Nickel-rich Layered Oxide Cathodes Research Articles

Hydrogen-bonded organic framework modified separator for simultaneously enhancing the safety and electrochemical performance of Ni-rich lithium-ion battery

Nickel-rich layered oxide cathode (LiNixCoyMn1−x−yO2, x > 0.5, NCM) shows substantial potential for applications in longer-range electrical vehicles. However, the rapid capacity decay and serious safety concerns impede its practical viability. This work provides a hydrogen-bonded organic framework (HOF) modification strategy to simultaneously improve the electrochemical performance, thermal stability and incombustibility of separator. Melamine cyanurate (MCA), as a low-cost and reliable flame-retardant HOF, was implemented in the separator modification layer, which can prevent the battery short circuit even at a high temperature. In addition, the supermolecule properties of MCA provide unique physical and chemical microenvironment for regulating ion-transport behavior in electrolyte. The MCA coating layer enabled the nickel-rich layered oxide cathode with a high-capacity retention of 90.3% after 300 cycles at 1.0 C. Collectively, the usage of MCA in lithium-ion batteries (LIBs) affords a simple, low-cost and efficient strategy to improve the security and service life of nickel-rich layered cathodes.

The Role of Zinc Triflate Additive for Improved Electrochemical Performance of Nickel-Rich Layered Oxide Lithium Battery Cathode via Suppression of Interfacial Parasitic Reactions

Nickel-rich layered oxide cathode materials with low cobalt content, such as LiNi0.90Mn0.05Co0.05O2 (NMC90), have the potential to enable cost-effective, high-energy-density lithium-metal batteries. However, NMC90 cathode materials are prone to severe parasitic reactions at higher voltages during prolonged cycling. The addition of small percentages of electrolyte additives to the neat commercial electrolyte can significantly enhance the overall electrochemical performance of lithium-metal batteries. This study investigates the effects of zinc triflate (Zn(Otf)2) as an electrolyte additive on the enhancement of the electrochemical performances of lithium-metal batteries comprising nickel-rich layered oxide cathode materials. X-ray photoelectron spectroscopy analysis revealed that Zn(Otf)2 decomposition leads to enhanced fluorination at the interfacial layers, which contributes to improved chemical stability. Utilizing operando electrochemical mass spectroscopy, we demonstrate that Zn(Otf)2 additives effectively suppress the electrolyte degradation, which is otherwise detrimental to electrochemical performance. Electrochemical studies show that the inclusion of only ∼1% Zn(Otf)2 as additive in neat commercial electrolyte enhances the electrochemical performance indicated by a 10% improvement in discharge capacity after 150 cycles. This study paves the way for researchers to develop novel fluorinated triflate based electrolyte additives aimed at enhancing the stabilization of interfaces for lithium ion, and potentially also Li-metal batteries.

Revealing the Nanoscopic Corrosive Degradation Mechanism of Nickel-Rich Layered Oxide Cathodes at Low State-of-Charge Levels: Corrosion Cracking and Pitting.

Ni-rich layered oxides have received significant attention as promising cathode materials for Li-ion batteries due to their high reversible capacity. However, intergranular and intragranular cracks form at high state-of-charge (SOC) levels exceeding 4.2 V (vs. Li/Li+), representing a prominent failure mechanism of Ni-rich layered oxides. The nanoscale crack formation at high SOC levels is attributed to a significant volume change resulting from a phase transition between the H2 and H3 phases. Herein, in contrast to the electrochemical crack formation at high SOC levels, another mechanism of chemical crack and pit formation on a nanoscale is directly evidenced in fully lithiated Ni-rich layered oxides (low SOC levels). This mechanism is associated with intergranular stress corrosion cracking, driven by chemical corrosion at elevated temperatures. The nanoscopic chemical corrosion behavior of Ni-rich layered oxides during aging at elevated temperatures is investigated using high-resolution transmission electron microscopy, revealing that microcracks can develop through two distinct mechanisms: electrochemical cycling and chemical corrosion. Notably, chemical corrosion cracks can occur even in a fully discharged state (low SOC levels), whereas electrochemical cracks are observed only at high SOC levels. This finding provides a comprehensive understanding of the complex failure mechanisms of Ni-rich layered oxides and provides an opportunity to improve their electrochemical performance.

