Decoding the Structural Controversy of Li- and Mn-Rich Cathodes through Synthesis-Dependent Domain Evolution
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Decoding the Structural Controversy of Li- and Mn-Rich Cathodes through Synthesis-Dependent Domain Evolution
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  • Minji Kim
    Minji Kim
    Department of Materials Science and Engineering, Korea University, Seoul 02841, Republic of Korea
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    Orcidhttps://orcid.org/0000-0002-9136-0866
  • Dohyun Kim
    Dohyun Kim
    Department of Materials Science and Engineering, Korea University, Seoul 02841, Republic of Korea
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  • Hyeona Jo
    Hyeona Jo
    Department of Materials Science and Engineering, Korea University, Seoul 02841, Republic of Korea
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  • Keun Chan Yoo
    Keun Chan Yoo
    Department of Materials Science and Engineering, Korea University, Seoul 02841, Republic of Korea
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  • Hyeokjun Park*
    Hyeokjun Park
    Department of Materials Science and Engineering, Korea University, Seoul 02841, Republic of Korea
    *Email: [email protected]
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    Orcidhttps://orcid.org/0000-0003-3367-8881
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ACS Applied Energy Materials

Cite this: ACS Appl. Energy Mater. 2026, XXXX, XXX, XXX-XXX
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https://doi.org/10.1021/acsaem.5c03989
Published March 13, 2026

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Abstract

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Li- and Mn-rich layered oxides (LMR) have attracted significant research interest because of their potential merits of low cost and high capacity that exceed current Ni-rich cathodes. Despite nearly two decades of intensive investigations, however, the structural nature of LMRs, particularly with respect to Li2MnO3-like domains has remained under debate. Early structure models described LMRs as an intergrowth of monoclinic Li2MnO3 (C2/m) and rhombohedral LiTMO2 (R3̅m) phases. In contrast, subsequent studies revealed that these structural signatures can also arise from local Li–Mn ordering within a single solid-solution framework. These conflicting interpretations have complicated a clear understanding of the structure–property relationships and impeded progress toward the commercial implementation of LMRs. In this perspective, we present a unified view showing that the structural state of LMRs is determined not solely by bulk composition but critically by synthesis conditions. By integrating evidence related to precursor chemistry and calcination parameters, we elaborate on how cation homogeneity, the distribution of excess Li, Mn oxidation states, and diffusion kinetics collectively dictate whether Li2MnO3 forms extended slabs or nanoscale, delocalized structural motifs. Through a comparative assessment of synthesis routes, we review how LMRs span a continuous structural spectrum rather than conforming to a simple binary phase model. Finally, we outline synthesis-driven design principles for controlling the evolution of Li2MnO3 domains, providing practical guidelines to develop structurally robust, high-energy LMR cathodes.

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Introduction

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The rapid expansion of electric vehicles and grid-scale energy storage has intensified the demand for lithium-ion batteries (LIBs) that combine high energy density with low cost and long-term sustainability. (1) In this context, the reliance on earth-abundant transition metals and the development of high-capacity cathode materials have become central to both economic competitiveness and supply chain resilience. (2,3) Li- and Mn-rich layered oxides (LMRs, typically written as xLi2MnO3·(1 – x)LiTMO2, TM: 3d-transition metal) have garnered considerable attention as a promising high-energy cathode for LIBs. (4,5) Specific capacities of LMRs often exceed ∼250 mAh g–1 by harnessing lattice-oxygen redox, outperforming many Ni-rich systems while relying on Mn-rich compositions, which offer cost and sustainability advantages. (6) Despite this promise, commercialization remains hindered by severe voltage decay, (7,8) large hysteresis, (9,10) oxygen release, (5,11,12) and structural degradation (13,14) upon cycling, all of which erode energy efficiency and cycle life.
A major unresolved issue is that the fundamental structure of LMRs remains controversial because the crystal structure has a profound impact on oxygen-redox behavior. (15) LMRs are often viewed as consisting of two structural motifs: a monoclinic Li2MnO3-like component (C2/m) and a rhombohedral LiTMO2-like component (R3̅m). The longstanding debate centers on whether these features represent two coexisting phases or local monoclinic ordering within a single solid-solution lattice. Early structural studies, exploiting high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), and X-ray diffraction (XRD), suggested the presence of distinct Li2MnO3-type domains intergrown with LiMO2 layers, leading to the widespread adoption of a two-phase composite model. (1,3,6) However, as analytical methods advanced, several studies challenged this rigid two-phase picture. Studies relying on nuclear magnetic resonance (NMR), pair distribution function (PDF) analysis, and advanced diffraction refinements indicated that LMRs may instead form a single-phase solid-solution with varying degrees of local Li–Mn ordering rather than macroscopic phase separation. (16) Parallel studies showed that excess-Li localization, not discrete phase boundaries, governs the emergence of Li2MnO3-like features, Mn clustering, and oxygen-redox reversibility. (17,18) These results contributed to a shift in the community’s interpretation toward a continuum model, where the degree of Li/TM ordering and domain definition varies smoothly rather than discretely. Most recently, a viewpoint has emerged: the structural state of LMRs is synthesis-dependent, not solely composition-dependent. Systematic comparisons between materials of identical nominal composition revealed that precursor homogeneity, thermal history, and oxygen partial pressure can tune the system across a range from clearly resolved Li2MnO3–LiTMO2 domains and nearly homogeneous monoclinic solid-solutions. (19−21) This framework reconciles prior contradictions showing why early studies, often based on solid state or poorly mixed precursors, observed strong two-phase characteristics, while later sol–gel or coprecipitation approaches produced solid-solution-like behavior.
In this Perspective, we revisit the conventional definitions of LMR structures and highlight the critical role of synthesis conditions in shaping their structural characteristics. That is, the structure of LMRs may not be an inherent material property but rather a synthesis-derived outcome. We trace the evolution of structural interpretation, starting from an initial two-phase model to lithium localization-based ordering, and ultimately to a structural continuum dependent on synthesis conditions. Based on this, we aim to provide a contextual framework for interpreting existing results from LMR studies under different synthesis conditions. Accordingly, considering Li2MnO3-like and LiTMO2-like features as synthesis-tunable structural motifs can serve as a renewed perspective and a conceptual strategy for rational materials design for the LMR community. This synthesis-structure–property perspective provides concrete guidance for tailoring domain size, Li–Mn ordering, and oxygen-redox stability, thereby accelerating the development of high-energy and durable Li–Mn-rich layered cathodes toward commercial implementation.

