Design Strategies of Spinel Oxide Frameworks Enabling Reversible Mg-Ion Intercalation.

ConspectusReversible Mg2+ intercalation in metal oxide frameworks is a key enabler for an operational Mg-ion battery with high energy density needed for the next generation of energy storage technologies. While functional Mg-ion batteries have been achieved in structures with soft anions (e.g., S2- and Se2-), they do not meet energy density requirements to compete with the current rechargeable lithium-ion batteries due to their low insertion potentials. It emphasizes the necessity of finding an oxide-based cathode that operates at high potentials. A leading hypothesis to explain the limited availability of oxide Mg-ion cathodes is the belief that Mg2+ has sluggish diffusion kinetics in oxides due to strong electrostatic interactions between the Mg2+ ions and oxide anions in the lattice. From this assessment, it can be hypothesized that such rate limiting kinetic shortcomings can be mitigated by tailoring an oxide framework through creating less stable Mg2+-O2- coordination.Based on theoretical calculations and preliminary experimental data, oxide spinels have been identified as promising cathode candidates with storage capacity, insertion potential, and cation mobility that meet the requirements for a secondary Mg-ion battery. However, spinels with a single redox metal, such as MgCr2O4 or MgMn2O4, were not found to demonstrate sufficiently reversible Mg-ion intercalation at high redox potentials when coupled with nonaqueous Mg-electrolytes. Therefore, a materials development effort was initiated to design, synthesize, and evaluate a new class of solid-solution oxide spinels that can satisfy the required properties needed to create a sustainable Mg-ion cathode. These were designed by bringing together electrochemically active metals with stable redox potentials and charged states against the electrolyte, for instance, Mn3+, in combination with a structural stabilization component, typically Cr3+. Furthermore, common spinel structural defects that degrade performance, i.e., antisite inversion, were controlled to see correlation between structures and electrochemical overpotentials, thus controlling overall hysteresis. The designed materials were characterized by both short- and long-range structure in both ex situ and in situ modes to confirm the nature of solid-solution and to correlate structural changes and redox activity to electrochemical performance. Consistent and reproducible results were observed for facile bulk Mg2+-ion activity without phase transformations, leading to enhanced energy storage capability based on reversible intercalation of Mg2+, enabled by understanding the variables that control the electrochemical performance of the spinel oxide. Based on these observations, with proper materials design, it is possible to develop an oxide cathode material that has many of the desired properties of a Li-ion intercalation cathode, representing a significant mile marker in the quest for high energy density Mg-ion batteries.This Account describes strategies for the design and development of new spinel oxide intercalation materials for high-energy Mg-ion battery cathodes through a combination of theoretical and experimental approaches. We will review the key factors that govern the kinetics of Mg2+ diffusion in spinel oxides and illustrate how material complexity correlates with the electrochemical Mg2+ activity in oxides and is supported by secondary characterization. The understanding gained from the fundamental studies of cation diffusion in oxide cathodes will be beneficial for chemists and materials scientists who are developing rechargeable batteries.

Monitoring Structural Changes during Electrochemical Cycling of Solid-Solution Spinel Oxide MgCrVO4.

Rechargeable magnesium-ion batteries (MIBs) hold significant promise as an alternative to conventional lithium-ion technology driven by their natural abundance and low-cost, high-energy density, and safety features. Spinel oxides, including MgCrVO4, have emerged as a prospective cathode material for MIBs due to their promising combination of capacity, operating potential, and cation mobility. However, the structural evolution, phase stability, and processes of Mg mobility in MgCrVO4 during electrochemical cycling are poorly understood. In this study, we synthesized a single-phase, solid solution of spinel oxide MgCrVO4 and employed operando X-ray diffraction to couple physical properties with structural changes during cycling. Our results revealed a two-phase reaction mechanism coupled with a solid-solution-like reaction, highlighting the complicated transformation between two distinct phases in the MgCrVO4 lattice during Mg (de)intercalation. Rietveld refinement of the operando data provided valuable insights into the mechanism of the Cr/V-based spinel oxide, shedding light on the transition between the two phases and their roles in Mg-ion (de)intercalation. This study contributes to a deeper understanding of the structural dynamics in multivalent cathode materials and sets the stage for the development of advanced Mg-ion cathodes with enhanced performance and stability.

