Cation-disordered Rocksalt Research Articles

Screening Na-Excess Cation-Disordered Rocksalt Cathodes with High Performance.

The practical application of Na-ion cathode materials is currently restricted by their low energy density and sluggish dynamics, while the cation-disordered rocksalt (DRX) structures offer a possible solution to the challenge. In this study, among the 24 candidates containing d0 elements, we use mixing temperature as a descriptor to screen the synthesizable Na-excess DRX, and we have identified Na1.2Mn0.4Mo0.4O2 as the most promising candidate that exhibits a Na percolating fraction of 53%, which is higher than that of Li1.2Mn0.4Ti0.4O2 (35%) proposed in the previous study due to the larger lattice constant in Na-excess DRX cathodes. More importantly, Na1.2Mn0.4Mo0.4O2 is predicted to have a capacity of 228 mAh/g with an energy density of 552 Wh/kg derived from percolation theory and cluster-expansion Monte Carlo simulations, which is higher than that of Na1.3Nb0.3Mn0.4O2 and Na1.14Mn0.57Ti0.29O2 synthesized recently. For a better understanding, the redox mechanism is explored, which involves Mo4+/Mo6+, Mn3+/Mn4+, and O2-/On- (0 < n < 2), indicating the participation of anionic redox. Meanwhile, the Na+ diffusion prefers a divacancy mechanism via an o-t-o diffusion channel with a low diffusion barrier of 0.29 eV. This study expands the family of DRX for the cathode of Na-ion batteries with enhanced performance.

Thin film synthesis, structural analysis, and magnetic properties of novel ternary transition metal nitride MnCoN2

Recent high-throughput computational searches have predicted many novel ternary nitride compounds providing new opportunities for materials discovery in underexplored phase spaces. Nevertheless, there are hardly any predictions and/or syntheses that incorporate only transition metals into new ternary nitrides. Here, we report on the synthesis, structure, and properties of MnCoN2, a new ternary nitride material comprising only transition metals and N. We find that crystalline MnCoN2 can be stabilized over its competing binaries, and over a tendency of this system to become amorphous, by controlling growth temperature within a narrow window slightly above ambient condition. We find that single-phase MnCoN2 thin films form in a cation-disordered rocksalt crystal structure. X-ray photoelectron spectroscopy analysis suggests that MnCoN2 is sensitive to oxygen through various oxides and hydroxides binding to cobalt on the surface. X-ray absorption spectroscopy is used to verify that Mn3+ and Co3+ cations exist in an octahedrally coordinated environment, which is distinct from a combination of CoN and MnN binaries and in agreement with the rocksalt-based crystal structure prediction. Magnetic measurements suggest that MnCoN2 has a canted antiferromagnetic ground state below 10 K. We extract a Weiss temperature of θ=−49.7K, highlighting the antiferromagnetic correlations in MnCoN2. Published by the American Physical Society 2024

Interfacial deterioration in highly fluorinated cation-disordered rock-salt cathode: Carbonate-based electrolyte vs. ether-based electrolyte

Cation-disordered rock-salts (DRX) emerge as an intriguing class of high-capacity cathode materials, garnering significant attention in the development of advanced energy-storage systems. Fluorination strategies have been raised to regulate redox and structure for better DRX electrochemical performance. However, research on the interfacial processes during fluorinated DRX cycling remains limited. Here, we evaluate a highly fluorinated DRX, Li2Mn2/3Nb1/3O2F (LMNOF), in different electrolytes to correlate its cycling performance with distinct interfacial evolutions. During cycling in the carbonate-based electrolyte, a thick Mn-containing CEI forms on the LMNOF surface, leading to gradual capacity decay. Intriguingly, the addition of fluoroethylene carbonate (FEC) would bring about surface oxygen loss, Mn-ion dissolution and formation of a fluorinated surface layer by reacting with the LMNOF surface, which critically deteriorate the cycling performance. In comparison, the ether-based electrolyte is compatible with the LMNOF surface, resulting in a more favorable cycling stability. This work sheds light on the interfacial deterioration mechanism of LMNOF cathode in traditional carbonate-based electrolyte, emphasizing the importance of using advanced non-reactive electrolytes to enhance DRX performance.