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Brief Historical Overview of the Structural Controversy in LMRs

Understanding whether LMRs adopt a true two-phase composite or a single-phase solid-solution has been central to interpreting the role of Li2MnO3-like domains in their electrochemical behavior. Although both viewpoints originate from observations of Li/TM ordering within the same layered framework, they differ fundamentally in how the Li2MnO3 (C2/m) component and the LiTMO2 (R3̅m) component are structurally arranged. Figure 1 provides a comparative overview of these two interpretations. In the two-phase composite model, the material is viewed as an intergrowth of monoclinic Li2MnO3 (C2/m) slabs and rhombohedral LiTMO2 (R3̅m) slabs. As illustrated in Figure 1a, the two components retain distinct Li–TM arrangements: Li2MnO3 displays Li–Mn honeycomb ordering within the TM layers and characteristic Li in the transition-metal layer (LiTM), whereas LiTMO2 contains a random TM distribution without long-range honeycomb order. This structural distinction implies that the two motifs can be spatially separated within a particle, forming nanometer-scale domains with different symmetries. By contrast, the solid-solution model asserts that Li2MnO3-like features do not arise from discrete monoclinic phase separation but rather from local Li–Mn ordering embedded within a single averaged layered lattice. In this interpretation, the material maintains an overall R3̅m-like symmetry but locally exhibits varying degrees of Li/TM ordering. As depicted in the lower panel in Figure 1a, monoclinic-like environments emerge as short-range ordered clusters, not as independent structural phases. This view emphasizes the continuity of the oxygen close-packed lattice and argues that long-range monoclinic symmetry is rarely achieved at the particle scale.

Figure 1

Figure 1. Structural signatures and diagnostic characterization of Li2MnO3 domains in Li- and Mn-rich layered oxides. (a) Schematic illustration comparing the two structural interpretations of Li-rich layered oxides: a two-phase intergrowth model consisting of monoclinic Li2MnO3 (C2/m) and rhombohedral LiTMO2 (R3̅m) domains, and a solid-solution model in which Li–Mn ordering is embedded as local motifs within a single layered lattice. (b) Powder XRD patterns for Li-rich layered oxides with increasing Li2MnO3 content, showing the emergence and growth of monoclinic superstructure reflections. Reproduced from ref (22) under CC BY-NC-ND 4.0 license. Copyright 2019, The Electrochemical Society. (c) HAADF-STEM images and simulated atomic configurations demonstrating Li/Mn honeycomb ordering and the contrast differences between Li columns and TM columns, used to distinguish Li2MnO3-like local ordering from fully random TM distributions. Reproduced with permission from ref (23). Copyright 2012, American Chemical Society.

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Powder XRD patterns have served to distinguish between the two competing structural interpretations of LMRs. As shown in Figure 1b, (22) compositions varying with progressively higher Li excess exhibit additional reflections in the 20–23° (λ = 0.5 Å) region, which cannot be indexed within a simple R3̅m layered framework. Instead, these features correspond to monoclinic superstructure reflections─most notably the 020m, 110m and 111m peaks─commonly associated with the long-range honeycomb ordering of Li and Mn in the C2/m lattice. According to the two-phase interpretation, these superlattice reflections arise from Li2MnO3-like domains embedded within a LiTMO2 matrix, and their visibility is taken as evidence for a physically distinct monoclinic component. This interpretation is consistent with earlier diffraction analyses, (4,23,24) where increasing Li content systematically strengthened these monoclinic-type peaks, reflecting growth of Li–Mn ordered domains. In addition, high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) observations have also been used as evidence suggesting that two distinct structural components coexist within Li-rich layered oxides. As shown in Figure 1c, the Li2MnO3-like monoclinic domains exhibit strong Z-contrast arising from Li/Mn honeycomb ordering, which produces a periodic brightness pattern reflecting the clear distinction between TM-rich and Li-rich columns. (23) However, the LiTMO2 (R3̅m) regions within the same particle show a more uniform contrast, with the disappearance of such periodic features, indicating that the two structures are continuously connected. Based on these pronounced contrast differences and the presence of discernible interphase boundaries, the study interpreted the material not as a single solid-solution but rather as a two-phase composite containing structurally distinct domains. By contrast, HAADF-STEM images show continuous lattice contrast without abrupt domain boundaries, despite the presence of mild Li–Mn ordering in other report. (24) Rather than interpreting these features as evidence of spatially separated monoclinic and rhombohedral phases, the authors suggested that Li2MnO3-like environments are embedded as short-range ordered motifs within a single layered lattice. Importantly, this interpretation does not deny the existence of Li–Mn honeycomb ordering but instead challenges the assumption that such ordering necessarily corresponds to discrete phase separation. Together, these contrasting HAADF-STEM observations illustrate how similar local structural signatures have been used to support fundamentally different structural models.
Figure 2 presents a conceptual summary of representative experimental data sets arranged in chronological order to illustrate how interpretations of the structural nature of the Li2MnO3 domain in LMRs have evolved. Early studies often accepted a two-phase interpretation in which Li2MnO3 (C2/m) and LiTMO2 (R3̅m) structures coexist within the same particle. Later, however, new evidence suggested that these observations may instead arise from the local distribution (localization) of excess Li rather than from discrete phases. Most recently, a synthesis-dependent structural model has emerged, proposing that Li2MnO3-domain coherence varies with precursor chemistry, thermal history, and oxygen partial pressure─even when the overall composition remains the same.