Operando X-ray Diffraction Studies of the Mg-Ion Migration Mechanisms in Spinel Cathodes for Rechargeable Mg-Ion Batteries.

A promising high-voltage spinel oxide cathode material MgCrMnO4 with 18% Mg/Mn inversion was synthesized successfully. A new custom operando battery device was designed to study the cation migration mechanisms of the MgCrMnO4 cathode using 0.1 M Mg(TPFA)2 electrolyte dissolved in triglyme and activated carbon as the anode. For the first time in multivalent batteries, high-quality operando diffraction data enabled the accurate quantification of cation contents in the host structure. Besides the exceptional reversibility of 12% Mg2+ insertion in Mg1-xCrMnO4 (x ≤ 1), a partially reversible insertion of excess Mg2+ during overdischarging was also observed. Moreover, the insertion/extraction reaction was experimentally shown to be accompanied by a series of cation redistributions in the spinel framework, which were further supported by density functional theory calculations. The inverted Mn is believed to be directly involved in the cation migrations, which would cause voltage hysteresis and irreversible structural evolution after overdischarging. Tuning the Mg/Mn inversion rate could provide a direct path to further optimize spinel oxide cathodes for Mg-ion batteries, and more generally, the operando techniques developed in this work should play a key role in understanding the complex mechanisms involved in multivalent ion insertion systems.

Cation Additive Enabled Rechargeable LiOH-Based Lithium-Oxygen Batteries.

Lithium-oxygen (Li-O2 ) batteries have attracted extensive research interest due to their high energy density. Other than Li2 O2 (a typical discharge product in Li-O2 batteries), LiOH has proved to be electrochemically active as an alternative product. Here we report a simple strategy to achieve a reversible LiOH-based Li-O2 battery by using a cation additive, sodium ions, to the lithium electrolyte. Without redox mediators in the cell, LiOH is detected as the sole discharge product and it charges at a low charge potential of 3.4 V. A solution-based reaction route is proposed, showing that the competing solvation environment of the catalyst and Li+ leads to LiOH precipitation at the cathode. It is critical to tune the cell chemistry of Li-O2 batteries by designing a simple system to promote LiOH formation/decomposition.

Synthesis and Characterization of MgCr2S4 Thiospinel as a Potential Magnesium Cathode.

Magnesium-ion batteries are a promising energy storage technology because of their higher theoretical energy density and lower cost of raw materials. Among the major challenges has been the identification of cathode materials that demonstrate capacities and voltages similar to lithium-ion systems. Thiospinels represent an attractive choice for new Mg-ion cathode materials owing to their interconnected diffusion pathways and demonstrated high cation mobility in numerous systems. Reported magnesium thiospinels, however, contain redox inactive metals such as scandium or indium, or have low voltages, such as MgTi2S4. This article describes the direct synthesis and structural and electrochemical characterization of MgCr2S4, a new thiospinel containing the redox active metal chromium and discusses its physical properties and potential as a magnesium battery cathode. However, as chromium(III) is quite stable against oxidation in sulfides, removing magnesium from the material remains a significant challenge. Early attempts at both chemical and electrochemical demagnesiation are discussed.

Re-entrant lithium local environments and defect driven electrochemistry of Li- and Mn-rich Li-ion battery cathodes.

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.

Surface and Bulk Stabilization of Silicon Anodes with Mixed-Multivalent Additives: Ca(TFSI)2 and Mg(TFSI)2.

Silicon is drawing attention as an emerging anode material for the next generation of lithium-ion batteries due to its higher capacity compared with commercial graphite. However, silicon anions formed during lithiation are highly reactive with binder and electrolyte components, creating an unstable SEI layer and limiting the calendar life of silicon anodes. The reactivity of lithium silicide and the formation of an unstable SEI layer are mitigated by utilizing a mixture of Ca and Mg multivalent cations as an electrolyte additive for Si anodes to improve their calendar life. The effect of mixed salts on the bulk and surface of the silicon anodes was studied by multiple structural characterization techniques. Ca and Mg ions in the electrolyte formed relatively thermodynamically stable quaternary Li-Ca-Mg-Si Zintl phases in an in situ fashion and a more stable and denser SEI layer on the Si particles. These in turn protect silicon particles against side reactions with electrolytes in a coin cell. The full cell with the mixed cation electrolyte demonstrates enhanced calendar life performance with lower measured current and current leakage in comparison to that of the baseline electrolyte due to reduced side reactions. Electron microscopy, HR-XRD, and solid-state NMR results showed that electrodes with mixed cations tended to have less cracking on the electrode surface, and the presence of mixed cations enhances cation migration and formation of quaternary Zintl phases stabilizing the bulk and forming a more stable SEI in comparison to baseline electrolyte and electrolyte with single multivalent cations.