Enhancing performance and stability of LiNi0.8Co0.1Mn0.1O2 cathode via Na/Y dual doping for Lithium-Ion batteries

Nickel-rich layered oxide cathode materials face limitations in practical applications due to trade-offs between capacity and structural stability. As more Li+ is extracted during charging, the layered structure of nickel-rich materials becomes increasingly fragile. To address this, a double doping strategy with Na and Y is proposed in this study to enhance the strength of the layered structure. The research findings demonstrate that Na doping enlarges the spacing between Li layers in the crystal structure, while Y doping improves the reversibility of the H2-H3 phase transition but narrows the Li layer spacing in nickel-rich materials. Na and Y double doping, the advantages of Na in enlarging the Li layer, and Y in improving the H2-H3 phase transition can be harnessed simultaneously. This double doping strategy ensures that the laminar structure of the cathode material remains stable even when it is highly detached, effectively solving the trade-off between the capacity and structural stability of nickel-rich laminar cathode materials. The application in LiNi0.8Co0.1Mn0.1O2 shows that the capacity and cycle life of cathode materials can be significantly improved after Na/Y double doping. These findings open up opportunities for practical applications of nickel-rich cathode materials in lithium-ion batteries.

Tuning the Interface Stability of Nickel-Rich NCM Cathode Against Aggressive Structural Collapse via the Synergistic Effect of Additives.

Nickel-rich layered oxides are envisaged as one of the most promising alternative cathode materials for lithium-ion batteries, considering their capabilities to achieve ultrahigh energy density at an affordable cost. Nonetheless, with increasing Ni content in the cathodes comes a severe extent of Ni4+ redox side reactions on the interface, leading to fast capacity decay and structural stability fading over extended cycles. Herein, dual additives of bis(vinylsulfonyl)methane (BVM) and lithium difluorophosphate (LiDFP) are adopted to synergistically generate the F-, P-, and S-rich passivation layer on the cathode, and the Ni4+ activity and dissolution at high voltage are restricted. The sulfur-rich layer formed by the polymerization of BVM, combined with the Li3PO4 and LiF phases derived from LiDFP, alleviates the problems of increased impedance, cracks, and an irreversible H2-H3 phase transition. Consequently, the Ni-rich LiNixM1-xO2 (x > 0.95) button half-cell cycled in LiDFP + BVM electrolyte exhibits a significant discharging capacity of 181.4 mAh g-1 at 1 C (1 C = 200 mA g-1) with retention of 83.7% after 100 cycles, surpassing the performance of the commercial electrolyte (160.7 mAh g-1) with retention of 53.3%. Remarkably, the NCM95||graphite pouch cell exhibits a remarkable capacity retention of 95.5% after 200 cycles. This work inspires the rational design of electrolyte additives for ultrahigh-energy batteries with nickel-rich layered oxide cathodes.

Kirkendall effect-induced uniform stress distribution stabilizes nickel-rich layered oxide cathodes

Nickel-rich layered oxide cathodes promise ultrahigh energy density but is plagued by the mechanical failure of the secondary particle upon (de)lithiation. Existing approaches for alleviating the structural degradation could retard pulverization, yet fail to tune the stress distribution and root out the formation of cracks. Herein, we report a unique strategy to uniformize the stress distribution in secondary particle via Kirkendall effect to stabilize the core region during electrochemical cycling. Exotic metal/metalloid oxides (such as Al2O3 or SiO2) is introduced as the heterogeneous nucleation seeds for the preferential growth of the precursor. The calcination treatment afterwards generates a dopant-rich interior structure with central Kirkendall void, due to the different diffusivity between the exotic element and nickel atom. The resulting cathode material exhibits superior structural and electrochemical reversibility, thus contributing to a high specific energy density (based on cathode) of 660 Wh kg−1 after 500 cycles with a retention rate of 86%. This study suggests that uniformizing stress distribution represents a promising pathway to tackle the structural instability facing nickel-rich layered oxide cathodes.