Figure 2

Figure 2. Chronological evolution of structural interpretations of Li2MnO3domain in LMRs. (a) 6Li MAS NMR spectra of Li2MnO3 samples prepared at 1000 °C (blue) and 850 °C (black). Reproduced with permission from ref (25). Copyright 2005, Elsevier. (b) Convergent-beam electron diffraction (CBED) patterns comparing LiMn0.5Ni0.5O2 and Li1.048[Mn0.333Ni0.333Co0.333]0.952O2. Reproduced with permission from ref (26). Copyright 2006, Elsevier. (c) HAADF-STEM imaging identifying localized excess-Li regions responsible for Li2MnO3-like contrast in LMR particles. Reproduced with permission from ref (17). Copyright 2020, Wiley. (d) X-ray diffraction superlattice peaks (20–25°) comparing DS-LMR (delocalized excess-Li) and LS-LMR (localized excess-Li). Reproduced with permission from ref (18). Copyright 2021, Wiley. (e) Scanning electron microscopy and XRD analysis correlating superstructure evolution and stacking faults with precursor-dependent synthesis pathways (Solid state and Sol–gel method). Reproduced from ref (21) under CC BY 4.0 license. Copyright 2021, American Chemical Society. (f) In situ STEM tracking of sol–gel precursors during heating, revealing atomic-level TM mixing. Reproduced with permission from ref (27). Copyright 2022, Elsevier.

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The early two-phase interpretation was primarily supported by analyses such as XRD, NMR, and convergent beam electron diffraction (CBED). Bréger et al. reported that 6Li magic-angle spinning (MAS) NMR spectra of Li2MnO3 samples subjected to different thermal treatments exhibit nearly identical resonance features as shown in Figure 2a, indicating that the local Li environment remains stable. (25) These results strongly support the idea that Li2MnO3 structural blocks persist as an independent monoclinic phase within the LMR structure. Similarly, Thackeray et al. showed through CBED patterns (Figure 2b) that intense reflections correspond to R3̅m symmetry, while weaker reflections match C2/m symmetry. (26) In certain compositions, all reflections were indexed solely to C2/m. These findings reinforced the interpretation that two structurally distinct phases coexist within LMR particles, solidifying the two-phase intergrowth model as the prevailing viewpoint at the time. However, the two-phase model alone could not explain several structural signatures, such as contrast variations in HAADF-STEM images and changes in XRD superlattice peaks, prompting researchers to reconsider the governing structural variable. A new perspective emerged, proposing that the key factor is not “phase separation” but rather the degree of Li localization in the transition-metal layer. Hwang et al. clearly distinguished localized-LMR (L-LMR) from delocalized-LMR (D-LMR) using HAADF-STEM images (Figure 2c), showing that the coherence of Li2MnO3-like ordering varies dramatically depending on the strength and periodicity of Li contrast even in materials of identical composition. (17) This marked a conceptual shift: LMRs can appear two-phase-like or solid-solution-like depending on the extent of Li ordering, rather than on the actual presence of discrete phases.
Building on this idea, Hwang et al. also quantitatively demonstrated that the monoclinic superlattice peaks (020m, 110m, 111m) in the 20–25° region of XRD patterns (Figure 2d) are highly sensitive to the degree of excess-Li delocalization. (18) Li-excess delocalized (DS-LMR) samples exhibit weaker and broader peaks, indicating a highly delocalized structure with diminished Li–Mn honeycomb ordering, whereas Li-excess localized (LS-LMR) samples retain sharp, intense peaks reflective of strong Li2MnO3-like coherence. These observations provided direct evidence that LMR structures represent a continuum of Li-ordering states, rather than a sharply defined two-phase boundary. Recent studies further demonstrate that structural differences arise not from composition but from the synthetic pathway. Figure 2e highlights that the structural state of LMRs is strongly dictated by the precursor synthesis route. (21) Sol–gel precursors, which provide atomic-level cation homogeneity, suppress the formation of Li2MnO3-rich domains and yield a near–solid-solution structure. In contrast, solid state precursors with heterogeneous particle mixing promote early Mn-rich reactions during calcination, stabilizing more distinct Li2MnO3-like domains. Furthermore, recent in situ STEM heating experiments directly visualized the collapse of Li2MnO3-like stripe ordering with increasing temperature (27) (Figure 2f). Above ∼800 °C, the structure transformed into a nearly homogeneous layered phase, providing compelling evidence that ordering in LMRs is a nonequilibrium feature that can shift depending on calcination parameters. Taken together, the data sets in Figure 2 show that the framework for understanding Li2MnO3 domains should move beyond the binary debate of “two-phase vs. solid-solution.” Instead, LMR structures are best described as a synthesis-governed continuum, influenced by local Li ordering, precursor homogeneity, thermal conditions and atmosphere.

Synthesis-Driven Transformation of Li2MnO3-Like Domains

As established in the previous section, the long-standing debate over whether LMRs adopt a two-phase intergrowth of Li2MnO3 and LiTMO2 or a single-phase monoclinic solid-solution cannot be resolved without first acknowledging the strong influence of synthesis conditions. An expanding body of literature shows that precursor chemistry, mixing homogeneity, and calcination conditions (e.g. temperature, atmosphere) fundamentally shape the emergence, size, and coherence of Li2MnO3-like domains. Therefore, before comparing competing structural interpretations, it is essential to recognize that the Li2MnO3 domain is not merely a crystallographic signature but also a synthesis-derived construct. Figure 3 highlights representative examples demonstrating how precursor type and homogeneity, calcination temperature, and atmospheric environment reshape the observable domain structure in LMR materials.