Mixed-Anion Contact Ion-Pair Formation Enabling Improved Performance of Halide-Free Mg-Ion Electrolytes.

Discovery of stable and efficient electrolytes that are compatible with magnesium metal anodes and high-voltage cathodes is crucial to enabling energy storage technologies that can move beyond existing Li-ion systems. Many promising electrolytes for magnesium anodes have been proposed with chloride-based systems at the forefront; however, Cl-containing electrolytes lack the oxidative stability required by high-voltage cathodes. In this work, we report magnesium trifluoromethanesulfonate (triflate) as a viable coanion for Cl-free, mixed-anion magnesium electrolytes. The addition of triflate to electrolytes containing bis(trifluoromethane sulfonyl) imide (TFSI-) anions yields significantly improved Coulombic efficiency, up to a 100 mV decrease in the plating/stripping overpotential, improved tolerance to trace H2O, and improved oxidative stability (0.35 V improvement compared to that of hybrid TFSI-Cl electrolytes). Based on 19F nuclear magnetic resonance and Raman spectroscopy measurements, we propose that these improvements in performance are driven by the formation of mixed-anion contact ion pairs, where both triflate and TFSI- are coordinated to Mg2+ in the electrolyte bulk. The formation of this mixed-anion magnesium complex is further predicted by the density functional theory to be thermodynamically driven. Collectively, this work outlines the guiding principles for the improved design of next-generation electrolytes for magnesium batteries.

Synthesis, structural and electrochemical properties of V4O9 cathode for lithium batteries.

Single-phase three-dimensional vanadium oxide (V4O9) was synthesized by reduction of V2O5 using a gas stream of ammonia/argon (NH3/Ar). The as-synthesized oxide, prepared by this simple gas reduction method was subsequently electrochemically transformed into a disordered rock salt type-"Li3.7V4O9" phase while cycling over the voltage window 3.5 to 1.8 V versus Li. The Li-deficient phase delivers an initial reversible capacity of ∼260 mAhg-1 at an average voltage of 2.5 V vs. Li+/Li0. Further cycling to 50 cycles yields a steady 225 mAhg-1. Ex situ X-ray diffraction studies confirmed that (de) intercalation phenomena follows a solid-solution electrochemical reaction mechanism. As demonstrated, the reversibility and capacity utilization of this V4O9 is found to be superior to battery grade, micron-sized V2O5 cathodes in lithium cells.

Quantitative Analysis of Origin of Lithium Inventory Loss and Interface Evolution over Extended Fast Charge Aging in Li Ion Batteries.

During the extreme fast charging (XFC) of lithium-ion batteries, lithium inventory loss (LLI) and reaction mechanisms at the anode/electrolyte interface are crucial factors in performance and safety. Determining the causes of LLI and quantifying them remain an essential challenge. We present mechanistic research on the evolution and interactions of aging mechanisms at the anode/electrolyte interface. We used NMC532/graphite pouch cells charged at rates of 1, 6, and 9 C up to 1000 cycles for our investigation. The cell components were characterized after cycling using electrochemical measurements, inductively coupled plasma optical emission spectroscopy, 7Li solid-state nuclear magnetic resonance spectroscopy, and high-performance liquid chromatography/mass spectrometry. The results indicate that cells charged at 1 C exhibit no Li plating, and the increase of SEI thickness is the dominant source of the Li loss. In contrast, Li loss in cells charged at 9 C is related to the formation of the metallic plating layers (42%) the SEI layer (38.1%) and irreversible intercalation into the bulk graphite (19%). XPS analysis suggests that the charging rate has little influence on the evolution of SEI composition. The interactions between competing aging mechanisms were evaluated by a correlation analysis. The quantitative method established in this work provides a comprehensive analytical framework for understanding the synergistic coupling of anodic degradation mechanisms, forecasting SEI failure scenarios, and assessing the XFC lithium-ion battery capacity fade.

Functionalized Silicon Particles for Enhanced Half- and Full-Cell Cycling of Si-Based Li-Ion Batteries.