Stabilizing LiNi0.8Co0.1Mn0.1O2 cathode by combined moisture and HF digestion/adsorption for high-performance lithium metal batteries

Nickel-rich layered oxide cathodes such as LiNi0.8Co0.1Mn0.1O2 are promising to significantly increase the energy density of lithium metal batteries beyond 350 Wh kg−1. However, serious issues regarding cycle stability still remain when matching with conventional non-aqueous carbonate electrolytes that contain fluorine such as lithium hexafluorophosphate (LiPF6). Hydrolysis of LiPF6 generates corrosive hydrofluoric acid (HF), which destroys the cathode structure and accelerates the cathodic dissolution/anodic deposition of transition metal (TM) ions. Here, we demonstrate that ball milling NCM811 with carbon-coated aluminum nitride (AlN-C) remarkably enhances the capacity retention. AlN-C acts both as a scavenger and as an adsorption center to digest and adsorb H2O and HF, respectively. Thereby, it prevents the dissolution of TM ions, which would result in capacity decay and damage to the lithium metal anode. It is demonstrated that the addition of AlN-C via wet ball milling with NCM811 enables retaining a specific capacity of 149.9 mA h g−1 after 250 cycles (capacity retention: 85.2 %) at 1 C even in a high moisture electrolyte containing ∼0.2 % (v/v) H2O. Therefore, this work shows up a pathway to a rational enhancement of the capacity retention and cycle life of nickel-rich cathodes.

Microstructures of layered Ni-rich cathodes for lithium-ion batteries.

Millions of electric vehicles (EVs) on the road are powered by lithium-ion batteries (LIBs) based on nickel-rich layered oxide (NRLO) cathodes, and they suffer from a limited driving range and safety concerns. Increasing the Ni content is a key way to boost the energy densities of LIBs and alleviate the EV range anxiety, which are, however, compromised by the rapid performance fading. One unique challenge lies in the worsening of the microstructural stability with a rising Ni-content in the cathode. In this review, we focus on the latest advances in the understanding of NLRO microstructures, particularly the microstructural degradation mechanisms, state-of-the-art stabilization strategies, and advanced characterization methods. We first elaborate on the fundamental mechanisms underlying the microstructural failures of NRLOs, including anisotropic lattice evolution, microcracking, and surface degradation, as a result of which other degradation processes, such as electrolyte decomposition and transition metal dissolution, can be severely aggravated. Afterwards, we discuss representative stabilization strategies, including the surface treatment and construction of radial concentration gradients in polycrystalline secondary particles, the fabrication of rod-shaped primary particles, and the development of single-crystal NRLO cathodes. We then introduce emerging microstructural characterization techniques, especially for identification of the particle orientation, dynamic changes, and elemental distributions in NRLO microstructures. Finally, we provide perspectives on the remaining challenges and opportunities for the development of stable NRLO cathodes for the zero-carbon future.

Multiscale Probing and Redesign of the Solid-State Synthesis Toward Defect-Free Ni-Rich Layered Cathodes

Nickel-rich lithium layered oxides (LiNixCoyMnzO2, NCM, x+y+z=1, x≥0.6)) have received tremendous attention as the most promising cathode materials for the practical development of high-energy lithium-ion batteries. However, they commonly suffer from rapid capacity decay along with structural and morphological degradation. Previous studies have unraveled that the general failure mechanism involves the mechanical deterioration of electrode particles, originating from micro-cracking in particles due to the build-up of significant anisotropic strains during phase transition and the chemical parasitic reactions with electrolytes through the crevice created. Such chemo-mechanical failures are triggered and aggravated by various structural defects, including internal void spaces, surface reconstruction layers, and intragranular nanopores, typical features of the conventionally synthesized nickel-rich layered oxide materials. It remains elusive how these defects are formed regardless of the use of single-crystalline or polycrystalline particles. A fundamental understanding of the general defect formations is thus indispensable to clarify how the synthesis process induces the formation of intrinsic defects from the precursor to the final product stage and how these defects affect the electrochemical degradation at the primary- and secondary-particle levels. Critical questions that require in-depth study include how the spatially inhomogeneous solid-state reaction begins at the interface of reacting precursors, propagates during the synthesis, and triggers the generation of defects. In this presentation, I will show the hidden synthetic mechanism of nickel-rich layered oxide materials using a combination of high-end and multi-length-scale analysis methods, including aberration-corrected TEM, in situ heating TEM with gas control, and in situ XRD. The kinetic interplay in synthesis of nickel-rich lithium layered oxide and its implications will be discussed in detail. Furthermore, the microstructural pore defects of NCN9235 during the heating process were quantitatively characterized. Based on our mechanistic understanding, we propose a redesign of solid-state synthesis pathway to achieve structurally integrated nickel-rich layered oxide cathodes.