Figure 3

Figure 3. Synthesis-dependent evolution of Li2MnO3-like domains in LMRs. (a) STEM–EDS elemental maps comparing cathodes prepared from solid state, and sol–gel precursors. Reproduced from ref (21) under CC BY 4.0 license. Copyright 2021, American Chemical Society. (b) Schematic illustration of the different synthesis route and FAULTS-refined XRD patterns of LMR samples annealed precursor at 900 °C for 3 h prepared by SG (Sol–gel) and CP (Coprecipitation) method. Reproduced from ref (28) under CC BY 3.0 license. Copyright 2022, Royal Society of Chemistry. (c) In situ HT XRD patterns for carbonate-derived (CO3-LRLO) and hydroxide-derived (OH-LRLO) Li-rich layered oxides. Reproduced with permission from ref (29). Copyright 2025, Wiley. (d) In situ Raman spectra showing distinct phase evolution pathways during calcination: lithium carbonate precursors rapidly develop C2/m Li2MnO3-like modes, whereas lithium hydroxide precursors progress through spinel-like intermediates prior to layered ordering. Reproduced with permission from ref (30). Copyright 2024, Royal Society of Chemistry. (e) EDS mapping of samples heated at low-temperature (∼700 °C, left) and high-temperature (∼1100 °C, right), showing the transition from well-defined Li2MnO3 domains to fused, single-solution-like lattices at elevated temperatures. Reproduced with permission from ref (19). Copyright 2024, Royal Society of Chemistry. (f) Effect of oxygen partial pressure during calcination, where high pO2 promotes extended Li2MnO3-like ordering and faulted monoclinic slabs, while reduced pO2 collapses ordering and yields more homogeneous monoclinic solid-solutions. Reproduced with permission from ref (20). Copyright 2023, American Chemical Society.

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From a thermodynamic perspective, LMRs of identical composition are expected to converge toward the same equilibrium structure, irrespective of synthesis route, provided sufficient time at high temperature. However, in practical synthesis, the applied thermal budget is finite, and cation rearrangement is often kinetically limited. Consequently, the structural differences observed among LMRs synthesized from different precursors are more appropriately interpreted as kinetically trapped and/or templated configurations, rather than as manifestations of distinct thermodynamic driving forces. Figure 3a,b first demonstrate how decisively the precursor preparation routes determine the final structure of LMRs. Solid state precursors, produced by mechanically mixing simple carbonate or oxide powders, exhibit relatively high cation inhomogeneity at the precursor stage. As shown in the elemental maps in Figure 3a, LMRs prepared from solid state precursors exhibit pronounced Mn-rich regions and incomplete dispersion of Ni and Co. However, the sol–gel route, which offers a high degree of elemental homogeneity throughout the solution-based process, yields significantly improved compositional uniformity of LMRs. (21) These differences in elemental homogeneity of precursors arising from distinct preparation methods directly dictate the nucleation and spatial development of Li2MnO3-like domains during calcination. As shown in XRD patterns in Figure 2e, (21) SS-LMNCO (LMRs prepared by solid state precursors) show strong peaks in the 1.4–2.0 Å–1 region corresponding to Li2MnO3-like short-range ordering, indicating the persistence of residual Li2MnO3-type domains. However, these peaks are markedly suppressed in SG-LMNCO (LMRs prepared by sol–gel precursors), demonstrating more complete Li–TM interdiffusion and a convergence toward a solid-solution-like structure with weakened monoclinic ordering. Heterogeneous precursors facilitate local Li–Mn clustering, which promotes the formation of thick monoclinic slabs, whereas homogeneous precursors suppress long-range Li–Mn ordering and instead produce more dispersed domains. Figure 3b also compares the effects of precursors prepared by sol–gel (SG) and coprecipitation (CP) method on the structure of LMRs. (28) It is noteworthy that solid state calcination using coprecipitated precursors has been adopted as standard protocols to produce commercial layered oxide cathodes currently, which is also expected for the case of LMRs. XRD patterns reveal that CP-derived LMNO exhibits stronger monoclinic ordering in the superstructure region than SG-derived LMNO, which can be attributed to the presence of lithium sources together with transition metal elements at the molecular level in the precursor. Such method-dependent structural variations in LMRs, even when both approaches employ solution-based processes, indicate that the degree of elemental homogeneity critically governs domain crystallography. Figure 3c,d provide clear evidence of how different types of precursors govern the development of Li2MnO3 domains. In comparative studies of TM precursors by leveraging in situ high-temperature X-ray diffraction (HT-XRD) measurements, (29) TM carbonate-derived cathodes (CO3-LRLO) exhibit a markedly different phase evolution behavior during calcination compared to TM hydroxide-derived cathodes (OH-LRLO). Carbonate-based precursors undergo multistep decomposition through several oxide intermediates, during which pronounced monoclinic-related reflections persist over a broad temperature window, indicating the early development and growth of Li2MnO3-like C2/m domains. In contrast, hydroxide-derived precursors transform through a spinel-like intermediate phase, which provides a continuous cation redistribution pathway and facilitates enhanced Li–TM interdiffusion prior to the formation of the layered structure. Consequently, OH-LRLO samples tend to exhibit thinner and more spatially dispersed Li2MnO3-like motifs, whereas CO3-LRLO samples favor the formation of thicker and more coherent monoclinic slabs. In addition to TM precursors, the type of lithium sources (i.e., lithium carbonate vs lithium hydroxide) also modulates the formation pathway of Li2MnO3-like domains even with the same TM hydroxide precursor. These structural differences are reflected in the in situ Raman spectra shown in Figure 3d. (30) Phase evolution during the synthesis of LMRs using lithium carbonate (upper panel in Figure 3d) displays early and intense C2/m-related Raman bands upon heating, followed by the emergence of strong long-range monoclinic ordering at higher temperatures. The synthesis trajectory with lithium hydroxide (bottom panel in Figure 3d), however, shows prolonged coexistence of transient spinel intermediate and layered features, and delayed development of C2/m vibrational modes. Such discrepancies were attributed to differences in the thermochemical reactivity of the lithium sources, which stem from their relative thermodynamic stability. Lithium hydroxide becomes reactive at lower temperatures, whereas lithium carbonate participates in the synthesis reaction only at higher temperatures after pyrolysis of the transition-metal precursor. These observations demonstrate that precursor identity directly controls the thermochemical formation and growth kinetics of Li2MnO3 domains upon calcination of LMRs.
Synthesis pathway governed by precursor chemistry and its resultant kinetics strongly influences the structural evolution of LMR cathodes, as exemplified in the previous results. These observations highlight that the degree of atomic-level cation mixing achieved during precursor synthesis governs the subsequent crystallographic and structural development of LMRs. Nevertheless, variations in calcination parameters primarily influence the structural properties of LMR cathodes through thermodynamic stabilization of different crystallographic motifs. Figure 3e,f highlight the role of calcination parameters such as temperature and atmosphere (oxygen partial pressure, pO2) as a structural tuning variable. EDS results in Figure 3e demonstrate that calcination temperature is one of the most critical parameters governing domain fusion. (19) At lower temperatures (∼700 °C), the initial segregation of transition metals is largely preserved, and Li2MnO3-like domains remain clearly defined, consistent with a two-phase interpretation. At higher temperatures (∼1100 °C), however, extensive cation interdiffusion eliminates domain boundaries and produces a nearly single-phase solid-solution. Thus, increasing temperature drives a continuous evolution from composite, nanodomain to solid-solution structures by determining the thermodynamically most stable equilibrium state at given temperatures. In addition, a recent study elucidated that samples annealed under high oxygen partial pressure (air or O2-rich conditions) develop larger Li2MnO3 domains with higher stacking-fault densities as shown in Figure 3f. (20) Elevated pO2 stabilizes Mn4+ and strengthens Li–Mn ordering, promoting monoclinic layer stacking. Conversely, reducing pO2 increases Mn3+ content and creates oxygen vacancies, which disrupt Li–Mn honeycomb ordering and suppress stacking faults, shrinking Li2MnO3 slabs or even transforming the material into a solid-solution-like monoclinic phase. Figure 3 illuminates that the distribution and coherence of Li2MnO3 domains are not intrinsic crystallographic properties, but synthesis-governed outcomes. Thus, the long-standing debate over whether LMRs are “two-phase” or “solid-solution” arises not from crystallographic ambiguity alone, but from differences in synthesis conditions that shape the observed structure.