Vinylene carbonate (VC) and polyethylene oxide (PEO) have been investigated as functional agents that mimic the solid electrolyte interphase (SEI) chemistry of silicon (Si). VC and PEO are known to contribute to the stability of Si-based lithium-ion batteries as an electrolyte additive and as a SEI component, respectively. In this work, covalent surface functionalization was achieved via a facile route, which involves ball-milling the Si particles with sacrificial VC and PEO. Thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy indicate that the additives are strongly bound to Si. In particular, MAS NMR shows Si-R or Si-O-R groups, which confirm functionalization of the Si after milling in VC or PEO. Particle size analysis by dynamic light scattering reveals that the additives facilitate particle size reduction and that the functionalized particles result in more stable dispersions based on zeta potential measurements. Raman mapping of the electrodes fabricated from the VC and PEO-coated active material with a polyacrylic acid (PAA) binder reveals a more homogenous distribution of Si and the carbon conductive additive compared to the electrodes prepared from the neat Si. Furthermore, the VC-milled Si strikingly exhibited the highest capacity in both half- and full-cell configurations, with more than 200 mAh g-1 measured capacity compared to the neat Si in the half-cell format. This is linked to an improved electrode processing based on the Raman and zeta potential measurements as well as a thinner SEI (with more organic components for the functionalized Si relative to the neat Si) based on XPS analysis of the cycled electrodes. The effect of binder was also investigated by comparing PAA with P84 (polyimide type), where an increased capacity is observed in the latter case.

Pair distribution function analysis and solid state NMR studies of silicon electrodes for lithium ion batteries: understanding the (de)lithiation mechanisms.

Lithium ion batteries (LIBs) containing silicon negative electrodes have been the subject of much recent investigation, because of the extremely large gravimetric and volumetric capacities of silicon. The crystalline-to-amorphous phase transition that occurs on electrochemical Li insertion into crystalline Si, during the first discharge, hinders attempts to link the structure in these systems with electrochemical performance. We apply a combination of local structure probes, ex situ (7)Li nuclear magnetic resonance (NMR) studies, and pair distribution function (PDF) analysis of X-ray data to investigate the changes in short-range order that occur during the initial charge and discharge cycles. The distinct electrochemical profiles observed subsequent to the first discharge have been shown to be associated with the formation of distinct amorphous lithiated silicide structures. For example, the first process seen on the second discharge is associated with the lithiation of the amorphous Si, forming small clusters. These clusters are broken in the second process to form isolated silicon anions. The (de)lithiation model helps explain the hysteresis and the steps in the electrochemical profile observed during the lithiation and delithiation of silicon.

Conversion reaction mechanisms in lithium ion batteries: study of the binary metal fluoride electrodes.

Materials that undergo a conversion reaction with lithium (e.g., metal fluorides MF(2): M = Fe, Cu, ...) often accommodate more than one Li atom per transition-metal cation, and are promising candidates for high-capacity cathodes for lithium ion batteries. However, little is known about the mechanisms involved in the conversion process, the origins of the large polarization during electrochemical cycling, and why some materials are reversible (e.g., FeF(2)) while others are not (e.g., CuF(2)). In this study, we investigated the conversion reaction of binary metal fluorides, FeF(2) and CuF(2), using a series of local and bulk probes to better understand the mechanisms underlying their contrasting electrochemical behavior. X-ray pair-distribution-function and magnetization measurements were used to determine changes in short-range ordering, particle size and microstructure, while high-resolution transmission electron microscopy (TEM) and electron energy-loss spectroscopy (EELS) were used to measure the atomic-level structure of individual particles and map the phase distribution in the initial and fully lithiated electrodes. Both FeF(2) and CuF(2) react with lithium via a direct conversion process with no intercalation step, but there are differences in the conversion process and final phase distribution. During the reaction of Li(+) with FeF(2), small metallic iron nanoparticles (<5 nm in diameter) nucleate in close proximity to the converted LiF phase, as a result of the low diffusivity of iron. The iron nanoparticles are interconnected and form a bicontinuous network, which provides a pathway for local electron transport through the insulating LiF phase. In addition, the massive interface formed between nanoscale solid phases provides a pathway for ionic transport during the conversion process. These results offer the first experimental evidence explaining the origins of the high lithium reversibility in FeF(2). In contrast to FeF(2), no continuous Cu network was observed in the lithiated CuF(2); rather, the converted Cu segregates to large particles (5-12 nm in diameter) during the first discharge, which may be partially responsible for the lack of reversibility in the CuF(2) electrode.

