Anode-Free Lithium-Sulfur Batteries with a Rare-Earth Triflate as a Dual-Function Electrolyte Additive.

Anode-free lithium-sulfur batteries feature a cell design with a fully lithiated cathode and a bare current collector as an anode to control the total amount of lithium in the cell. The lithium stripping and deposition are key factors in designing an anode-free full cell to realize a practical cell configuration. To realize effective anode protection and achieve a good performance of the anode-free full cell, manipulation of the electrolyte chemistry toward the modification of the solid-electrolyte interphase on the anode is considered a feasible approach. In this study, the use of neodymium triflate, Nd(OTf)3, as a dual-function electrolyte additive is demonstrated to promote homogeneous catalysis on the cathode conversion reactions and the anode stabilization. Nd(OTf)3 not only facilitates the conversion reaction by promoting the polysulfide adsorption but also effectively protects the lithium-metal anode and stabilizes the lithium stripping and deposition during cycling. With this electrolyte modification, both Li∥Li2S half cells and Ni∥Li2S anode-free full cells support a high areal capacity of 5.5-7.0 mA h cm-2 and maintain a high Coulombic efficiency of 94-95% during cycling.

A Class of Sodium Transition-Metal Sulfide Cathodes With Anion Redox.

Sodium-ion batteries (SIBs) are entering commercial relevance as a sustainable and low-cost alternative to lithium-ion batteries. Improving the energy density of SIBs is critical to enable their widespread adoption. Here, a new class of cathode materials Na6MS4 (M = Co, Mn, Fe, and Zn) that exhibit high charge-storage capacity is reported. Using Na6CoS4 as a prototypical example, a six-electron conversion reaction dominated by anion redox is observed, confirmed through various electrochemical and spectroscopic techniques. After the initial cycle, Na6CoS4 delivers a high capacity of 392 mA h g-1 with a long lifespan of over 500 cycles. The reaction involves, initially, the transformation of crystalline Na6CoS4 to a nearly amorphous structure consisting of mainly CoS and sulfur nanoparticles, which then reversibly cycles between nearly amorphous a-CoS/S and a-Na6CoS4. Such anion-redox-driven conversion-type cathodes hold the potential to enable energy-dense, stable SIBs.

Electrolyte-Enabled High-Voltage Operation of a Low-Nickel, Low-Cobalt Layered Oxide Cathode for High Energy Density Lithium-Ion Batteries.

The lithium-ion battery industry acknowledges the need to reduce expensive metals, such as cobalt and nickel, due to supply chain challenges. However, doing so can drastically reduce the overall battery energy density, attenuating the driving range for electric vehicles. Cycling to higher voltages can increase the capacity and energy density but will consequently exacerbate cell degradation due to the instability at high voltages. Herein, an advanced localized high-concentration electrolyte (LHCE) is utilized to enable long-term cycling of a low-Ni, low-Co layered oxide cathode LiNi0.60Mn0.31Co0.07Al0.02O2 (NMCA) in full cells with graphite or graphite-silicon anodes at 4.5 V (≈4.6 vs Li+/Li). NMCA cells with the LHCE deliver a high initial capacity of 194 mA h g-1 at C/10 rate along with 73% capacity retention after 400 cycles compared to 49% retention in a baseline carbonate electrolyte. This is facilitated by reduced impedance growth, active material loss, and gas evolution with the NMCA cathode. These improvements are attributed to the formation of robust, inorganic-rich interphase layers on both the cathode and anode throughout cycling, which are induced by a favorable salt decomposition in the LHCE. This study demonstrates the efficacy of electrolytes toward facilitating the operation of high-energy-density, long-life, and cost-effective cathodes.

Formation and Detriments of Residual Alkaline Compounds on High-Nickel Layered Oxide Cathodes.

