Spinel LiMn Research Articles

Co-axially electrospun Li-rich layered Oxide@Spinel core-shell heterostructure nanofibers for enhanced stability and electrochemical performance

Lithium-rich layered oxides (LLO) possessing high specific capacity has the limitation of voltage fade, poor high C-rate performance and low conductivity. Spinel coating on LLO surface is known to mitigate the voltage fade, however, enabling high C-rate performance remains challenging. In this study, LLO nanofiber core with composition 0.6Li2MnO3·0.4LiMn0.25Ni0.38Co0.37O2 is prepared by electrospinning process and the same is coated with spinel LiMn1.5Ni0.5O4 shell to obtain LLO/spinel (LLO/S) core-shell heterostructure. The spinel shell coating is accomplished (i) by a novel co-axial (CA) electrospinning process and (ii) by wet chemical (WC) approach. The CA electrospinning process provides a uniform core-shell structure compared to the WC process. The electron microscopy studies reveal the fibrous microstructure in LLO/S heterostructures with energy dispersive spectroscopy compositional mapping showing the spinel composition on the surface. Higher concentration (>10 wt.%) of spinel coating are shown to break the fibers into particulates. X-ray diffraction and high-resolution transmission electron microscopy analysis confirm the spinel structure formation along with layered structure. While the capacity is slightly compromised compared to the pristine LLO nanofiber, the LLO/S heterostructure with 10 wt.% spinel coating exhibits a high reversible capacity of 268 mAhg-1 with minimal capacity loss during the 1st cycle (with coulombic efficiency 83.5%) and an excellent high C-rate capability (88 mAhg-1 at 10C-rate and 55 mAhg-1 at 20C-rate). The electrochemical studies also demonstrate the importance of optimal spinel content in the coating and the method of spinel coating on the layered material surface. The encapsulation of LLO with spinel layer which has 3D-diffusion pathways for Li-ion transport facilitates high ionic and electronic conductivity and hence leads to enhanced electrochemical performance of LLO/S heterostructured cathodes.

A novel morphology of high voltage LiMn1.5Ni0.5O4 cathode material with niobium-doping

Spinel LiMn1.5Ni0.5O4 (LMNO) is one of the promising cathode materials for the next generation Li-ion batteries due to its voltage platform. However, the dissolution of the transition metal at high voltage is the biggest obstacle that LMNO suffers from. In this study, we successfully suppressed transition metal dissolution in LMNO by the morphology control from regular octahedron to spherical. Niobium was integrated as a dopant, which restricted the growth of (111) crystal face, and increased the indices of crystal faces by homogenizing the surface energy. By changing to a smaller surface area with spherical morphology, the contact area with the electrolyte was reduced, thus suppressing the dissolution of the Mn ion. Consequently, the niobium-doped LMNOexhibited superior rate performance, capacity retention with 74.1% at 1C after 500 cycles in half-cell, and thermal stability compared to pristine LMNO.

Developing a High‐Performing Spinel LiMn2O4 Cathode Material with Unique Morphology, Fast Cycling and Scaled Manufacture

AbstractHigh power application of Li‐battery remains a challenge due to the lack of stable fast‐charging cathode materials. Lithium manganese oxide (LMO) cathode is very promising due to its high operating voltage and fast charging ability; however, the associated Mn‐dissolution is one of the main hindrances to its practical applicability. In this work, we demonstrate for the first time the use of a commercially scalable method through a proprietary Calix flash calcination (CFC) technology to develop high‐performance electrode materials where a novel CXL LMO material was manufactured and tested. CXL LMO|Li metal cell showed a reversible specific capacity of 110 mAh/g with 99 % retention after 100 cycles and showed excellent rate performance up to 20 C current rate (~20 mA/cm2 current density). CXL LMO|Graphite cell (areal capacity 1 mAh/cm2) was also reported with 86 % capacity retention over more than 500 cycles. Cross‐section morphology revealed a unique multi‐layered structure that was retained at the core of the novel LMO material. It obtained lesser Mn dissolution compared to commercial LMO. The scalable synthesis procedure through CFC technology, can be broadly applicable to produce unique electrode morphology as demonstrated here for the CXL LMO representing a promising pathway for electrode manufacturing for high‐power Li‐batteries.

Recent Progress of High Voltage Spinel LiMn1.5Ni0.5O4 Cathode Material for Lithium-Ion Battery: Surface Modification, Doping, Electrolyte, and Oxygen Deficiency.

High voltage spinel LiMn1.5Ni0.5O4 (LMNO) is a promising energy storage material for the next generation lithium batteries with high energy densities. However, due to the major controversies in synthesis, structure, and interfacial properties of LMNO, its unsatisfactory performance is still a challenge hindering the technology's practical applications. Herein, this paper provides general characteristics of LiMn1.5Ni0.5O4 such as spinel structure, electrochemical properties, and phase transition. In addition, factors such as electrolyte decomposition and morphology of LMNO that influence the electrochemical performances of LMNO are introduced. The strategies that enhance the electrochemical performances including coating, doping, electrolytes, and oxygen deficiency are comprehensively discussed. Through the discussion of the present research status and presentation of our perspectives on future development, we provide the rational design of LMNO in realizing lithium-ion batteries with improved electrochemical performances.

