mn-rich cathode materials 0.33Li2MnO3·0.67LiNi0.4Co0.2Mn0.4O2 for lithium-ion batteries (high-energy Ni-Co-Mn oxides, HE-NCM) via their heat treatment with trimesic acid (TA) or terephthalic acid at 600 °C under argon. We established the optimal regimes of the treatment-the amounts of HE-NCM, acid, temperature, and time-resulting in a significant improvement of the electrochemical behavior of cathodes in Li cells. It was shown that upon treatment, some lithium is leached out from the surface, leading to the formation of a surface layer comprising rock-salt-like phase Li0.4Ni1.6O2. The analysis of the structural and surface studies by X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy confirmed the formation of the above surface layer. We discuss the possible reactions of HE-NCM with the acids and the mechanism of the formation of the new phases, Li0.4Ni1.6O2 and spinel. The electrochemical characterizations were performed by testing the materials versus Li anodes at 30 °C. Importantly, the electrochemical results disclose significantly improved cycling stability (much lower capacity fading) and high-rate performance for the treated materials compared to the untreated ones. We established a lower evolution of the voltage hysteresis with cycling for the treated cathodes compared to that for the untreated ones. Thermal studies by differential scanning calorimetry also demonstrated lower (by ∼32%) total heat released in the reactions of the materials treated with fluoroethylene carbonate (FEC)-dimethyl carbonate (DEC)/LiPF6 electrolyte solutions, thus implying their significant surface stabilization because of the surface treatment. It was established by a postmortem analysis after 400 cycles that a lower amount of transition-metal cations dissolved (especially Ni) and a reduced number of surface cracks were formed for the 2 wt % TA-treated HE-NCMs compared to the untreated ones. We consider the proposed method of surface modification as a simple, cheap, and scalable approach to achieve a steady and superior electrochemical performance of HE-NCM cathodes.

Electrochemical Activation of Li2MnO3 Electrodes at 0 °C and Its Impact on the Subsequent Performance at Higher Temperatures.

This work continues our systematic study of Li- and Mn- rich cathodes for lithium-ion batteries. We chose Li2MnO3 as a model electrode material with the aim of correlating the improved electrochemical characteristics of these cathodes initially activated at 0 °C with the sstructural evolution of Li2MnO3, oxygen loss, formation of per-oxo like species (O22-) and the surface chemistry. It was established that performing a few initial charge/discharge (activation) cycles of Li2MnO3 at 0 °C resulted in increased discharge capacity and higher capacity retention, and decreased and substantially stabilized the voltage hysteresis upon subsequent cycling at 30 °C or at 45 °C. In contrast to the activation of Li2MnO3 at these higher temperatures, Li2MnO3 underwent step-by-step activation at 0 °C, providing a stepwise traversing of the voltage plateau at >4.5 V during initial cycling. Importantly, these findings agree well with our previous studies on the activation at 0 °C of 0.35Li2MnO3·0.65Li[Mn0.45Ni0.35Co0.20]O2 materials. The stability of the interface developed at 0 °C can be ascribed to the reduced interactions of the per-oxo-like species formed and the oxygen released from Li2MnO3 with solvents in ethylene carbonate-methyl-ethyl carbonate/LiPF6 solutions. Our TEM studies revealed that typically, upon initial cycling both at 0 °C and 30 °C, Li2MnO3 underwent partial structural layered-to-spinel (Li2Mn2O4) transition.

Horizons for Li-Ion Batteries Relevant to Electro-Mobility: High-Specific-Energy Cathodes and Chemically Active Separators.

Li-ion batteries (LIBs) today face the challenge of application in electrified vehicles (xEVs) which require increased energy density, improved abuse tolerance, prolonged life, and low cost. LIB technology can significantly advance through more realistic approaches such as: i) stable high-specific-energy cathodes based on Li1+ x Niy Coz Mnw O2 (NCM) compounds with either Ni-rich (x = 0, y → 1), or Li- and Mn-rich (0.1 < x < 0.2, w > 0.5) compositions, and ii) chemically active separators and binders that mitigate battery performance degradation. While the stability of such cathode materials during cell operation tends to decrease with increasing specific capacity, active material doping and coatings, together with carefully designed cell-formation protocols, can enable both high specific capacities and good long-term stability. It has also been shown that major LIB capacity fading mechanisms can be reduced by multifunctional separators and binders that trap transition metal ions and/or scavenge acid species. Here, recent progress on improving Ni-rich and Mn-rich NCM cathode materials is reviewed, as well as in the search for inexpensive, multifunctional, chemically active separators. A realistic overview regarding some of the most promising approaches to improving the performance of rechargeable batteries for xEV applications is also presented.

Understanding the Role of Minor Molybdenum Doping in LiNi0.5Co0.2Mn0.3O2 Electrodes: from Structural and Surface Analyses and Theoretical Modeling to Practical Electrochemical Cells.