High-nickel layered oxides LiNixM1-xO2 (x ≥ 0.9) have emerged as promising cathode materials for automotive batteries due to their high energy density and lower cost. However, the formation and accumulation of surface alkaline compounds during storage hinder their mass production and commercialization. Here, a validated chemical method is employed to deconvolute and quantify the evolution of each residual lithium compound in four representative cathodes during ambient-air storage, viz., LiNiO2 (LNO), LiNi0.95Co0.05O2 (NC), LiNi0.95Mn0.05O2 (NM), and LiNi0.95Al0.05O2 (NA). Furthermore, the activation energy of the reaction between water and the cathode is determined by measuring the leached LiOH concentration at various temperatures. While residual lithium and time-of-flight secondary-ion mass spectrometry measurements collectively reveal that the air stability overall follows the trend of NM > NA ≈ NC > LNO, the aged NM exhibits the highest charge-transfer resistance and the worst electrochemical performance among the cathodes. In situ, X-ray diffraction and scanning transmission electron microscopy unveil that the aged NM is plagued by a large area of resistive spinel-like M3-xLixO4 phases, leading to aggravated particle reaction heterogeneity. Finally, a one-step recalcination method is demonstrated effective in fully restoring the degraded cathodes. This work provides insights into overcoming air sensitivity issues of high-Ni cathodes.

Structure and Properties of Na2S-SiS2-P2S5-NaPO3 Glassy Solid Electrolytes.

In the development of sodium all-solid-state batteries (ASSBs), research efforts have focused on synthesizing highly conducting and electrochemically stable solid-state electrolytes. Glassy solid electrolytes (GSEs) have been considered very promising due to their tunable chemistry and resistance to dendrite growth. For these reasons, we focus here on the atomic-level structures and properties of GSEs in the compositional series (0.6-0.08y)Na2S + (0.4 + 0.08y)[(1 - y)[(1 - x)SiS2 + xPS5/2] + yNaPO3] (NaPSiSO). The mechanical moduli, glass transition temperatures, and temperature-dependent conductivity were determined and related to their short-range order structures that were determined using Raman, Fourier transform infrared, and 31P and 29Si magic angle spinning nuclear magnetic resonance spectroscopies. In addition, the conductivity activation energies were modeled using the Christensen-Martin-Anderson-Stuart model. These GSEs appear to be highly crystallization-resistant in the supercooled liquid region where no measurable crystallization below 450 °C could be observed in differential scanning calorimetry studies. Additionally, these GSEs were found to be highly conducting, with conductivities on the order of 10-5 (Ω cm)-1 at room temperature, and processable in the supercooled state without crystallization. For all these reasons, these NaPSiSO GSEs are considered to be highly competitive and easily processable candidate GSEs for enabling sodium ASSBs.

Mitigating Sodium Ordering for Enhanced Solid Solution Behavior in Layered NaNiO2 Cathodes.

The O-type layered nickel oxides suffer from undesired cooperative Jahn-Teller distortion stemming from Ni3+ ions and undergo multiple biphasic structural transformations during the insertion/extraction of large Na+ ions, posing a significant challenge to stabilize the structural integrity. We present here a systematic investigation of the impact of substituting 5 % divalent (Mg2+) or trivalent (Al3+ or Co3+) ions for Ni3+ to alleviate Na+ion ordering and perturb the Jahn-Teller effect to enhance structural stability. We gauge a fundamental understanding of the Mg-O and Na-O or Mg-O-Na bonding interactions, noting that the ionicity of the Mg-O bond deshields the electronic cloud of oxygen from Na+ ions. Furthermore, calculations of the Van Vleck distortion modes reveal a relaxation of NiO6 octahedra from Jahn-Teller distortion and a reduced electron density at the interlayer with Mg2+ substitution. Long-range (operando X-ray diffraction) and short-range (magic angle spinning nuclear magnetic resonance) structural analyses provide insights into reduced ordering, allowing a stable continuous solid solution. Overall, Mg-substitution results in a high-capacity retention of ~96 % even after 100 cycles, showcasing the potential of this strategy for overcoming the structural instabilities and enhancing the performance of sodium-ion batteries.

Rechargeable Metal-Sulfur Batteries: Key Materials to Mechanisms.

Rechargeable metal-sulfur batteries are considered promising candidates for energy storage due to their high energy density along with high natural abundance and low cost of raw materials. However, they could not yet be practically implemented due to several key challenges: (i) poor conductivity of sulfur and the discharge product metal sulfide, causing sluggish redox kinetics, (ii) polysulfide shuttling, and (iii) parasitic side reactions between the electrolyte and the metal anode. To overcome these obstacles, numerous strategies have been explored, including modifications to the cathode, anode, electrolyte, and binder. In this review, the fundamental principles and challenges of metal-sulfur batteries are first discussed. Second, the latest research on metal-sulfur batteries is presented and discussed, covering their material design, synthesis methods, and electrochemical performances. Third, emerging advanced characterization techniques that reveal the working mechanisms of metal-sulfur batteries are highlighted. Finally, the possible future research directions for the practical applications of metal-sulfur batteries are discussed. This comprehensive review aims to provide experimental strategies and theoretical guidance for designing and understanding the intricacies of metal-sulfur batteries; thus, it can illuminate promising pathways for progressing high-energy-density metal-sulfur battery systems.