Unlocking fast Li-ion transport in micrometer-sized Mn-based cation-disordered rocksalt cathodes

The development of cation-disordered rocksalt (DRX) cathodes has garnered worldwide attention due to their high capacity, broad chemical space and excellent structural flexibility. However, their low intrinsic Li-ion conductivity necessitates extensive particle pulverization, typically achieved through ball-milling process, which impedes large-scale production. In this work, we present a proton-exchange assisted strategy to activate the Li-ion transport in Mn-based DRX cathodes. Short-range spinel-like ordering is observed to form within the DRX matrix after the post treatment, which significantly enhances the intrinsic Li ion mobility. Notably, more than 280 mAh g−1 discharge capacity can be delivered at a slow rate from micrometer-sized particles with an overall disordered cation arrangement, which retains more than 150 mAh g−1 when cycled at a very high rate of 2000 mA g−1. Furthermore, we also demonstrate that the electrochemical performance of the post-treated cathodes can be further optimized by fine-tuning the reaction parameters.

Is There Hope for Ni-Based Disordered Rock Salt Cathode Materials?

Li-ion batteries achieved in the last 3 decades extremely high energy densities, making them the energy storage devices of choice for the electrification of our society. Despite this improvement, their energy density is still low as compared to gasoline, motivating further research towards materials with better performances. State of the art positive electrodes are nowadays layered materials with a ratio Li:M of 1:1, with M being one or multiple transition metals. LiNiO2 is a noteworthy example. Disordered rock salt (DRX) materials were instead thought to be electrochemically inactive until the development of a percolation theory,1 which demonstrated that lithium-rich materials (Li:M>1.1) with a cation disordered rock-salt structure (DRX) can achieve high reversible specific capacities. The general formula of these lithium-rich compounds can be written as Li1+y(MM′)1−yO2 where the Li content ranges usually from 1.05 to 1.33. With M is indicated a redox active specie (Mn, Ni, Fe, Cr, V) and M’ is typically a d0 element, which is redox inactive during charge and discharge and well accommodates the disordered structure.2 Materials with such structures have been shown to deliver extremely high specific capacities, resulting in equally high specific energies.3 In our recent work we investigated two DRX compounds based on Ni-redox. First, Li2NiO3, which is layered (with monoclinic distortion), but that decomposes to a disordered rock salt structure with cycling. The material displays interesting defect chemistry but fast capacity fading.4 More recently, we developed a class of Li-rich compounds with the chemical composition Li2yNiyTi2-3yO2 (y = 0.50, 0.55, 0.60, 0.67). These samples were prepared via solid-state reaction at three different temperatures (700 °C, 800 °C, 900 °C). By X-ray and neutron diffraction, we demonstrated a pure phase solid solution at high temperature, yet, by decreasing the synthesis temperature and increasing the Li content, phase separation occurs into a rock salt-type and a Li2TiO3 phase. The synthesis process has been also verified by DFT and by in situ X-ray diffraction. In all DRX materials synthesized, the electrochemical performances revealed a strong voltage hysteresis between charge and discharge and fast capacity fade.5,6 This raises then the question of whether any Ni-based DRX material can provide high capacity, high rate capability and stability, while avoiding the commonly encountered large hysteresis, or whether this can only be achieved in Mn-based compounds. In this presentation, by discussing our own work and recent literature reports, we aim at answering this question. Bibliography Urban, Alexander, Jinhyuk Lee, and Gerbrand Ceder. “The Configurational Space of Rocksalt-Type Oxides for High-Capacity Lithium Battery Electrodes.” Advanced Energy Materials4, 13: 1400478.Chen, Dongchang, Juhyeon Ahn, and Guoying Chen. “An Overview of Cation-Disordered Lithium-Excess Rocksalt Cathodes.” ACS Energy Letters, 2021, 1358–76.Clément et al., Cation-disordered rocksalt transition metal oxides and oxyfluorides for high energy lithium-ion cathodes, Energy & Environmental Science, 2020, 13 (2), 345-373Bianchini et al., From LiNiO2 to Li2NiO3: Synthesis, Structures and Electrochemical Mechanisms in Li-Rich Nickel Oxides, Chem. Mater. 2020, 32, 9211−9227Reitano, et al. Manuscript submitted, 2024.Li, Biao, Khagesh Kumar, Indrani Roy, Anatolii V. Morozov, Olga V. Emelyanova, Leiting Zhang, Tuncay Koç, et al. “Capturing Dynamic Ligand-to-Metal Charge Transfer with a Long-Lived Cationic Intermediate for Anionic Redox.” Nature Materials21, 10: 1165–74.