Three-Dimensional Octahedral Nanocrystals of Cu2O/CuF2 Grown on Porous Cu Foam Act as a Lithophilic Skeleton for Dendrite-Free Lithium Metal Anode.

Metallic-lithium (Li) anodes are highly sought-after for next-generation energy storage systems due to their high theoretical capacity and low electrochemical potential. However, the commercialization of Li anodes faces challenges, including uncontrolled dendrite growth and volume changes during cycling. To address these issues, we developed a novel three-dimensional (3D) copper current collector. Here, we propose a two-step method to fabricate Cu2O/CuF2 octahedral nanocrystals (ONCs) onto 3D Cu current collectors. The resulting Cu foam with distributed ONCs provides active electrochemical sites, promoting uniform Li nucleation and dendrite-free Li deposition. The stable Cu2O/CuF2 ONCs@CF metallic current collector serves as a reliable host for dendrite-free lithium metal anodes. Additionally, the highly porous copper foam with a preconstructed conductive framework of Cu2O/CuF2 ONCs@CF effectively reduces local current density, suppressing volume changes during Li stripping and plating. The symmetric cell using Cu2O/CuF2 ONCs@CF metallic current collector exhibits excellent stability, maintaining over 1600 h at 1 mA cm-2 and a highly stable Coulombic efficiency of 98% over 100 cycles at the same current density, outperforming Li@CuF metallic current collectors. Furthermore, in a full-cell configuration paired with nickel-rich layered oxide cathode materials (Li@Cu2O/CuF2 ONCs@CF//NMC-811), the proposed setup demonstrates exceptional rate performance and an extended cycle life. In conclusion, our work presents a promising strategy to address Li anode challenges and highlights the exceptional performance of the Cu2O/CuF2 ONCs@CF metallic current collector, offering potential for high-capacity and long-lasting lithium-based energy storage systems.

Stabilizing Ni-rich LiNi0.8Co0.1Mn0.1O2 cathode by generating ion-conductive polymer coating layer with 1, 3-dioxolane introducing electrolyte for lithium-ion batteries

The employment of electrolyte-film forming additive is a facile and effective strategy to improve the cycling performance of aggressive Nickel-rich layered oxide cathode LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode for high energy lithium-ion batteries (LIBs). Here we report a homogeneous and dense polymer cathode-electrolyte-interface (CEI) film generated via in-situ electrooxidation polymerization of 1, 3-Dioxolane (DOL) in a conventional carbonate-based electrolyte. It is found that the electrolyte modification with 15% DOL is the most effective in balancing the interfacial stability and Li-ion diffusion kinetics of NCM811 cathode, while also achieving its comparable rate capability and greatly improving cycling performance. Morphological and elemental characterizations demonstrate that the 15% DOL-derived CEI layer not only alleviates the impacts of harmful interfacial reactions and hinders the particle disintegration, but also suppresses the irreversible lattice transition of the NCM811 cathode surface to the inactive rock salt phase. Moreover, it is proved that the F-rich interfacial layer displays excellent Li-ion transport kinetics. As a result, the cell exhibits high capacity retention of 85.2% and 78.1% after 200 cycles at cut-off voltages of 4.3 V and 4.5 V at 1 C in the 15% DOL-modified electrolyte. Therefore, creating a stable and effective Li-ion conductive interfacial protective film on the cathode surface by optimizing an electrolyte functional additive is an economical and available approach to develop the highly stabilized Ni-rich cathode for high-energy LIBs applications.

O3 to O1 Phase Transitions in Highly Delithiated NMC811 at Elevated Temperatures.

Nickel-rich layered oxide cathodes such as NMC811 (LixNi0.8Mn0.1Co0.1O2) currently have the highest practical capacities of cathodes used commercially, approaching 200 mAh/g. Lithium is removed from NMC811 via a solid-solution behavior when delithiated to xLi > 0.10, maintaining the same layered (O3 structure) throughout as observed via operando diffraction measurements. Although it is possible to further delithiate NMC811, it is kinetically challenging, and there are significant side reactions between the electrolyte and cathode surface. Here, small format, NMC811-graphite pouch cells were charged to high voltages at elevated temperatures and held for days to access high states of delithiation. Rietveld refinements on high-resolution diffraction data and indexing of selected area electron diffraction patterns, both acquired ex situ, show that NMC811 undergoes a partial and reversible transition from the O3 to the O1 phase under these conditions. The O1 phase fraction depends not only on the concentration of intercalated lithium but also on the hold temperature and hold time, indicating that the phase transition is kinetically controlled. 1H NMR spectroscopy shows that the proton concentration decreases with O1 phase fraction and is not, therefore, likely to be driving the O3-O1 phase transition.