High-Loading Lithium-Sulfur Batteries with Solvent-Free Dry-Electrode Processing.

Lithium-sulfur (Li-S) batteries, with their high energy density, nontoxicity, and the natural abundance of sulfur, hold immense potential as the next-generation energy storage technology. To maximize the actual energy density of the Li-S batteries for practical applications, it is crucial to escalate the areal capacity of the sulfur cathode by fabricating an electrode with high sulfur loading. Herein, ultra-high sulfur loading (up to 12 mg cm-2 ) cathodes are fabricated through an industrially viable and sustainable solvent-free dry-processing method that utilizes a polytetrafluoroethylene binder fibrillation. Due to its low porosity cathode architecture formed by the binder fibrillation process, the dry-processed electrodes exhibit a relatively lower initial capacity compared to the slurry-processed electrode. However, its mechanical stability is well maintained throughout the cycling without the formation of electrode cracking, demonstrating significantly superior cycling stability. Additionally, through the optimization of the dry-processing, a single-layer pouch cell with a loading of 9 mg cm-2 and a novel multi-layer pouch cell that uses an aluminum mesh as its current collector with a total loading of 14 mg cm-2 are introduced. To address the reduced initial capacity of dry-processed electrodes, strategies such as incorporating electrocatalysts or employing prelithiated active materials are suggested.

Delineating the Effects of Transition-Metal-Ion Dissolution on Silicon Anodes in Lithium-Ion Batteries.

Silicon anode is an appealing alternative to enhance the energy density of lithium-ion batteries due to its high capacity, but it suffers from severe capacity fade caused by its fast degradation. The crossover of dissolved transition-metal (TM) ions from the cathode to the anode is known to catalyze the decomposition of electrolyte on the graphite anode surface, but the relative impact of dissolved Mn2+ versus Ni2+ versus Co2+ on silicon anode remains to be delineated. Since all three TM ions can dissolve from LiNi1-x-yMnxCoyO2 (NMC) cathodes and migrate to the anode, here a LiFePO4 cathode is paired with SiOx anode and assess the impact by introducing a specific amount of Mn2+ or Ni2+ or Co2+ ions into the electrolyte. It is found that Mn2+ ions cause a much larger increase in SiOx electrode thickness during cycling due to increased electrolyte decomposition and solid-electrolyte interphase (SEI) formation compared to Ni2+ and Co2+ ions, similar to previous findings with graphite anode. However, with a lower impedance, the SEI formed with Mn2+ protects the Si anode from excessive degradation compared to that with Co2+ or Ni2+ ions. Thus, Mn2+ ions have a less detrimental effect on Si anodes than Co2+ or Ni2+ ions, which is the opposite of that seen with graphite anodes.

Interphase Stabilization of LiNi0.5 Mn1.5 O4 Cathode for 5 V-Class All-Solid-State Batteries.

Employing high voltage cobalt-free spinel LiNi0.5 Mn1.5 O4 (LNMO) as a cathode is promising for high energy density and cost-effectiveness, but it has challenges in all-solid-state batteries (ASSBs). Here, it is revealed that the limitation of lithium argyrodite sulfide solid electrolyte (Li6 PS5 Cl) with the LNMO cathode is due to the intrinsic chemical incompatibility and poor oxidative stability. Through a careful analysis of the interphase of LNMO, it is elucidated that even the halide solid electrolyte (Li3 InCl6 ) with high oxidative stability can be decomposed to form resistive interphase layers with LNMO in ASSBs. Interestingly, with Fe-doping and a Li3 PO4 protective layer coating, LNMO with Li3 InCl6 displays stable cycle performance with a stabilized interphase at a high voltage (≈4.7 V) in ASSBs. The enhanced interfacial stability with the extended electrochemical stability window through doping and coating enables high electrochemical stability with LNMO in ASSBs. This work provides guidance for employing high-voltage cathodes in ASSBs and highlights the importance of stable interphases to enable stable cycling in ASSBs.