A Novel Approach to Continuous and Scalable Synthesis of Cation-Disordered Rocksalt Cathodes

Cation disordered rocksalts (DRX) are an emerging class of high energy density LIB cathodes that can utilize earth-abundant and low-cost redox active transition metals. The DRX cathodes can be synthesized through a rich chemistry of transition metals, where commonly, metal-oxide precursors are combined with lithium source via ball-milling and calcined to achieve cation disordered phase. In this work, we present a new alternative synthesis method to the traditional solid-state synthesis, which provides scalable and continuous production of cathode precursors. A soft synthesis method in aqueous media was adopted to produce Mn-rich cathode precursors in large scale, through which homogenous mixing of the introduced transition metal cations was achieved. Here we report the electrochemical and structural properties of as-synthesized DRX cathodes with various Mn-compositions.

Enhanced Electrochemical Performance of Disordered Rocksalt Cathode in a Localized High Concentration Electrolyte

Lithium (Li) transition metal oxides with layered structure, commonly employed as cathodes in Li-ion batteries, exhibit limited capacity, and employ less abundant and costly materials, raising sustainability concerns amid surging battery demand. Addressing this, lithium rich cation disordered rock salt cathode (DRX) materials have garnered substantial attention as they offer high capacity and cost benefits. Manganese (Mn) based DRXs, in particular, show promise due to the utilization of earth abundant materials and good thermal stability of Mn. However, these cathodes often face challenges when cycled in state-of-the-art carbonate-based electrolytes. These include severe side reactions between the cathode and the electrolyte, transition metal dissolution and structural instability of the cathode particles all of which result in fast capacity fading. In this work, an advanced localized high concentration electrolyte (LHCE) is developed to mitigate these problems and enable stable cycling of Li1.2Mn0.6Ti0.2O2 (LMTO). The developed LHCE exhibits high voltage stability, forming an ultrathin and stable electrode/electrolyte interphase. Consequently, Li||LMTO half cells with the developed LHCE demonstrate increased capacity, enhanced cycling stability and superior rate capabilities compared to the cells with the conventional electrolyte. For instance, the Li||LMTO cells cycled in LHCE show higher initial capacity of 205.2 mAh/g, and a capacity retention of 72.5 % in contrast to an initial capacity of 187.7 mAh/g and a capacity retention of 19.9 % observed in Li||LMTO cells with the conventional electrolyte after 200 cycles at a current density of 20 mA/g. This work paves the way for the development of practical DRX cathode- based high-energy Li batteries.