Doping LiNi0.5Co0.2Mn0.3O2 (NCM523) cathode material by small amount of Mo6+ ions, around 1 mol %, affects pronouncedly its structure, surface properties, and electronic and electrochemical behavior. Cathodes comprising Mo6+-doped NCM523 exhibited in Li cells higher specific capacities, higher rate capabilities, lower capacity fading, and lower charge-transfer resistance that relates to a more stable electrode/solution interface due to doping. This, in turn, is ascribed to the fact that the Mo6+ ions tend to concentrate more at the surface, as a result of a synthesis that always includes a necessary calcination, high-temperature stage. This phenomenon of the Mo dopant segregation at the surface in NCM523 material was discovered in the present work for the first time. It appears that Mo doping reduces the reactivity of the Ni-rich NCM cathode materials toward the standard electrolyte solutions of Li-ion batteries. Using density functional theory (DFT) calculations, we showed that Mo6+ ions are preferably incorporated at Ni sites and that the doping increases the amount of Ni2+ ions at the expense of Ni3+ ions, due to charge compensation, in accord with X-ray absorption fine structure (XAFS) spectroscopy measurements. Furthermore, DFT calculations predicted Ni-O bond length distributions in good agreement with the XAFS results, supporting a model of partial substitution of Ni sites by molybdenum.

Remarkably Improved Electrochemical Performance of Li- and Mn-Rich Cathodes upon Substitution of Mn with Ni.

Li- and Mn-rich transition-metal oxides of layered structure are promising cathodes for Li-ion batteries because of their high capacity values, ≥250 mAh g-1. These cathodes suffer from capacity fading and discharge voltage decay upon prolonged cycling to potential higher than 4.5 V. Most of these Li- and Mn-rich cathodes contain Ni in a 2+ oxidation state. The fine details of the composition of these materials may be critically important in determining their performance. In the present study, we used Li1.2Ni0.13Mn0.54Co0.13O2 as the reference cathode composition in which Mn ions are substituted by Ni ions so that their average oxidation state in Li1.2Ni0.27Mn0.4Co0.13O2 could change from 2+ to 3+. Upon substitution of Mn with Ni, the specific capacity decreases but, in turn, an impressive stability was gained, about 95% capacity retention after 150 cycles, compared to 77% capacity retention for Li1.2Ni0.13Mn0.54Co0.13O2 cathodes when cycled at a C/5 rate. Also, a higher average discharge voltage of 3.7 V is obtained for Li1.2Ni0.27Mn0.4Co0.13O2 cathodes, which decreases to 3.5 V after 150 cycles, while the voltage fading of cathodes comprising the reference material is more pronounced. The Li1.2Ni0.27Mn0.4Co0.13O2 cathodes also demonstrate higher rate capability compared to the reference Li1.2Ni0.13Mn0.54Co0.13O2 cathodes. These results clearly indicate the importance of the fine composition of cathode materials containing the five elements Li, Mn, Ni, Co, and O. The present study should encourage rigorous optimization efforts related to the fine composition of these cathode materials, before external means such as doping and coating are applied.

High-Capacity Layered-Spinel Cathodes for Li-Ion Batteries.

Li and Mn-rich layered oxides with the general structure x Li2 MnO3 ⋅(1-x) LiMO2 (M=Ni, Mn, Co) are promising cathode materials for Li-ion batteries because of their high specific capacity, which may be greater than 250 mA h g(-1) . However, these materials suffer from high first-cycle irreversible capacity, gradual capacity fading, limited rate capability and discharge voltage decay upon cycling, which prevent their commercialization. The decrease in average discharge voltage is a major issue, which is ascribed to a structural layered-to-spinel transformation upon cycling of these oxide cathodes in wide potential ranges with an upper limit higher than 4.5 V and a lower limit below 3 V versus Li. By using four elements systems (Li, Mn, Ni, O) with appropriate stoichiometry, it is possible to prepare high capacity composite cathode materials that contain LiMn1.5 Ni0.5 O4 and Lix Mny Niz O2 components. The Li and Mn-rich layered-spinel cathode materials studied herein exhibit a high specific capacity (≥200 mA h g(-1) ) with good capacity retention upon cycling in a wide potential domain (2.4-4.9 V). The effect of constituent phases on their electrochemical performance, such as specific capacity, cycling stability, average discharge voltage, and rate capability, are explored here. This family of materials can provide high specific capacity, high rate capability, and promising cycle life. Using Co-free cathode materials is also an obvious advantage of these systems.

Sonochemical synthesis of LiNi0.5Mn1.5O4 and its electrochemical performance as a cathode material for 5 V Li-ion batteries.

LiNi0.5Mn1.5O4 was synthesized as a cathode material for Li-ion batteries by a sonochemical reaction followed by annealing, and was characterized by XRD, SEM, HRTEM and Raman spectroscopy in conjunction with electrochemical measurements. Two samples were prepared by a sonochemical process, one without using glucose (sample-S1) and another with glucose (sample-S2). An initial discharge specific capacity of 130 mA h g(-1) is obtained for LiNi0.5Mn1.5O4 at a relatively slow rate of C/10 in galvanostatic charge-discharge cycling. The capacity retention upon 50 cycles at this rate was around 95.4% and 98.9% for sample-S1 and sample-S2, respectively, at 30°C.