Influence of Synthesis-Driven Li2MnO3 Domains on Electrochemical Behavior

While the preceding sections establish that the structural manifestation of Li2MnO3-like domains in LMRs is strongly governed by synthesis conditions, an equally important question concerns how such synthesis-driven structural variations translate into electrochemical behavior. Because the oxygen redox of LMR cathodes is intrinsically grounded in the Li2MnO3-like phase, it is essential to establish a synthesis-structure–property relationship of LMR cathodes particularly to improve oxygen-redox properties. The electrochemical data summarized in Figure 4 illustrate trends that emerge when structural differences originate from controlled synthesis variables we considered in the previous section. Figure 4a compares the initial charge–discharge profiles of LMNCO synthesized via solid state (SS) and sol–gel (SG) precursor routes. Despite having identical nominal compositions, the two samples exhibit distinct voltage responses during the first cycle. The SG-derived sample shows a smoother voltage increase during the high-voltage activation region, whereas the SS-derived sample displays a more pronounced plateau-like feature. The stronger Li2MnO3-like domain coherence in SS-derived materials can be attributed to variations in lithium transport pathways rather than intrinsic redox thermodynamics. In systems with more coherent Li2MnO3 domains, Li extraction from Li-rich layers is expected to proceed through spatially confined channels, leading to more sluggish kinetics and sharper voltage features. In contrast, more delocalized Li–Mn ordering in SG-derived materials facilitates distributed Li migration, resulting in smoother electrochemical responses. (21)

Figure 4

Figure 4. Synthesis-dependent electrochemical manifestations associated with Li2MnO3 domain regulation in LMR cathodes. (a) First-cycle charge–discharge profiles of LMNCO cathodes synthesized via sol–gel (SG) and solid state (SS) precursor routes. Reproduced from ref (21) under CC BY 4.0 license. Copyright 2021, American Chemical Society. (b) Charge–discharge curves and corresponding dQ/dV profiles of carbonate-derived (CO3-LRLO) and hydroxide-derived (OH-LRLO) Li-rich layered oxides collected at selected cycles (1st–300th) at 25 °C within a voltage window of 2.0–4.8 V. Reproduced with permission from ref (29). Copyright 2025, Wiley. (c) Voltage–capacity profiles of LLO cathodes prepared with lithium carbonate (LLO-LC) and lithium hydroxide monohydrate (LLO-LHM) during cycling following rate capability tests. Reproduced with permission from ref (30). Copyright 2024, Royal Society of Chemistry. (d) Differential capacity (dQ/dV) plots of LS-LMR and DS-LMR cathodes at the 1st, 50th, and 100th cycles. Reproduced with permission from ref (18). Copyright 2021, Wiley. (e) Voltage–capacity profiles of LMR cathodes calcined at 750 and 1000 °C, respectively, together with their cycling performance evaluated in the voltage range of 2.0–4.5 V after electrochemical activation. Reproduced with permission from ref (19). Copyright 2024, Royal Society of Chemistry. (f) Electrochemical behavior of LNMO-X cathodes calcined under different oxygen partial pressures (X = 1, 0.1, and 0.01) and air atmosphere (X = 20). Reproduced with permission from ref (20). Copyright 2023, American Chemical Society.

