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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., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

A novel LiMn 0.5 Ni 0.5 O 2 cathode with a predominant, partially-disordered lithiated-spinel structure has been prepared by a 'low temperature' (LT) synthesis. Li/LT-LiMn 0.5 Ni 0.5 O 2 cells operate between 5.0 and 2.5 V with good cycling stability, yielding a capacity of 225 mA h g -1 , principally by redox reactions on the nickel ions on distinct voltage plateaus at ∼3.6 V and ∼4.6 V.

The composition, structure and phase transformations occurring on cathode surfaces greatly affect the performance of Li-ion batteries. Li-Ion diffusion and surface-electrolyte interaction are two major phenomena that impact the capacity and cell impedance. The effects of surface reconstruction (SR) of cathode materials on the performance of Li-ion batteries are of current interest. However, the origin and evolution of the SR are still not well understood. In this work, density functional theory (DFT) calculations are used to investigate the processes taking place during surface segregation and reconstruction. Facet dependent segregation was found in Li(Ni 1-x-y Mn x Co y )O 2 (NMC) cathodes. Specifically, Co tends to segregate to the (104) surface of the primary particles within the transition metal layer, while Ni ions tend to segregate to the (012) surface in the Li layer, forming a SR. Experimental evidence shows the SR to be epitaxial with the bulk of the as-synthesized material, and the new SR phase is pinned to the NMC unit cell leading to a strained SR. Here, we show that strain can stabilize a spinel structure of the SR layers. Understanding the effects of surface strain opens a new avenue for the design of cathode materials with enhanced surface properties.

Embedding a lithiated cobalt oxide spinel (Li 2 Co 2 O 4 , or LiCoO 2 ) component or a nickel-substituted LiCo 1- x Ni x O 2 analogue in structurally integrated cathodes such as xLi 2 MnO 3 ·(1- x)LiM'O 2 (M' = Ni/Co/Mn) has been recently proposed as an approach to advance the performance of lithium-ion batteries. Here, we first revisit the phase stability and electrochemical performance of LiCoO 2 synthesized at different temperatures using density functional theory calculations. Consistent with previous studies, we find that the occurrence of low- and high-temperature structures (i.e., cubic lithiated spinel LT-LiCoO 2 ; or Li 2 Co 2 O 4 ( Fd3̅ m) vs trigonal-layered HT-LiCoO 2 ( R3̅ m), respectively) can be explained by a small difference in the free energy between these two compounds. Additionally, the observed voltage profile of a Li/LiCoO 2 cell for both cubic and trigonal phases of LiCoO 2 , as well as the migration barrier for lithium diffusion from an octahedral (O h ) site to a tetrahedral site (T d ) in Fd3̅ m LT-Li 1- x CoO 2 , has been calculated to help understand the complex electrochemical charge/discharge processes. A search of LiCo x M 1- x O 2 lithiated spinel (M = Ni or Mn) structures and compositions is conducted to extend the exploration of the chemical space of Li-Co-Mn-Ni-O electrode materials. We predict a new lithiated spinel material, LiNi 0.8125 Co 0.1875 O 2 ( Fd3̅ m), with a composition close to that of commercial, layered LiNi 0.8 Co 0.15 Al 0.05 O 2 , which may have the potential for exploitation in structurally integrated, layered spinel cathodes for next-generation lithium-ion batteries.

Atomic layer deposition (ALD) of the well-known Al 2 O 3 on a LiCoO 2 system is compared with that of a newly developed AlW x F y material. ALD coatings (∼1 nm thick) of both materials are shown to be effective in improving cycle life through mitigation of surface-induced capacity losses. However, the behaviors of Al 2 O 3 and AlW x F y are shown to be significantly different when coated directly on cathode particles versus deposition on a composite electrode composed of active materials, carbons, and binders. Electrochemical impedance spectroscopy, galvanostatic intermittent titration techniques, and four-point measurements suggest that electron transport is more limited in LiCoO 2 particles coated with Al 2 O 3 compared with that in particles coated with AlW x F y . The results show that proper design/choice of coating materials (e.g., AlW x F y ) can improve capacity retention without sacrificing electron transport and suggest new avenues for engineering electrode-electrolyte interfaces to enable high-voltage operation of lithium-ion batteries., Competing Interests: The authors declare no competing financial interest.