A Kinetic Indicator of Ultrafast Nickel-Rich Layered Oxide Cathodes

Elucidating high-rate cycling-induced nonequilibrium electrode reactions is crucial for developing extreme fast charging (XFC) batteries. Herein, we unveiled the distinct rate capabilities of a series of Ni-rich layered oxide (NRLO) cathodes by quantitatively establishing their dynamic structure–kinetics relationships. Contrary to conventional views, we discovered electrode kinetic properties obtained ex-situ near equilibrium states failed to assess the effective rate capability of NRLOs at ultrafast C rates. Further, the kinetic phase heterogeneity, characterized by the dynamic separations in in-situ X-ray diffraction patterns and deviations in NRLO c-axis lattice parameters, exclusively correlated with the capacity reduction under XFC and became an effective indicator of the NRLO rate capability. Enhancing the cycling temperature boosted the rate capability of studied NRLOs by ∼10%, which was further verified to mitigate the kinetic phase heterogeneity during XFC. Overall, this study lays the groundwork for tuning the kinetic phase heterogeneity of electrodes to develop ultrafast batteries.

Doping Strategy in Nickel-Rich Layered Oxide Cathode for Lithium-Ion Battery

Doping Strategy in Nickel-Rich Layered Oxide Cathode for Lithium-Ion Battery

A Comparative Analysis on Thermal Stability of Delithiated Nickel-Rich LiNi0.8Co0.15Al0.05O2 and LiNi0.8Co0.1Mn0.1O2 in Pouch Cells

Abstract As two typical nickel-rich layered oxide cathodes, LiNi0.8Co0.15Al0.05O2 (NCA) and LiNi0.8Co0.1Mn0.1O2 (NCM811) are widely applicated in commercial high-energy batteries for electric vehicles. However, a comprehensive assessment of their thermal characteristics in a full cell is currently lacking. In this article, we conducted a monomer level thermal runaway test on NCA|SiC pouch cell and NCM811|SiC pouch cell through the accelerated rate calorimetry (ARC) test. The results showed that the {T1, T2, T3} of NCA|SiC pouch cell and NCM811|SiC pouch cell are {113.8 °C, 230.4 °C, 801.4 °C} and {91.3 °C, 202.1 °C, 745 °C}, respectively. Then the thermal stability of NCA and NCM811 was tested by differential scanning calorimeter coupled with thermal gravimetric analysis, and mass spectrometry (DSC-TG-MS). The results showed that the phase transition temperature of NCA is higher than that of NCM811. However, when NCA and NCM811 were mixed with anode electrode materials or electrolyte, NCA produced significantly more heat than NCM811. By confirming the thermal properties of NCA|SiC pouch cell and NCM811|SiC pouch cell, a deeper understanding of battery thermal runaway was achieved, which is helpful for the design of high-safety lithium-ion batteries in the future.

High-performance Li/LiNi0.8Co0.1Mn0.1O2 batteries enabled by optimizing carbonate-based electrolyte and electrode interphases via triallylamine additive

Lithium (Li) metal batteries (LMBs), paired with high-energy–density cathode materials, are promising to meet the ever-increasing demand for electric energy storage. Unfortunately, the inferior electrode–electrolyte interfaces and hydrogen fluoride (HF) corrosion in the state-of-art carbonate-based electrolytes lead to dendritic Li growth and unsatisfactory cyclability of LMBs. Herein, a multifunctional electrolyte additive triallylamine (TAA) is proposed to circumvent those issues. The TAA molecule exhibits strong nucleophilicity and contains three unsaturated carbon–carbon double bonds, the former for HF elimination, the later for in-situ passivation of aggressive electrodes. As evidenced theoretically and experimentally, the preferential oxidation and reduction of carbon–carbon double bonds enable the successful regulation of components and morphologies of electrode interfaces, as well as the binding affinity to HF effectively blocks HF corrosion. In particular, the TAA-derived electrode interfaces are packed with abundant lithium-containing inorganics and oligomers, which diminishes undesired parasitic reactions of electrolyte and detrimental degradation of electrode materials. When using the TAA-containing electrolyte, the cell configuration with Li anode and nickel-rich layered oxide cathode and symmetrical Li cell deliver remarkably enhanced electrochemical performance with regard to the additive-free cell. The TAA additive shows great potential in advancing the development of carbonate-based electrolytes in LMBs.