Effect of Oxidative Synthesis Conditions on the Performance of Single-Crystalline LiMn2- x Mx O4 (M = Al, Fe, and Ni) Spinel Cathodes in Lithium-Ion Batteries.

LiMn2 O4 (LMO) spinel cathode materials attract much interest due to the low price of manganese and high power density for lithium-ion batteries. However, the LMO cathodes suffer from the Mn dissolution problem at particle surfaces, which accelerates capacity fade. Herein, the authors report that the oxidative synthesis condition is a key factor in the cell performance of single-crystalline LiMn2- x Mx O4 (0.03 ≤ x ≤ 0.1, M = Al, Fe, and Ni) cathode materials prepared at 1000 °C. The use of oxygen flow during the spinel-phase formation minimizes the presence of oxygen vacancies generated at 1000 °C, thereby yielding a stoichiometrically doped LMO product; otherwise, the spinel cathode prepared in atmospheric air readily loses capacity due to the oxygen vacancies in the structure. As a way of circumventing the use of oxygen flow, a one-pot, two-step heating in air at 1000 °C and subsequently at 600 °C is used to yield the stoichiometric LMO product. The lithiation heating at 1000-600 °C resulted in a significant improvement in the cycling stability of the prepared LMO cathode in graphite-based full cells. This study on oxidative synthesis conditions also confirms the advantage of minimizing the surface area of the cathode particles.

Effect of Electrochemical Pre-Lithiation on Layered Oxide Cathodes for Anode-Free Lithium-metal Batteries.

Due to high energy density and lower manufacturing cost, anode-free lithium-metal batteries (AFLMBs) are attracting increasing attention. The challenges for developing them lie in inferior Coulombic efficiency and short cycle life due to the highly reactive lithium metal. Herein, an electrochemical pre-lithiation strategy is applied to layered oxide cathodes, specifically LiNiO2 and LiCoO2 , aiming to provide an additional lithium source and understand the effect on the cathode structure for AFLMBs. The mechanism for accommodating the excess Li depends on the structural stability of the cathodes where LiNiO2 forms lithiated Li2 NiO2 with the excess lithium in the crystalline lattice while the excess lithium in LiCoO2 forms a Li2 O phase. More importantly, an optimal amount of Li excess is necessary to maintain decent cycle stability and specific capacity in AFLMB, with 40% excess Li for LiNiO2 and 150% for LiCoO2 . While the pre-lithiation process causes particle pulverization depending on the amount of Li excess, LiCoO2 offers a much better cycle performance than LiNiO2 with a promising capacity retention of 80% after 300 cycles in AFLMB (vs 76% after 100 cycles for 40% Li excess in LiNiO2 ). This study provides a promising avenue for developing tailor-made layered oxide cathodes for AFLMBs.

Polycarbonate-Based Solid-Polymer Electrolytes for Solid-State Sodium Batteries.

Solid-polymer electrolytes comprised of polypropylene carbonate (PPC) and varied sodium bis(fluorosulfonyl)imide (NaFSI) salt concentrations are investigated for implementation as a conductive solid polymer electrolyte into solid-state cathode composites utilizing a sodium-layered oxide active material. The ionic conductivity generally increases with NaFSI salt content, reaching ≈1 mS cm-1 at 80 °C at the highest salt concentration (PPC:NaFSI = 0.5:1). Through an all-in-one slurry casting method, Na2/3Ni1/3Mn2/3O2 cathode composites are fabricated in which the dispersed PPC electrolyte acts as the primary binder. Enabled by a bilayer polymer electrolyte system, cycling performance with the PPC cathode electrolyte is optimized with respect to salt concentration and anode material. The best cyclability is achieved with a moderate salt concentration electrolyte (PPC:NaFSI = 5:1), showcasing an initial capacity of 83 mA h g-1 with a remarkable 80% capacity retention after 150 cycles at C/5 rate and 60 °C. The superior performance of the lower salt concentration electrolyte is attributed to better electrochemical stability, as confirmed by linear sweep voltammetry and online electrochemical mass spectrometry measurements. These results underscore the potential of carbonate-based polymer electrolytes and the importance of balancing electrolyte conductivity and stability in cell design.