In situ NMR observation of the formation of metallic lithium microstructures in lithium batteries.

Lithium metal has the highest volumetric and gravimetric energy density of all negative-electrode materials when used as an electrode material in a lithium rechargeable battery. However, the formation of lithium dendrites and/or 'moss' on the metal electrode surface can lead to short circuits following several electrochemical charge-discharge cycles, particularly at high rates, rendering this class of batteries potentially unsafe and unusable owing to the risk of fire and explosion. Many recent investigations have focused on the development of methods to prevent moss/dendrite formation. In parallel, it is important to quantify Li-moss formation, to identify the conditions under which it forms. Although optical and electron microscopy can visually monitor the morphology of the lithium-electrode surface and hence the moss formation, such methods are not well suited for quantitative studies. Here we report the use of in situ NMR spectroscopy, to provide time-resolved, quantitative information about the nature of the metallic lithium deposited on lithium-metal electrodes.

Resolving the different silicon clusters in Li12Si7 by 29Si and (6,7)Li solid-state NMR spectroscopy.

Structural signatures: The analysis of Si-Si and Si-Li connectivities by solid-state NMR spectroscopy allows the different types of silicon clusters to be discriminated in the model lithium silicide compound Li(12)Si(7) (see picture, Si clusters red and blue, Li ions gray). The results provide new NMR spectroscopic strategies with which to differentiate and study the structures formed in silicon-based electrode materials.

Probing the Reactivity of the Active Material of a Li-Ion Silicon Anode with Common Battery Solvents.

Calculations and modeling have shown that replacing the traditional graphite anode with silicon can greatly improve the energy density of lithium-ion batteries. However, the large volume change of silicon particles and high reactivity of lithiated silicon when in contact with the electrolyte lead to rapid capacity fading during charging/discharging processes. In this report, we use specific lithium silicides (LS) as model compounds to systematically study the reaction between lithiated Si and different electrolyte solvents, which provides a powerful platform to deconvolute and evaluate the degradation of various organic solvents in contact with the active lithiated Si-electrode surface after lithiation. Nuclear Magnetic Resonance (NMR) characterization results show that a cyclic carbonate such as ethylene carbonate is chemically less stable than a linear carbonate such as ethylmethyl carbonate, fluoroethylene carbonate, and triglyme as they are found to be more stable when mixed with LS model compounds. Guided by the experimental results, two ethylene carbonate (EC)-free electrolytes are studied, and the electrochemical results show improvements with graphite-free Si electrodes relative to the traditional ethylene-carbonate-based electrolytes. More importantly, the study contributes to our understanding of the significant fundamental chemical and electrochemical stability differences between silicon and traditional graphite lithium-ion battery (LIB) anodes and suggests a focused development of electrolytes with specific chemical stability vs lithiated silicon which can passivate the surface more effectively.

Identifying the local structures formed during lithiation of the conversion material, iron fluoride, in a Li ion battery: a solid-state NMR, X-ray diffraction, and pair distribution function analysis study.

The structural transformations that occur when FeF(3) is cycled at room temperature in a Li cell were investigated using a combination of X-ray diffraction (XRD), pair distribution function (PDF) analysis, and magic-angle-spinning NMR spectroscopy. Two regions are seen on discharge. The first occurs between Li = 0 and 1.0 and involves an insertion reaction. This first region actually comprises two steps: First, a two-phase reaction between Li = 0 and 0.5 occurs, and the Li(0.5)FeF(3) phase that is formed gives rise to a Li NMR resonance due to Li(+) ions near both Fe(3+) and Fe(2+) ions. On the basis of the PDF data, the local structure of this phase is closer to the rutile structure than the original ReO(3) structure. Second, a single-phase intercalation reaction occurs between Li = 0.5 and 1.0, for which the Li NMR data indicate a progressive increase in the concentration of Fe(2+) ions. In the second region, the conversion reaction, superparamagnetic, nanosized ( approximately 3 nm) Fe metal is formed, as indicated by the XRD and NMR data, along with some LiF and a third phase that is rich in Li and F. The charge process involves the formation of a series of intercalation phases with increasing Fe oxidation state, which, on the basis of the Li NMR and PDF data, have local structures that are similar to the intercalation phases seen during the first stage of the discharge process. The solid-state NMR and XRD results for the rutile phase FeF(2) are presented for comparison, and the data indicate that an insertion reaction also occurs, which is accompanied by the formation of LiF. This is followed by the formation of Fe nanoparticles and LiF via a conversion reaction.