Rapid in-Situ Electrochemical Formation of Partially Disordered Spinel from Mn-Rich Disordered Rocksalt Cathodes

We present the development of an electrochemical formation method that enables rapid and in-situ formation of a partially disordered spinel phase from an initially disordered rocksalt (DRX) cathode. Recent studies on Mn-rich DRX materials have demonstrated the emergence of a spinel-like phase during cycling, resulting in improved capacity retention, energy density, and rate capability compared to materials which do not transform1,2,3. However, this transformation process typically requires weeks of cycling at relatively low rates, posing significant challenges for the commercialization of such materials.To gain a deeper understanding of this transformation process, we carry-out a systematic study to determine whether the formation process of these spinel-like materials can be accelerated through a precycling formation process. By employing a novel electrochemical approach to purposefully stimulate the transformation, we successfully reduce the time required from several weeks to as little as one day for Mn-rich DRX. Extended cycling and synchrotron X-ray diffraction confirm that these materials exhibit both equivalent performance and resulting structure to those obtained through conventional cycling over a much longer duration. Further characterization of this material using HAADF and 4-D STEM reveals the complex local structure of the spinel-like partial ordering. It is hoped that such a practical electrochemical formation method will allow for an acceleration of research on these earth-abundant and energy-dense materials. Li, L.; Lun, Z.; Chen, D.; Yue, Y.; Tong, W.; Chen, G.; Ceder, G.; Wang, C. Fluorination-Enhanced Surface Stability of Cation-Disordered Rocksalt Cathodes for Li-Ion Batteries. Adv Funct Mater 2021, 31 (25), 2101888. https://doi.org/10.1002/adfm.202101888.Ahn, J.; Giovine, R.; Wu, V. C.; Koirala, K. P.; Wang, C.; Clément, R. J.; Chen, G. Ultrahigh-Capacity Rocksalt Cathodes Enabled by Cycling-Activated Structural Changes. Adv. Energy Mater. 2023. https://doi.org/10.1002/aenm.202300221. Cai, Z.; Ouyang, B.; Hau, H.-M.; Chen, T.; Giovine, R.; Koirala, K. P.; Li, L.; Ji, H.; Ha, Y.; Sun, Y.; Huang, J.; Chen, Y.; Wu, V.; Yang, W.; Wang, C.; Clément, R. J.; Lun, Z.; Ceder, G. In Situ Formed Partially Disordered Phases as Earth-Abundant Mn-Rich Cathode Materials. Nat. Energy 2023, 1–10. https://doi.org/10.1038/s41560-023-01375-9.

Chemical Origin of in Situ Carbon Dioxide Outgassing from a Cation-Disordered Rock Salt Cathode.

In situ carbon dioxide (CO2) outgassing is a common phenomenon in lithium-ion batteries (LiBs), primarily due to parasitic side reactions at the cathode-electrolyte interface. However, little is known about the chemical origins of the in situ CO2 released from emerging Li-excess cation-disordered rock salt (DRX) cathodes. In this study, we selectively labeled various carbon sources with 13C in cathodes containing a representative DRX material, Li1.2Mn0.4Ti0.4O2 (LMTO), and performed differential electrochemical mass spectrometry (DEMS) during galvanostatic cycling in a carbonate-based electrolyte. When charging LMTO cathodes, electrolyte solvent (EC) decomposition is the dominant source of the CO2 outgassing. The amount of EC-originated CO2 is strongly correlated with the total surface area of carbon black in the electrode, revealing the critical role of electron-conducting carbon additives in the electrolyte degradation mechanisms. In addition, unusual bimodal CO2 evolution during the first cycle is found to originate from carbon black oxidation. Overall, the underlying chemical origin of in situ CO2 release during battery cycling is highly voltage- and cycle-dependent. This work further provides insights into improving the stability of DRX cathodes in LiBs and is envisioned to help guide future relevant material design to mitigate parasitic reactions in DRX-based batteries.