Delineating the Impact of Transition-Metal Crossover on Solid-Electrolyte Interphase Formation with Ion Mass Spectrometry.

Lithium-metal batteries (LMB) employing cobalt-free layered-oxide cathodes are a sustainable path forward to achieving high energy densities, but these cathodes exhibit substantial transition-metal dissolution during high-voltage cycling. While transition-metal crossover is recognized to disrupt solid-electrolyte interphase (SEI) formation on graphite anodes, experimental evidence is necessary to demonstrate this for lithium-metal anodes. In this work, advanced high-resolution 3D chemical analysis is conducted with time-of-flight secondary-ion mass spectrometry (TOF-SIMS) to establish spatial correlations between the transition metals and electrolyte decomposition products found on cycled lithium-metal anodes. Insights into the localization of various chemistries linked to crucial processes that define LMB performance, such as lithium deposition, SEI growth, and transition-metal deposition are deduced from a precise elemental and spatial analysis of the SEI. Heterogenous transition-metal deposition is found to perpetuate both heterogeneous SEI growth and lithium deposition on lithium-metal anodes. These correlations are confirmed across various lithium-metal anodes that are cycled with different cobalt-free cathodes and electrolytes. An advanced electrolyte that is stable to higher voltages is shown to minimize transition-metal crossover and its effects on lithium-metal anodes. Overall, these results highlight the importance of maintaining uniform SEI coverage on lithium-metal anodes, which is disrupted by transition-metal crossover during operation at high voltages.

Irreparable Interphase Chemistry Degradation Induced by Temperature Pulse in Lithium-Ion Batteries.

While it is widely recognized that the operating temperature significantly affects the energy density and cycle life of lithium-ion batteries, the consequence of electrode-electrolyte interphase chemistry to sudden environmental temperature changes remains inadequately understood. Here, we systematically investigate the effects of a temperature pulse (T pulse) on the electrochemical performance of LiNi0.8 Mn0.1 Co0.1 O2 (NMC811) pouch full cells. By utilizing advanced characterization tools, such as time-of-flight secondary-ion mass spectrometry, we reveal that the T pulse can lead to an irreversible degradation of cathode-electrolyte interphase chemistry and architecture. Despite negligible immediate impacts on the solid-electrolyte interphase (SEI) on graphite anode, aggregated cathode-to-anode chemical crossover gradually degrades the SEI by catalyzing electrolyte reduction decomposition and inducing metallic dead Li formation because of insufficient cathode passivation after the T pulse. Consequently, pouch cells subjected to the T pulse show an inferior cycle stability to those free of the T pulse. This work unveils the effects of sudden temperature changes on the interphase chemistry and cell performance, emphasizing the importance of a proper temperature management in assessing performance.

Intercalation-type catalyst for non-aqueous room temperature sodium-sulfur batteries.

Ambient-temperature sodium-sulfur (Na-S) batteries are potential attractive alternatives to lithium-ion batteries owing to their high theoretical specific energy of 1,274 Wh kg-1 based on the mass of Na2S and abundant sulfur resources. However, their practical viability is impeded by sodium polysulfide shuttling. Here, we report an intercalation-conversion hybrid positive electrode material by coupling the intercalation-type catalyst, MoTe2, with the conversion-type active material, sulfur. In addition, MoTe2 nanosheets vertically grown on graphene flakes offer abundant active catalytic sites, further boosting the catalytic activity for sulfur redox. When used as a composite positive electrode and assembled in a coin cell with excess Na, a discharge capacity of 1,081 mA h gs-1 based on the mass of S with a capacity fade rate of 0.05% per cycle over 350 cycles at 0.1 C rate in a voltage range of 0.8 to 2.8 V is realized under a high sulfur loading of 3.5 mg cm-2 and a lean electrolyte condition with an electrolyte-to-sulfur ratio of 7 µL mg-1. A fundamental understanding of the electrocatalysis of MoTe2 is further revealed by in-situ synchrotron-based operando X-ray diffraction and ex-situ time-of-flight secondary ion mass spectrometry.