Recent reports have indicated that a manganese oxide spinel component, when embedded in a relatively small concentration in layered xLi 2 MnO 3 ·(1-x)LiMO 2 (M = Ni, Mn, or Co) electrode systems, can act as a stabilizer that increases their capacity, rate capability, cycle life, and first-cycle efficiency. These findings prompted us to explore the possibility of exploiting lithiated cobalt oxide spinel stabilizers by taking advantage of (1) the low mobility of cobalt ions relative to that of manganese and nickel ions in close-packed oxides and (2) their higher potential (∼3.6 V vs Li 0 ) relative to manganese oxide spinels (∼2.9 V vs Li 0 ) for the spinel-to-lithiated spinel electrochemical reaction. In particular, we revisited the structural and electrochemical properties of lithiated spinels in the LiCo 1-x Ni x O 2 (0 ≤ x ≤ 0.2) system, first reported almost 25 years ago, by means of high-resolution (synchrotron) X-ray diffraction, transmission electron microscopy, nuclear magnetic resonance spectroscopy, electrochemical cell tests, and theoretical calculations. The results provide a deeper understanding of the complexity of intergrown layered/lithiated spinel LiCo 1-x Ni x O 2 structures when prepared in air between 400 and 800 °C and the impact of structural variations on their electrochemical behavior. These structures, when used in low concentrations, offer the possibility of improving the cycling stability, energy, and power of high energy (≥3.5 V) lithium-ion cells.

The commercial introduction of the lithium-ion (Li-ion) battery nearly 25 years ago marked a technological turning point. Portable electronics, dependent on energy storage devices, have permeated our world and profoundly affected our daily lives in a way that cannot be understated. Now, at a time when societies and governments alike are acutely aware of the need for advanced energy solutions, the Li-ion battery may again change the way we do business. With roughly two-thirds of daily oil consumption in the United States allotted for transportation, the possibility of efficient and affordable electric vehicles suggests a way to substantially alleviate the Country's dependence on oil and mitigate the rise of greenhouse gases. Although commercialized Li-ion batteries do not currently meet the stringent demands of a would-be, economically competitive, electrified vehicle fleet, significant efforts are being focused on promising new materials for the next generation of Li-ion batteries. The leading class of materials most suitable for the challenge is the Li- and manganese-rich class of oxides. Denoted as LMR-NMC (Li-manganese-rich, nickel, manganese, cobalt), these materials could significantly improve energy densities, cost, and safety, relative to state-of-the-art Ni- and Co-rich Li-ion cells, if successfully developed.1 The success or failure of such a development relies heavily on understanding two defining characteristics of LMR-NMC cathodes. The first is a mechanism whereby the average voltage of cells continuously decreases with each successive charge and discharge cycle. This phenomenon, known as voltage fade, decreases the energy output of cells to unacceptable levels too early in cycling. The second characteristic is a pronounced hysteresis, or voltage difference, between charge and discharge cycles. The hysteresis represents not only an energy inefficiency (i.e., energy in vs energy out) but may also complicate the state of charge/depth of discharge management of larger systems, especially when accompanied by voltage fade. In 2012, the United States Department of Energy's Office of Vehicle Technologies, well aware of the inherent potential of LMR-NMC materials for improving the energy density of automotive energy storage systems, tasked a team of scientists across the National Laboratory Complex to investigate the phenomenon of voltage fade. Unique studies using synchrotron X-ray absorption (XAS) and high-resolution diffraction (HR-XRD) were coupled with nuclear magnetic resonance spectroscopy (NMR), neutron diffraction, high-resolution transmission electron microscopy (HR-TEM), first-principles calculations, molecular dynamics simulations, and detailed electrochemical analyses. These studies demonstrated for the first time the atomic-scale, structure-property relationships that exist between nanoscale inhomogeneities and defects, and the macroscale, electrochemical performance of these layered oxides. These inhomogeneities and defects have been directly correlated with voltage fade and hysteresis, and a model describing these mechanisms has been proposed. This Account gives a brief summary of the findings of this recently concluded, approximately three-year investigation. The interested reader is directed to the extensive body of work cited in the given references for a more comprehensive review of the subject.