Enhanced Electrochemical Performance of Disordered Rocksalt Cathodes in a Localized High‐Concentration Electrolyte

Enhanced Electrochemical Performance of Disordered Rocksalt Cathodes in a Localized High‐Concentration Electrolyte

Nb-doping of cation-disordered rocksalt oxides with B2O3 surface modification for superior performance cathode

As the growing price and inadequate reserves of cobalt, the demand for cobalt-free materials with superior energy density to apply in Li-ion batteries has increased distinctly. Li-rich cation disordered rocksalt (DRX) material has aroused research hotspot because of high specific capacity and wide compositional space. However, irreversible oxygen loss as well as sluggish kinetic raise the problem in large polarization and inevitable capacity decay in cycling process, which have impeded the commercialization of these electrode materials. In this work, we have synthesized cobalt-free boron trioxide (B2O3)-modified Li1.2Ni0.3Ti0.3Nb0.2O2 compounds with cation disordered rocksalt structure through mechanochemical method. It is a fact that B2O3-modified cathodes possess outstanding cyclic stability as well as rate properties. Particularly, the Li1.2Ni0.3Ti0.3Nb0.2O2 electrode with 2.0 wt% B2O3 displayed a competitive capacity of 192.4 mAh/g at 10 mA g−1 and retained 134.7 mAh/g after 100 charge/discharge times. The redox mechanism is explored through ex-situ XPS measurement, verifying the reversible cationic redox of Ni2+/Ni4+ accompanying small Ti4+/Ti3+ reduction and anionic O2−/O− evolution, which results in unusual high capacity. Such an optimized surface modification combines with the Nb doping, can promote Li ion transport, reduce polarization, protect cathode from reacting with electrolyte. These findings provide important implications to improve performance of DRX cathodes.

Dialing in the Voltage Window: Reconciling Interfacial Degradation and Performance Decay for Cation-Disordered Rocksalt Cathodes

Li-excess, cation-disordered rocksalt (DRX) cathode materials possess promising electrochemical properties and resource-friendly compositions, making them attractive Li-ion cathode materials. A key drawback of DRX materials is high interfacial reactivity that leads to electrolyte degradation, which ultimately causes a decay in cell performance. In this work, differential electrochemical mass spectrometry (DEMS) is used to study electrolyte degradation processes during initial cycling of DRX cathodes. Comparing outgassing during cycling in six unique voltage windows with upper cutoff voltages of 4.6 or 4.8 V vs Li/Li+ and lower cutoff voltages of 1.5, 1.85, or 2 V vs Li/Li+ reveals the high- and low-voltage processes that separately contribute to degradation at the cathode-electrolyte interface. Charging to high voltages is shown to drive oxidative degradation, consistent with conventional understanding of interfacial reactivity at the cathode-electrolyte interface. Surprisingly, discharging below 2.0 V vs Li/Li+ is also revealed to drive reductive degradation at the same interface, which induces elevated CO2 evolution on the following charge. Subsequently, extended cycling of electrolyte-lean DRX-graphite full-cells shows that performance decay is exacerbated by cycling in voltage ranges that induce interfacial degradation. Post-mortem analysis also indicates notable loss of active Li and dissolution of Mn and Ti from the DRX cathode. Collectively, these analyses demonstrate a clear link between electrolyte degradation and performance decay during cycling of DRX materials. This work highlights the necessity of voltage window optimization to maximize DRX cycling performance and the importance of cell design when evaluating cycling stability.

Regulating d0 transition metals and facilitating high-performance Li-excess cation-disordered rock salt cathode materials

A systematic study was performed on Ti-doped Li1.2Mn0.43+TixMn0.4−x4+O2, which revealed the fast kinetics of Li diffusion with an improvement in the electrochemical property of MT0−1, thus providing a guideline for DRXs cathode materials design.

Performance evaluation of lithium metal rechargeable batteries with a lithium excess cation-disordered rocksalt based positive electrode under high mass loading and lean electrolyte conditions

Operation of 500 W h kg−1 class rechargeable batteries was demonstrated. Non-destructive XCT analysis revealed volume expansion of the lithium metal electrode as the primary reason for the capacity fading.