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The impact of precursor-dependent domain evolution becomes more evident during extended cycling, as shown in Figure 4b. CO3-LRLO and OH-LRLO LMRs display markedly different voltage evolution behaviors over 300 cycles, despite comparable initial capacities. The CO3-LRLO sample exhibits larger voltage hysteresis and more pronounced voltage decay, whereas the OH-LRLO sample maintains relatively stable voltage profiles. These trends align with structural observations (Figure 3c), where carbonate precursors favor early formation of thicker Li2MnO3-like slabs due to higher reaction onset temperatures and multistep decomposition processes. Such slab-like domains impose longer Li diffusion lengths and stronger local structural constraints, which accumulate as kinetic polarization during repeated cycling. Conversely, hydroxide-derived precursors promote more homogeneous cation redistribution through spinel-like intermediates, yielding finer and more dispersed Li2MnO3 motifs that are less detrimental to Li transport. (29)
Overall, the electrochemical differences observed in Figure 4a,b are closely associated with precursor-dependent modulation of lithium-ion transport, arising from differences in Li2MnO3 domain coherence and spatial distribution. A similar relationship between lithium transport and electrochemical behavior is observed when varying lithium sources, as shown in Figure 4c. LLO cathodes synthesized using lithium carbonate (LLO-LC) and lithium hydroxide monohydrate (LLO-LHM) exhibit distinct voltage–capacity profiles during cycling following rate capability tests. The LLO-LC sample shows more pronounced voltage drops upon repeated cycling, whereas the LLO-LHM sample retains a higher average discharge voltage. These differences are consistent with the distinct thermochemical activity of the lithium sources: lithium hydroxide becomes reactive at lower temperatures, allowing earlier and more uniform incorporation of Li into the layered lattice, while lithium carbonate reacts later, promoting localized Li accumulation and more coherent Li2MnO3 domain formation. As a result, LLO-LHM exhibits more stable voltage evolution during cycling, which is consistent with its more dispersed Li2MnO3 domain distribution. (30)
In addition to precursor-driven differences, calcination conditions play a critical role in defining Li2MnO3 domain characteristics and their electrochemical consequences. Figure 4d further highlights how the degree of Li2MnO3 ordering, regulated through synthesis conditions, manifests in differential capacity (dQ/dV) profiles. Here, LS-LMR and DS-LMR samples were prepared with identical compositions but under different calcination temperatures and annealing durations, thereby controlling whether excess Li remained localized or became delocalized within the layered lattice. LS-LMR samples, characterized by localized excess-Li ordering and stronger monoclinic coherence, display sharper and more distinct redox peaks that evolve significantly with cycling. In contrast, DS-LMR samples show broader and more diffuse dQ/dV features with less pronounced evolution over 100 cycles. (18) The role of calcination temperature in governing electrochemical behavior is summarized in Figure 4e. Samples calcined at lower temperatures (e.g., 750 °C) retain more distinct Li2MnO3 domains and exhibit larger polarization and faster capacity decay upon cycling. In contrast, samples calcined at higher temperatures (e.g., 1000 °C) show reduced polarization and improved capacity retention after electrochemical activation. Structural analyses (Figure 3e) indicate that higher calcination temperatures promote domain fusion and enhanced cation interdiffusion, effectively shortening Li diffusion pathways and reducing kinetic bottlenecks. Accordingly, the improved electrochemical stability at higher temperatures can be rationalized as a consequence of enhanced Li mobility arising from structurally fused domains rather than from changes in bulk composition. (19) Finally, Figure 4f illustrates a systematic correlation between Li2MnO3 domain characteristics and average discharge voltage evolution in LMR samples. Materials with more coherent Li2MnO3 ordering show a faster decline in average discharge voltage during cycling, whereas samples with more dispersed or weakened domain features maintain higher voltages over prolonged cycling. (20)
The electrochemical results in Figure 4 provide a consistent narrative linking synthesis, structure, and performance. Variations in precursor chemistry, lithium source, and calcination conditions dictate the spatial distribution and coherence of Li2MnO3-like domains, which in turn modulate lithium mobility and kinetic polarization during cycling. While the absolute electrochemical performance varies across material systems, the underlying trend remains robust: synthesis pathways that suppress excessive Li2MnO3 domain growth and promote distributed Li–Mn ordering generally favor more homogeneous Li transport and improved electrochemical stability. This perspective offers a practical framework for interpreting diverse electrochemical behaviors reported for Li-rich layered oxides without invoking contradictory structural models.

Conclusions and Outlook

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The structural identity of LMRs cannot be discussed without careful consideration of the synthesis conditions under which they are formed. The long-standing debate over whether Li2MnO3 exists as a distinct monoclinic component intergrown with LiTMO2 or instead manifests as short-range ordering within a single layered lattice has often been framed as a disagreement about the intrinsic crystallography of these materials. However, as illustrated in Figure 3, these discrepancies arise primarily from differences in precursor chemistry, elemental mixing uniformity, calcination temperature, oxygen partial pressure, and thermal history─rather than from composition alone. Depending on these synthesis variables, nominally identical materials can occupy vastly different positions along a structural continuum, ranging from thick and coherent Li2MnO3-like slabs to highly fused monoclinic solid-solution structures exhibiting only diffuse Li–Mn ordering. Notably, these synthesis-driven structural variations are also reflected in electrochemical behavior, as summarized in Figure 4. Differences in precursor selection and calcination conditions lead to systematic changes in voltage profiles, dQ/dV characteristics, and voltage evolution during cycling, indicating that Li2MnO3domain evolution influences electrochemical response beyond crystallographic distinctions alone.
Recognizing this synthesis-governed structural continuum is therefore essential before addressing the controversies surrounding Li2MnO3 domains. Figure 5 synthesizes this perspective by illustrating how each stage of synthesis─from precursor formation to final heat treatment─systematically determines the coherence, extent, and spatial distribution of Li2MnO3-like ordering. The schematic begins by comparing three representative precursor synthesis routes: solid state, coprecipitation, and sol–gel. Each method produces a fundamentally different degree of atomic-scale uniformity, which in turn dictates the nucleation and growth pathway of Li–Mn ordering during calcination. Solid state precursors, generated by mechanically blending micron-scale oxides or carbonates, inherently contain large compositional fluctuations. These Mn-rich or Li-rich regions persist during the early stages of heating and serve as nucleation centers for Li-excess clusters that subsequently develop into extended monoclinic Li2MnO3-like slabs. Materials derived from such precursors frequently display intense superstructure reflections, distinct Li–Mn honeycomb ordering in TEM, and XRD patterns resembling a two-phase intergrowth. By contrast, wet-chemical routes fundamentally alter this structural evolution by enabling far more homogeneous cation distributions. Coprecipitation (CP) yields hydroxide precursors with uniform metal-ion distributions across submicron aggregates, while sol–gel (SG) methods achieve near-molecular-level mixing via chelation or polymeric networks. These highly uniform precursors significantly reduce the driving force for Li–Mn segregation, suppressing the formation of thick Li2MnO3 slabs and instead favoring short-range or spatially diffuse Li–Mn ordering. As a result, CP- and SG-derived materials exhibit broadened or weakened superstructure reflections, diffuse domain boundaries, indicative of partially delocalized excess Li motifs.