Real-time NMR investigations of structural changes in silicon electrodes for lithium-ion batteries.

Lithium-ion batteries (LIBs) containing silicon negative electrodes have been the subject of much recent investigation because of the extremely large gravimetric and volumetric capacity of silicon. The crystalline-to-amorphous phase transition that occurs on electrochemical Li insertion into crystalline Si, during the first discharge, hinders attempts to link structure in these systems with electrochemical performance. We apply a combination of static, in situ and magic angle sample spinning, ex situ (7)Li nuclear magnetic resonance (NMR) studies to investigate the changes in local structure that occur in an actual working LIB. The first discharge occurs via the formation of isolated Si atoms and smaller Si-Si clusters embedded in a Li matrix; the latter are broken apart at the end of the discharge, forming isolated Si atoms. A spontaneous reaction of the lithium silicide with the electrolyte is directly observed in the in situ NMR experiments; this mechanism results in self-discharge and potential capacity loss. The rate of this self-discharge process is much slower when CMC (carboxymethylcellulose) is used as the binder.

Using Mixed Salt Electrolytes to Stabilize Silicon Anodes for Lithium-Ion Batteries via in Situ Formation of Li-M-Si Ternaries (M = Mg, Zn, Al, Ca).

Replacing traditional graphite anode by Si anode can greatly improve the energy density of lithium-ion batteries. However, the large volume expansion and the formation of highly reactive lithium silicides during charging cause the continuous lithium and electrolyte consumption as well as the fast decay of Si anodes. In this work, by adding 0.1 M M(TFSI)x (M = Mg, Zn, Al and Ca) as a second salt into the electrolyte, we stabilize the anode chemistry through the in situ formation of Li-M-Si ternary phases during the charging process. First, lithium silicides and magnesium lithium silicides were synthesized as model compounds to investigate the influence of metal doping on the reactivity of lithiated Si. Using solid-state nuclear magnetic resonance spectroscopy, we show that Mg doping can dramatically suppress the chemical reactions between the lithium silicide compounds and common electrolyte solvents. New mixed salt electrolytes were prepared containing M(TFSI)x as a second salt to LiPF6 and tested in commercially relevant electrodes, which show higher capacity, superior cyclability, and higher Coulombic efficiencies in both half-cell and full-cell configurations (except for Zn) when compared with standard electrolytes. Post-electrochemistry characterizations demonstrate that adding M salts leads to the co-insertion of M cations along with Li into Si during the lithiation process, stabilizing silicon anions by forming more stable Li-M-Si ternaries, which fundamentally changes the traditional Li-Si binary chemistry while minimally affecting silicon electrochemical profiles and theoretical capacities. This study opens a new and simple way to stabilize silicon anodes to enable widespread application of Si anodes for lithium-ion batteries.

Effect of Passivating Shells on the Chemistry and Electrode Properties of LiMn2O4 Nanocrystal Heterostructures.

Building a stable chemical environment at the cathode/electrolyte interface is directly linked to the durability of Li-ion batteries with high energy density. Recently, colloidal chemistry methods have enabled the design of core-shell nanocrystals of Li1+ xMn2- xO4, an important battery cathode, with passivating shells rich in Al3+ through a colloidal synthetic route. These heterostructures combine the presence of redox-inactive ions on the surface to minimize undesired reactions, with the coverage of each individual particle in an epitaxial manner. Although they improve electrode performance, the exact chemistry and structure of the shell as well as the precise effect of the ratio between the shell and the active core remain to be elucidated. Correlation of these parameters to electrode properties would serve to tailor the heterostructure design toward complete shutdown of undesired reactions. These knowledge gaps are the target of this study. Li1+ xMn2- xO4 nanocrystals with Al3+-rich shells of different thicknesses were synthesized. Multimodal characterization comprehensively revealed the elemental distribution, electronic state, and crystallinity in the heterostructures, which confirmed the potential of this approach to finely tune passivating layers. All of the modified nanocrystals improved the capacity retention while retaining charge storage compared to the bare counterpart, even under harsh conditions.