Poly(vinylferrocene) as an Ionomer and Sulfur-Confining Additive for Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries are promising owing to their high energy density, environmental benignity, and low cost. Most of the commonly used binders in Li-S battery cathodes are inert and have no significant effect on the challenges of sulfur as a cathode material, such as the polysulfide shuttle effect, low ionic/electronic conductivity, and a sluggish redox reaction. In this work, we demonstrate the use of poly(vinylferrocene) (PvFc) as a binder additive that can effectively increase the ionic conductivity of the cathode and act as a sulfide-confining agent. Electrochemical tests performed with PvFc as part of the binder mixture used to cast the cathodes demonstrate an increase in rate capability and cycle life when compared to the baseline samples. Ionic conductivity measurements and X-ray photoelectron spectroscopy suggest that the π-cation molecular interaction between the cyclopentadienyl rings from ferrocene and Li+ behaves like an ion couple with ferrocene acting as a static, covalently bound acceptor of Li+ ions that enhances their mobility through the cathode. This coupled with the affinity between the ferrocenyl cations and the Li salt anions, which provides more distribution of counterions for Li+ movement and improves accessibility to the cathode S reservoir, make PvFc a promising ionomer for Li-S batteries. In addition, the π-cation bonds between cyclopentadienyl and lithium polysulfides produce a sulfide-confining effect that mitigates capacity fade through polysulfide dissolution. This work demonstrates an expansion in the utility of PvFc as a component in Li-ion batteries, which so far is mostly limited to use as an active material in organometallic batteries.

Localized High-Concentration Electrolytes with Low-Cost Diluents Compatible with Both Cobalt-Free LiNiO2 Cathode and Lithium-Metal Anode.

High-nickel layered oxide cathodes and lithium-metal anode are promising candidates for next-generation battery systems due to their high energy density. Nevertheless, the instability of the electrode-electrolyte interphase is hindering their practical application. Localized high-concentration electrolytes (LHCEs) present a promising solution for achieving uniform lithium deposition and a stable cathode-electrolyte interphase. However, the limited choice of diluents and their high cost are restricting their implementation. Four novel cost-effective diluents and their performance with highly reactive LiNiO2 cathode and Li-metal anode are reported here. The results show that all the LHCE cells exhibit a Coulombic efficiency of >99.38% in Li | Cu cells and a capacity retention of >85% in Li | LiNiO2 cells after 250 cycles. Advanced characterizations unveil that the stable cell operation is due to well-tuned electrode-electrolyte interphases and Li deposition morphology. In addition, online electrochemical mass spectroscopy and differential scanning calorimetry reveal that the gas generation and heat-release are greatly reduced with the LHCEs presented. Overall, the study provides new insights into the role of diluents in LHCEs and offers valuable guidance for further optimization of LHCEs for high energy density lithium-metal batteries.

Battery Charge Curve Prediction via Feature Extraction and Supervised Machine Learning.

Real-time onboard state monitoring and estimation of a battery over its lifetime is indispensable for the safe and durable operation of battery-powered devices. In this study, a methodology to predict the entire constant-current cycling curve with limited input information that can be collected in a short period of time is developed. A total of 10 066 charge curves of LiNiO2 -based batteries at a constant C-rate are collected. With the combination of a feature extraction step and a multiple linear regression step, the method can accurately predict an entire battery charge curve with an error of < 2% using only 10% of the charge curve as the input information. The method is further validated across other battery chemistries (LiCoO2 -based) using open-access datasets. The prediction error of the charge curves for the LiCoO2 -based battery is around 2% with only 5% of the charge curve as the input information, indicating the generalization of the developed methodology for predicting battery cycling curves. The developed method paves the way for fast onboard health status monitoring and estimation for batteries during practical applications.

Thermal Stability and Outgassing Behaviors of High-nickel Cathodes in Lithium-ion Batteries.

LiNiO2 -based high-nickel layered oxide cathodes are regarded as promising cathode materials for high-energy-density automotive lithium batteries. Most of the attention thus far has been paid towards addressing their surface and structural instability issues brought by the increase of Ni content (>90 %) with an aim to enhance the cycle stability. However, the poor safety performance remains an intractable problem for their commercialization in the market, yet it has not received appropriate attention. In this review, we focus on the gas generation and thermal degradation behaviors of high-Ni cathodes, which are critical factors in determining their overall safety performance. A comprehensive overview of the mechanisms of outgassing and thermal runaway reactions is presented and analyzed from a chemistry perspective. Finally, we discuss the challenges and the insights into developing robust, safe high-Ni cathodes.