Figure 5

Figure 5. Schematic illustration of synthesis-driven control over Li2MnO3 domain structures in LMRs.

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Following precursor formation, the calcination step determines whether these precursor-derived heterogeneities are preserved or whether the structure evolves toward a fully fused solid-solution. Temperature is the dominant control factor. At moderate temperatures (∼700 to 800 °C), limited cation mobility preserves the initial segregation patterns, stabilizing Li-rich monoclinic domains and producing pronounced C2/m phase features together with well-defined Li2MnO3-like slabs. At sufficiently high temperatures (>900 °C), enhanced cation interdiffusion dissolves domain boundaries, yielding structures with diminished monoclinic reflections and XRD patterns approaching single-phase R3̅m-like behavior. The two pathways in Figure 5 symbolize this temperature-driven evolution: the upper pathway corresponds to domain-preserving conditions, while the lower represents extensive domain fusion. Oxygen partial pressure provides a second orthogonal axis of control. Elevated pO2 stabilizes Mn4+ and strengthens Li–Mn honeycomb ordering, enlarging and preserving Li2MnO3-like motifs. Slight reducing atmospheres partially convert Mn4+ to Mn3+, destabilize monoclinic symmetry, and accelerate Li/TM disordering. Under this lower pO2 condition, Li2MnO3 motifs may collapse entirely, producing a homogeneous monoclinic solid-solution. In connection with the electrochemical behaviors discussed in Figure 4, synthesis-driven Li2MnO3 domain regulation can be linked to variations in Li-ion transport and oxygen-redox participation, because the extent of domain localization governs the spatial distribution of Li-rich and Mn-rich coordination environments. This structural heterogeneity is therefore relevant to oxygen redox reversibility in LMR systems. These observations confirm that the Li2MnO3 domain is not a fixed structural entity but a synthesis-dependent feature that expands or contracts in response to redox and diffusion conditions during heat treatment. This perspective is highly complementary to recent findings showing that crystal-/microstructural properties of layered oxide cathodes are sensitively affected by synthesis pathways that are altered by subtle variations in temperature profiles, and/or precursor stoichiometries. (31−36)
In light of these considerations, the present insights support a unified framework: the manifestation of Li2MnO3 domains is fundamentally a product of synthesis, not an intrinsic characteristic of Li-rich layered oxides. By tuning precursor uniformity, calcination temperature, and oxygen environment, materials can be intentionally positioned across the structural spectrum─from strongly expressed Li2MnO3 intergrowths to nearly homogeneous solid-solutions. This perspective helps rationalize decades of conflicting structural interpretations and provides a conceptual basis for discussing performance optimization. Importantly, the electrochemical differences associated with Li2MnO3 domain characteristics in LMRs appear to be governed less by the precursor synthesis stage and more by postlithiation calcination conditions─starting with lithium source mixing─where factors such as temperature, atmosphere, and reaction pathways exert a stronger influence on oxygen redox behavior. Synthesis-directed domain engineering enables controlled activation of oxygen redox, mitigation of voltage decay, suppression of oxygen release, and enhancement of long-term stability. Incorporating these stage-specific considerations into future LMR synthesis guidelines is therefore expected to facilitate more practical and reproducible material design for high-performance applications. Accordingly, Figure 5 serves not only as a conceptual schematic but also as a practical blueprint for designing next-generation Li-rich Mn-based cathodes through deliberate control of Li2MnO3 domain behavior.

Author Information

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  • Corresponding Author
  • Authors
    • Minji Kim - Department of Materials Science and Engineering, Korea University, Seoul 02841, Republic of Korea;  Orcidhttps://orcid.org/0000-0002-9136-0866
    • Dohyun Kim - Department of Materials Science and Engineering, Korea University, Seoul 02841, Republic of Korea
    • Hyeona Jo - Department of Materials Science and Engineering, Korea University, Seoul 02841, Republic of Korea
    • Keun Chan Yoo - Department of Materials Science and Engineering, Korea University, Seoul 02841, Republic of Korea
  • Author Contributions

    M.K., D.K., H.J., K.C.Y., and H.P. conceived the idea and wrote the manuscript. H.P. supervised the work. All authors approved the final version of the manuscript.

  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korean government (MSIT; Nos. RS-2021-NR062019).

