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Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations
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The specific thermal capacity and heat dissipation rate for lithium ion cells containing LiNiO2 and mixed oxide (75%LiCoO2+ 25%LiNiO2) as cathode materials are compared. The experimental measurements were made using a radiative calorimeter consisting of a copper chamber maintained at -168 C by circulating liquid nitrogen and enclosed in a vacuum bell jar. The specific thermal capacity was determined based on warm-up and cool-down transients. The heat dissipation rate was calculated from the values measured for heat radiated and stored, and the resulting values were corrected for conductive heat dissipation through the leads. The specific heat was 1.117 J/ C-g for the LiNiO2 cell and 0.946 J/ C-g for the 75%LiCoO2,25%LiNiO2 cell. Endothermic cooling at the beginning of charge was very apparent for the cell containing 75%LiCoO2,25%LiNiO2 as the cathode. Exothermic heating began at a higher state of charge for the cell with the 75%LiCoO2,25%LiNiO2 cathode compared to the LiNiO2 cathode cell. During discharge, the rate of heat dissipation increased with increase in the discharge current for both types of cells. The maximum heat dissipated at C/5 discharge was 0.065 W and 0.04 W for the LiNiO2 and 75%LiCoO2,25%LiNiO2 cells, respectively, The thermoneutral potential showed variability toward the end of discharge. The plateau region of the curves was used to calculate average thermoneutral potentials of 3.698 V and 3.837 V for the LiNiO2 cell and the 75%LiCoO2,25%LiNiO2 cell, respectively.
LiCoO2 and LiNiO2 fibers have been investigated as alternatives to LiCoO2 and LiNiO2 powders used as lithium-intercalation compounds in cathodes of rechargeable lithium-ion electrochemical cells. In making such a cathode, LiCoO2 or LiNiO2 powder is mixed with a binder [e.g., poly(vinylidene fluoride)] and an electrically conductive additive (usually carbon) and the mixture is pressed to form a disk. The binder and conductive additive contribute weight and volume, reducing the specific energy and energy density, respectively. In contrast, LiCoO2 or LiNiO2 fibers can be pressed and sintered to form a cathode, without need for a binder or a conductive additive. The inter-grain contacts of the fibers are stronger and have fewer defects than do those of powder particles. These characteristics translate to increased flexibility and greater resilience on cycling and, consequently, to reduced loss of capacity from cycle to cycle. Moreover, in comparison with a powder-based cathode, a fiber-based cathode is expected to exhibit significantly greater ionic and electronic conduction along the axes of the fibers. Results of preliminary charge/discharge-cycling tests suggest that energy densities of LiCoO2- and LiNiO2-fiber cathodes are approximately double those of the corresponding powder-based cathodes.
Recent studies have suggested that Co-free, Ni-rich layered cathodes (e.g., doped LiNiO2) can provide promising battery performance for practical applications. However, these layered cathodes suffer from significant surface instability during various stages of the sample history, which generates inherent challenges for achieving stable battery performance and obtaining statistically representative characterization results. To reliably report the surface chemistry of these materials, delicate controls of stepwise sample preparation are required. In this study, we aim to reveal how the surface chemistry of LiNiO2 based materials changes with various environments, including human exhalation, sample storage, sample preparation, electrochemistry cycling, and surface doping. Our results demonstrate that the surface of these materials is highly reactive and prone to alter at various stages of sample handling and characterization. The sensitive surface could impact the interpretation of the surface chemical and structural information, including surface carbonate formation, transition metal reduction and dissolution, and surface reconstruction. Importantly, the heterogeneity of the surface degradation calls for a consolidation of nanoscale, high-resolution characterization, and ensemble-averaged methods in order to improve statistical representation. Furthermore, the doping chemistry can effectively mitigate the surface degradation and improve overall battery performance due to the enhanced surface oxygen retention. Our study highlights the necessity of strict measurements through complementary characterizations at multiple length scales to eliminate unintentional biased conclusions.
(LiFeO2)3LiNiO2 crystallizes in the triclinic P-1 space group. The structure is one-dimensional and consists of three LiFeO2 ribbons oriented in the (0, 1, 1) direction and one LiNiO2 ribbon oriented in the (0, 1, 1) direction. In each LiFeO2 ribbon, Li1+ is bonded in a linear geometry to two equivalent O2- atoms. Both Li–O bond lengths are 1.59 Å. Fe3+ is bonded in a linear geometry to two equivalent O2- atoms. Both Fe–O bond lengths are 1.42 Å. O2- is bonded in a distorted linear geometry to one Li1+ and one Fe3+ atom. In the LiNiO2 ribbon, Li1+ is bonded in a linear geometry to two equivalent O2- atoms. Both Li–O bond lengths are 1.58 Å. Ni3+ is bonded in a linear geometry to two equivalent O2- atoms. Both Ni–O bond lengths are 1.43 Å. O2- is bonded in a distorted linear geometry to one Li1+ and one Ni3+ atom.