Synthesis, Structural and Electrochemical Investigation of Disordered Rock Salt Compounds Based on Ni and Ti

Li-ion batteries achieved in the last 3 decades extremely high energy densities, making them the energy storage devices of choice for the electrification of our society. Despite this improvement, their energy density is still low as compared to gasoline, motivating further research towards materials with better performances. State of the art positive electrodes are nowadays layered materials with a ratio Li:M of 1:1, with M being one or multiple transition metals. Disordered rock salt (DRX) materials without a layered structure were thought to be electrochemically inactive. With the development of the percolation theory, 1(Urban, Lee, and Ceder) it was demonstrated that lithium-rich materials (Li:M>1) with a cation disordered rock-salt structure (DRX) can achieve high reversible specific capacities. The general formula of these lithium-rich compounds can be written Li1+y(MM′)1−yO2 where the Li content ranges usually from 1.05 to 1.33, essential to promote Li percolation pathways. With M is indicated a redox active specie (Mn, Ni, Fe, Cr, V) and M’ is typically a d0 element, which is redox inactive during charge and discharge and therefore stabilizes the disordered structure and acting as charge compensator.2 (Chen, Ahn, and Chen)In this work a class of Li-rich compounds with the chemical composition Li2yNiyTi2-3yO2 has been investigated (y = 0.50, 0.55, 0.60, 0.67). These samples were prepared via solid-state reaction at three different temperatures (700 °C, 800 °C, 900 °C). X-ray diffraction has been used to determine the crystal structure of the samples, revealing a predominant rock salt-type phase. However, by decreasing the synthesis temperature and increasing the Li content, phase separation occurs into a rock salt-type and a Li2TiO3 phase. The synthesis has been also verified by DFT and by in situ X-ray diffraction. Neutron diffraction experiment have been carried out to fully understand the cationic distribution in the samples. Finally, the electrochemical performances of the samples have been investigated in Li half cells, revealing a strong voltage hysteresis between charge and discharge.3 (Li et al.) Bibliography Urban, Alexander, Jinhyuk Lee, and Gerbrand Ceder. “The Configurational Space of Rocksalt-Type Oxides for High-Capacity Lithium Battery Electrodes.” Advanced Energy Materials 4, no. 13 (September 2014): 1400478. https://doi.org/10.1002/aenm.201400478.Chen, Dongchang, Juhyeon Ahn, and Guoying Chen. “An Overview of Cation-Disordered Lithium-Excess Rocksalt Cathodes.” ACS Energy Letters, March 17, 2021, 1358–76. https://doi.org/10.1021/acsenergylett.1c00203.Li, Biao, Khagesh Kumar, Indrani Roy, Anatolii V. Morozov, Olga V. Emelyanova, Leiting Zhang, Tuncay Koç, et al. “Capturing Dynamic Ligand-to-Metal Charge Transfer with a Long-Lived Cationic Intermediate for Anionic Redox.” Nature Materials 21, no. 10 (October 2022): 1165–74. https://doi.org/10.1038/s41563-022-01278-2

Direct Mapping of Fluorine in Cation Disordered Rocksalt Cathodes

Direct Mapping of Fluorine in Cation Disordered Rocksalt Cathodes

Atomic-scale probing of short-range order and its impact on electrochemical properties in cation-disordered oxide cathodes

Chemical short-range-order has been widely noticed to dictate the electrochemical properties of Li-excess cation-disordered rocksalt oxides, a class of cathode based on earth abundant elements for next-generation high-energy-density batteries. Existence of short-range-order is normally evidenced by a diffused intensity pattern in reciprocal space, however, derivation of local atomic arrangements of short-range-order in real space is hardly possible. Here, by a combination of aberration-corrected scanning transmission electron microscopy, electron diffraction, and cluster-expansion Monte Carlo simulations, we reveal the short-range-order is a convolution of three basic types: tetrahedron, octahedron, and cube. We discover that short-range-order directly correlates with Li percolation channels, which correspondingly affects Li transport behavior. We further demonstrate that short-range-order can be effectively manipulated by anion doping or post-synthesis thermal treatment, creating new avenues for tailoring the electrochemical properties. Our results provide fundamental insights for decoding the complex relationship between local chemical ordering and properties of crystalline compounds.