Surface Lattice Modulation through Chemical Delithiation toward a Stable Nickel-Rich Layered Oxide Cathode

Nickel-rich layered oxides (NLOs) are considered as one of the most promising cathode materials for next-generation high-energy lithium-ion batteries (LIBs), yet their practical applications are currently challenged by the unsatisfactory cyclability and reliability owing to their inherent interfacial and structural instability. Herein, we demonstrate an approach to reverse the unstable nature of NLOs through surface solid reaction, by which the reconstructed surface lattice turns stable and robust against both side reactions and chemophysical breakdown, resulting in improved cycling performance. Specifically, conformal La(OH)3 nanoshells are built with their thicknesses controlled at nanometer accuracy, which act as a Li+ capturer and induce controlled reaction with the NLO surface lattices, thereby transforming the particle crust into an epitaxial layer with localized Ni/Li disordering, where lithium deficiency and nickel stabilization are both achieved by transforming oxidative Ni3+ into stable Ni2+. An optimized balance between surface stabilization and charge transfer is demonstrated by a representative NLO material, namely, LiNi0.83Co0.07Mn0.1O2, whose surface engineering leads to a highly improved capacity retention and excellent rate capability with a strong capability to inhibit the crack of NLO particles. Our study highlights the importance of surface chemistry in determining chemical and structural behaviors and paves a research avenue in controlling the surface lattice for the stabilization of NLOs toward reliable high-energy LIBs.

Mo–F Co-Doping LiNi0.83Co0.11Mn0.06O2 Stabilizes the Structure and Induces Compact Primary Particle To Improve the Electrochemical Performance

The Li+/Ni2+ cation disorder, material pulverization, surface phase transition, and transition metal (TM) ion dissolution are important issues that plague nickel-rich layered oxide cathode materials. In this paper, doping LiNi0.83Co0.11Mn0.06O2 with Mo6+ cation and F– anion effectively alleviates the above problems. The Mo6+ reduces the cations mixing, and the strong electronegativity of F strengthens the bonding with transition metal ions to resist HF corrosion. Furthermore, compact primary particles with interfused and radially aligned morphology induced by Mo–F co-doping reduce stress damage during cycling. The enhancement of electrochemical performance by Mo–F co-doping is systematically researched in terms of structure, morphology, secondary spherical pulverization, structural phase transition, and dissolution of transition metal ions.

Elucidating local diffusion dynamics in nickel-rich layered oxide cathodes.

Elucidating Li-ion transport properties is essential for designing suitable methodologies to optimise electrochemical performance in Ni-rich cathodes for high energy density Li-ion batteries. Here, we report the local-scale Li-diffusion characteristics of a series of nickel-rich layered oxide cathodes, prepared via microwave methods, using muon spin relaxation methods. Our results detail the effects of cation dopants, selected for structure stability, on transport properties in candidate nickel-rich chemistries. We find that the local diffusion properties improve with increasing nickel content. Our results demonstrate that these observations are dependant on substitutional effects.

Operando visualization of kinetically induced lithium heterogeneities in single-particle layered Ni-rich cathodes

<h2>Summary</h2> Understanding how lithium-ion dynamics affect the (de)lithiation mechanisms of state-of-the-art nickel-rich layered oxide cathodes is crucial to improve electrochemical performance. Here, we directly observe two distinct kinetically induced lithium heterogeneities within single-crystal LiNi_xMn_yCo_(1−x−y)O₂ (NMC) particles using recently developed <i>operando</i> optical microscopy, challenging the notion that uniform (de)lithiation occurs within individual particles. Upon delithiation, a rapid increase in lithium diffusivity at the beginning of charge results in particles with lithium-poor peripheries and lithium-rich cores. The slow ion diffusion at near-full lithiation states—and slow charge transfer kinetics—also leads to heterogeneity at the end of discharge, with a lithium-rich surface preventing complete lithiation. Finite-element modeling confirms that concentration-dependent diffusivity is necessary to reproduce these phenomena. Our results demonstrate how kinetic limitations cause significant first-cycle capacity losses in Ni-rich cathodes.