Li- and Mn-rich layered oxides with composition xLi2MnO3·(1 -x)LiMO2 enable high capacity and energy density Li-ion batteries, but suffer from degradation with cycling. Evidence of atomic instabilities during the first charge are addressed in this work with X-ray absorption spectroscopy, first principles simulation at the GGA+U level, and existing literature. The pristine material of composition xLi2MnO3·(1 -x)LiMn0.5Ni0.5O2 is assumed in the simulations to have the form of LiMn2 stripes, alternating with NiMn stripes, in the metal layers. The charged state is simulated by removing Li from the Li layer, relaxing the resultant system by steepest descents, then allowing the structure to evolve by molecular dynamics at 1000 K, and finally relaxing the evolved system by steepest descents. The simulations show that about ¼ of the oxygen ions in the Li2MnO3 domains are displaced from their original lattice sites, and form oxygen-oxygen bonds, which significantly lowers the energy, relative to that of the starting structure in which the oxygen sublattice is intact. An important consequence of the displacement of the oxygen is that it enables about ⅓ of the (Li2MnO3 domain) Mn ions to migrate to the delithiated Li layers. The decrease in the coordination of the Mn ions is about twice that of the Ni ions. The approximate agreement of simulated coordination number deficits for Mn and Ni following the first charge with analysis of EXAFS measurements on 0.3Li2MnO3·0.7LiMn0.5Ni0.5O2 suggests that the simulation captures significant features of the real material.

Direct observations of structure-electrochemical activity relationships continue to be a key challenge in secondary battery research. (6)Li magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy is the only structural probe currently available that can quantitatively characterize local lithium environments on the subnanometer scale that dominates the free energy for site occupation in lithium-ion (Li-ion) intercalation materials. In the present study, we use this local probe to gain new insights into the complex electrochemical behavior of activated 0.5(6)Li2MnO3·0.5(6)LiMn(0.5)Ni(0.5)O2, lithium- and manganese-rich transition-metal (TM) oxide intercalation electrodes. We show direct evidence of path-dependent lithium site occupation, correlated to structural reorganization of the metal oxide and the electrochemical hysteresis, during lithium insertion and extraction. We report new (6)Li resonances centered at ∼1600 ppm that are assigned to LiMn6-TM(tet) sites, specifically, a hyperfine shift related to a small fraction of re-entrant tetrahedral TMs (Mn(tet)), located above or below lithium layers, coordinated to LiMn6 units. The intensity of the TM layer lithium sites correlated with tetrahedral TMs loses intensity after cycling, indicating limited reversibility of TM migrations upon cycling. These findings reveal that defect sites, even in dilute concentrations, can have a profound effect on the overall electrochemical behavior.

It is well known that Li-ion cells containing manganese oxide-based positive electrodes and graphite-based negative electrodes suffer accelerated capacity fade, which has been attributed to the deposition of dissolved manganese on the graphite electrodes during electrochemical cell cycling. However, the reasons for the accelerated capacity fade are still unclear. This stems, in part, from conflicting reports of the oxidation state of the manganese species in the negative electrode. In this communication, the oxidation state of manganese deposited on graphite electrodes has been probed by X-ray absorption near edge spectroscopy (XANES). The XANES features confirm, unequivocally, the presence of fully reduced manganese (Mn(0)) on the surface of graphite particles. The deposition of Mn(0) on the graphite negative electrode acts as a starting point to understand the consequent electrochemical behavior of these electrodes; possible reasons for the degradation of cell performance are proposed and discussed.

Tailoring the chemical reactivity of nanomaterials at the atomic level is one of the most important challenges in catalysis research. In order to achieve this elusive goal, fundamental understanding of the geometric and electronic structure of these complex systems at the atomic level must be obtained. This article reports the influence of the nanoparticle shape on the reactivity of Pt nanocatalysts supported on γ-Al(2)O(3). Nanoparticles with analogous average size distributions (∼0.8-1 nm), but with different shapes, synthesized by inverse micelle encapsulation, were found to display distinct reactivities for the oxidation of 2-propanol. A correlation between the number of undercoordinated atoms at the nanoparticle surface and the onset temperature for 2-propanol oxidation was observed, demonstrating that catalytic properties can be controlled through shape-selective synthesis.

The structure, size, and shape of gamma-Al(2)O(3)-supported Pt nanoparticles (NPs) synthesized by inverse micelle encapsulation have been resolved via a synergistic combination of imaging and spectroscopic tools. It is shown that this synthesis method leads to 3D NP shapes even for subnanometer clusters, in contrast to the raft-like structures obtained for the same systems via traditional deposition-precipitation methods. Furthermore, a high degree of atomic ordering is observed for the micellar NPs in H(2) atmosphere at all sizes studied, possibly due to H-induced surface reconstruction in these high surface area clusters. Our findings demonstrate that the influence of NP/support interactions on NP structure can be diminished in favor of NP/adsorbate interactions when NP catalysts are prepared by micelle encapsulation methods.