High-nickel layered oxides are enabling extraordinary growth of electric vehicles market due to its high energy density. Nonetheless, leading battery manufacturers are trying to cut down the manufacturing costs further by eliminating the dependency on cobalt in cathode materials. In this perspective, we explore several aspects that need to be considered to develop cobalt-free high-Ni layered oxides by reviewing the fundamental properties of LiNiO2. Furthermore, critical key factors for exploring alternative dopants and substituents are discussed for designing stable and inexpensive Co-free high-Ni layered oxides from a viewpoint of materials science and electrochemistry. Lastly, a perspective on the future research direction on Co-free high-Ni layered oxides are highlighted with respect to practical considerations.
Abstract In pursuit of the highest possible energy density, researchers shift their focus to the ultimate anode material, lithium metal (Li 0 ), and high‐capacity cathode materials with high nickel content (Ni > 80%). The combination of these aggressive electrodes presents unprecedented challenges to the electrolyte. Here, we report a hybrid electrolyte consisting of a highly fluorinated ionic liquid and a weakly solvating fluorinated ether, whose hybridization structure enables the reversible operation of a battery chemistry based on Li 0 and LiNiO 2 (Ni = 100%), delivering nearly theoretical capacity of the latter (up to 249 mAh g −1 ) for >300 cycles with retention of 78.6% and in absence of unwanted morphological changes in both electrodes. Extensive characterization assisted by molecular dynamic simulation and density functional theory calculations reveals the function of the fluorinated ether to be far more profound than simple dilution and viscosity reduction. Instead, it induces drastic changes in Li + ‐solvation environment, the consequence of which engenders simultaneous stabilization of electrode/electrolyte and interfacing via formation of respective interfacial chemistries. This study further unlocks fundamental knowledge underneath the prevailing “diluent strategy” that is extensively applied by the electrolyte researchers and opens more design space for the next‐generation electrolytes and interphases for these coveted battery chemistries.
Electrolytes play a critical role in stabilizing highly reactive lithium-metal anodes (LMAs) and high-voltage cathodes for rechargeable lithium-metal batteries (LMBs). Localized high concentration electrolytes (LHCEs) have achieved remarkable success in the context of LMBs. However, the state-of-the-art LHCEs are based on LiFSI salt, which is prohibitively expensive. Here, the utility of low-cost LiPF 6 salt in localized saturated electrolytes (LSEs) with a series of solvents and diluents in LMBs with cobalt-free LiNiO 2 cathode is systematically explored. Experimental and theoretical analyses reveal that the unique solvation structure formed not only changes the distribution of solvents and anions but also alters the atom–atom distances within them, leading to different reduction and oxidation stabilities compared to low-concentration electrolytes. In addition, LSEs help form LiF-rich interphase layers on the LMA and LiNiO 2 cathode, protecting the electrodes from degradation during cycling. Different LSEs also lead to differences in lithium plating morphology and impedance buildup during cycling, impacting the performance of LMBs. Finally, the solvent and diluent must be carefully selected for compatibility with a lithium salt when developing LHCEs and LSEs for LMBs.
LiNiO 2 and cobalt-free ultrahigh-Ni content cathodes suffer from rapid capacity loss and severe chemomechanical degradation, especially when operated at high voltages. Here, by cycling LiNiO 2 up to 4.7 V, we report the atomic-scale observation of O1 faulted phase-induced deactivation of LiNiO 2 . We found that although a thin layer of O3 phase forms on the particle surface by reversible O3 → O1 transformation during discharge, the bulk interior still maintains the O1 faulted phase, leading to rapid capacity loss of LiNiO 2 . Moreover, the atomic configuration of the O1/O3 interface is investigated comprehensively. We found that the misfit along the c axes of the O1 and O3 phases results in the formation of misfit dislocations, whereby cation mixing is promoted at dislocation cores. Further, a transition zone with continuous shear along the a-b plane is uncovered between the O1 and O3 phases for the first time. Besides, severe oxygen loss-induced pore formation and concurrent rock salt transformation are also identified.
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