References

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  • Abstract

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    Figure 1

    Figure 1. Structural signatures and diagnostic characterization of Li2MnO3 domains in Li- and Mn-rich layered oxides. (a) Schematic illustration comparing the two structural interpretations of Li-rich layered oxides: a two-phase intergrowth model consisting of monoclinic Li2MnO3 (C2/m) and rhombohedral LiTMO2 (R3̅m) domains, and a solid-solution model in which Li–Mn ordering is embedded as local motifs within a single layered lattice. (b) Powder XRD patterns for Li-rich layered oxides with increasing Li2MnO3 content, showing the emergence and growth of monoclinic superstructure reflections. Reproduced from ref (22) under CC BY-NC-ND 4.0 license. Copyright 2019, The Electrochemical Society. (c) HAADF-STEM images and simulated atomic configurations demonstrating Li/Mn honeycomb ordering and the contrast differences between Li columns and TM columns, used to distinguish Li2MnO3-like local ordering from fully random TM distributions. Reproduced with permission from ref (23). Copyright 2012, American Chemical Society.

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    Figure 2

    Figure 2. Chronological evolution of structural interpretations of Li2MnO3domain in LMRs. (a) 6Li MAS NMR spectra of Li2MnO3 samples prepared at 1000 °C (blue) and 850 °C (black). Reproduced with permission from ref (25). Copyright 2005, Elsevier. (b) Convergent-beam electron diffraction (CBED) patterns comparing LiMn0.5Ni0.5O2 and Li1.048[Mn0.333Ni0.333Co0.333]0.952O2. Reproduced with permission from ref (26). Copyright 2006, Elsevier. (c) HAADF-STEM imaging identifying localized excess-Li regions responsible for Li2MnO3-like contrast in LMR particles. Reproduced with permission from ref (17). Copyright 2020, Wiley. (d) X-ray diffraction superlattice peaks (20–25°) comparing DS-LMR (delocalized excess-Li) and LS-LMR (localized excess-Li). Reproduced with permission from ref (18). Copyright 2021, Wiley. (e) Scanning electron microscopy and XRD analysis correlating superstructure evolution and stacking faults with precursor-dependent synthesis pathways (Solid state and Sol–gel method). Reproduced from ref (21) under CC BY 4.0 license. Copyright 2021, American Chemical Society. (f) In situ STEM tracking of sol–gel precursors during heating, revealing atomic-level TM mixing. Reproduced with permission from ref (27). Copyright 2022, Elsevier.

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    Figure 3

    Figure 3. Synthesis-dependent evolution of Li2MnO3-like domains in LMRs. (a) STEM–EDS elemental maps comparing cathodes prepared from solid state, and sol–gel precursors. Reproduced from ref (21) under CC BY 4.0 license. Copyright 2021, American Chemical Society. (b) Schematic illustration of the different synthesis route and FAULTS-refined XRD patterns of LMR samples annealed precursor at 900 °C for 3 h prepared by SG (Sol–gel) and CP (Coprecipitation) method. Reproduced from ref (28) under CC BY 3.0 license. Copyright 2022, Royal Society of Chemistry. (c) In situ HT XRD patterns for carbonate-derived (CO3-LRLO) and hydroxide-derived (OH-LRLO) Li-rich layered oxides. Reproduced with permission from ref (29). Copyright 2025, Wiley. (d) In situ Raman spectra showing distinct phase evolution pathways during calcination: lithium carbonate precursors rapidly develop C2/m Li2MnO3-like modes, whereas lithium hydroxide precursors progress through spinel-like intermediates prior to layered ordering. Reproduced with permission from ref (30). Copyright 2024, Royal Society of Chemistry. (e) EDS mapping of samples heated at low-temperature (∼700 °C, left) and high-temperature (∼1100 °C, right), showing the transition from well-defined Li2MnO3 domains to fused, single-solution-like lattices at elevated temperatures. Reproduced with permission from ref (19). Copyright 2024, Royal Society of Chemistry. (f) Effect of oxygen partial pressure during calcination, where high pO2 promotes extended Li2MnO3-like ordering and faulted monoclinic slabs, while reduced pO2 collapses ordering and yields more homogeneous monoclinic solid-solutions. Reproduced with permission from ref (20). Copyright 2023, American Chemical Society.

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    Figure 4

    Figure 4. Synthesis-dependent electrochemical manifestations associated with Li2MnO3 domain regulation in LMR cathodes. (a) First-cycle charge–discharge profiles of LMNCO cathodes synthesized via sol–gel (SG) and solid state (SS) precursor routes. Reproduced from ref (21) under CC BY 4.0 license. Copyright 2021, American Chemical Society. (b) Charge–discharge curves and corresponding dQ/dV profiles of carbonate-derived (CO3-LRLO) and hydroxide-derived (OH-LRLO) Li-rich layered oxides collected at selected cycles (1st–300th) at 25 °C within a voltage window of 2.0–4.8 V. Reproduced with permission from ref (29). Copyright 2025, Wiley. (c) Voltage–capacity profiles of LLO cathodes prepared with lithium carbonate (LLO-LC) and lithium hydroxide monohydrate (LLO-LHM) during cycling following rate capability tests. Reproduced with permission from ref (30). Copyright 2024, Royal Society of Chemistry. (d) Differential capacity (dQ/dV) plots of LS-LMR and DS-LMR cathodes at the 1st, 50th, and 100th cycles. Reproduced with permission from ref (18). Copyright 2021, Wiley. (e) Voltage–capacity profiles of LMR cathodes calcined at 750 and 1000 °C, respectively, together with their cycling performance evaluated in the voltage range of 2.0–4.5 V after electrochemical activation. Reproduced with permission from ref (19). Copyright 2024, Royal Society of Chemistry. (f) Electrochemical behavior of LNMO-X cathodes calcined under different oxygen partial pressures (X = 1, 0.1, and 0.01) and air atmosphere (X = 20). Reproduced with permission from ref (20). Copyright 2023, American Chemical Society.

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    Figure 5

    Figure 5. Schematic illustration of synthesis-driven control over Li2MnO3 domain structures in LMRs.

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