Investigation on the Origin of Sluggish Anionic Redox Kinetics in Cation-Disordered Cathode

Cation-disordered rock salt (DRX) cathodes exhibit high specific capacity due to the simultaneous use of anionic and cationic redox reactions. However, DRX systems face severe challenges that limit their practical applications; a most important challenge is their poor rate performance. In this work, the structure and morphology of Li1.17Ti0.58Ni0.25O2 (LTNO) were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), etc. In combination with various electrochemical characterizations, we found that the sluggish kinetics of anionic redox within LTNO can be the key reason for the inferior rate performance. By sample relaxation at moderate temperature and X-ray absorption near edge structure (XANES), the ligand-to-metal charge transfer process is verified to occur between O and Ni and exhibits a prolonged characteristic time of 113.8 min. This time-consuming charge transfer process is verified to be the very fundamental origin of the slow kinetics of oxygen oxidation and reduction. This claim is further supported by the galvanostatic intermittent titration technique (GITT) at different temperatures. These findings provide essential guidance for understanding and further optimizing cathodes with anion redox reactions not only in the context of DRX cathodes but also conventional Li-rich cathodes.

Enhanced Li+ Diffusion and Lattice oxygen Stability by the High Entropy Effect in Disordered-Rocksalt Cathodes.

Cation-disordered Rocksalt oxides (DRXs) are a promising new class of cathode materials for Li-ion batteries due to their natural abundance, low cost and great electrochemical performance. High entropy strategy in Mn-based DRXs appears to be an effective strategy for improving the rate capability, but it suffers from challenges including capacity degradation. The present paper reports a new group of high entropy DRXs (HE DRX) based on Ni2+ -Nb5+ pair; the structural and chemical evolution upon cycling of DRXs with an increasing transition metal (TM) species are systematically investigated. An explanation is proposed for how the crystal field stability energy determines that HE DRX could exist in single Rocksalt solid solution structures. We further reveal that the charge compensation mechanism in HE DRX is the result of various TM synergistic effect. More importantly, through various in situ and ex situ techniques and theoretical calculation, the effective integration of more TM cation species within the HE DRX framework promotes better Li+ diffusion and improves lattice oxygen stability, consequently increasing capacity upon cycling.

Separating O-Redox and Mn-Redox Voltage Hysteresis in a Cation-Disordered Rock-Salt Cathode

Pronounced voltage hysteresis is commonly associated with oxygen redox in Li-excess cathode materials. However, they often involve coexisting transition-metal and oxygen redox, whose contributions to hysteresis are challenging to distinguish. In this work, a two-step aqueous redox titration was developed with the aid of mass spectrometry (MS) gas analyzer to quantify two coexisting solid-phase analytes, namely oxidized oxygen and Mn3+/4+ in a representative Li-excess cation-disordered rock salt (DRX) material. Two MS-countable gas molecules evolve from two separate titrant-analyte reactions, which allows decoupling Mn and O redox capacities. As incremental redox capacities are quantitatively decoupled, each redox voltage hysteresis can be further evaluated through deconvoluted energy efficiency and overvoltages. Overall, a low DRX operating efficiency arises not only from quasi-static voltage hysteresis of O redox, but also from asymmetric Mn-redox overvoltages. The results reveal that O redox is not always the only culprit for a low energy efficiency and slow kinetics, but instead discharging overvoltage, associated with transition-metal redox, can significantly drag down overall operating efficiency. This work further shows the potential of designing new analytical workflow to experimentally diagnose various DRX materials and inform improvement direction.