Preparation and Properties of Spinel LiMn1.90 Ni0.05 Cu0.05 O4

Spinel LiMn2O4 and LiMn1.90Ni0.05 Cu0.05O4 cathode materials were synthesized by a simple solution combustion method. The structure, morphology and properties of the two samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), battery test system and electrochemical workstation. The results show that the two samples are spinel lithium manganate structure, which can be indexed as Fd3m space group. Ni Cu co doping effectively reduces the particle size and agglomeration, improves the crystallinity of the materials, and makes LiMn1.90Ni 0.05 Cu0.05O4 samples show good crystal structure stability and magnification properties. The capacity retention rates of 64.53%,79.52%and 69.47%were obtained after 1000 cycles at current densities of 1 C,5 C and 10 C,respectively, which were higher than 43.75%,55.74%and 44.38%of the corresponding undoped LiMn2O4 samples.

Evolution of Spinel LiMn2O4 Single Crystal Morphology Induced by the Li2MnO3 Phase during Sintering

Evolution of Spinel LiMn₂O₄ Single Crystal Morphology Induced by the Li₂MnO₃ Phase during Sintering

High Li-ion diffusion coefficient in LiMn1.5Ni0.5O4 thin films for all-solid Li-ion battery applications

Among various choices of high-performance cathode materials, Ni substituted LiMn2O4 spinel LiMn1.5Ni0.5O4 (LMNO) has proved to be one of the solutions to yield a high-performance and high-energy density material, which can operate at a higher potential window. This study explores the high diffusion coefficient and electrochemical performance at wide current rates of LMNO thin films with less than 50 nm thickness, fabricated on SrTiO3 and SS substrates by the pulsed laser deposition method. The LMNO film with less thickness and the performance without binder and conducting carbon widen the Li-ion path and decrease diffusion length, resulting a higher diffusion coefficient on the order of 10−5 to 10−6 cm2/s, which is several orders higher than the previously obtained reports for bulk counterpart. The cycling stability and rate capability at different current densities of LMNO thin film electrodes are further investigated. Charge–discharge profile at varying current rates of 5, 10, 15, 20, 25, 50, 75, 100, and 125 mA/cm2 is obtained for 500 cycles. The as fabricated film shows a stable profile for 500 cycles with 1.3 and 2.3 μA h/cm2 areal discharge capacity at 25 and 5 mA current rates, respectively. Electrode interfacial properties of LMNO film (before and after cycles) are analyzed using impedance technique. This study indicates that the LMNO thin films can be employed as a cathode layer for fabricating the all-solid thin film batteries for energy applications.

Progress, Challenge, and Prospect of LiMnO2 : An Adventure toward High-Energy and Low-Cost Li-Ion Batteries.

Lithium manganese oxides are considered as promising cathodes for lithium-ion batteries due to their low cost and available resources. Layered LiMnO2 with orthorhombic or monoclinic structure has attracted tremendous interest thanks to its ultrahigh theoretical capacity (285mAhg-1 ) that almost doubles that of commercialized spinel LiMn2 O4 (148mAhg-1 ). However, LiMnO2 undergoes phase transition to spinel upon cycling cause by the Jahn-Teller effect of the high-spin Mn3+ . In addition, soluble Mn2+ generates from the disproportionation of Mn3+ and oxygen release during electrochemical processes may cause poor cycle performance. To address the critical issues, tremendous efforts have been made. This paper provides a general review of layered LiMnO2 materials including their crystal structures, synthesis methods, structural/elemental modifications, and electrochemical performance. In brief, first the crystal structures of LiMnO2 and synthetic methods have been summarized. Subsequently, modification strategies for improving electrochemical performance are comprehensively reviewed, including element doping to suppress its phase transition, surface coating to resist manganese dissolution into the electrolyte and impede surface reactions, designing LiMnO2 composites to improve electronic conductivity and Li+ diffusion, and finding compatible electrolytes to enhance safety. At last, future efforts on the research frontier and practical application of LiMnO2 have been discussed.

ВЛИЯНИЕ ДОПИРОВАНИЯ ИОНАМИ Al3+ НА АДСОРБЦИОННЫЕ СВОЙСТВА ОКСИДОВ Li1,33Mn1,67O4 СО СТРУКТУРОЙ ШПИНЕЛИ

This paper presents results adding ions Al3+ into structure of Li-Mn spinel with composition Li1,33Mn1,67O4. It has been established that doping with Al3+ ions leads to a noticeable increase in the specific surface area by 1,9–7,6 times and the increase of the pore volume by 9,5 times by comparison no doped spinel. Using scanning electron microscopy, it was proved that an increase in the concentration of introduced Al3+ ions is accompanied by a differentiation of two types of particles in shape, while the shape of large bulk agglomerates resembles a lamellar one.

Impedance, modulus and electrochemical studies of LiMn2- x - y Ce x Cu y O4 (0.01 ≤ x ≤ 0.05 and y = x) cathode materials

In this task, the improvement on the electrochemical performances, particularly, on the cyclability and capacity retention of cathode material, LiMn2-x-yCexCuyO4 is reported using the dual doping method. This way of substitution is performed to investigate the effect of simultaneous substitution of mono and trivalent cations Ce+ and Cu3+ respectively for Mn3+/4+ into LiMn2O4 cathode by making the average oxidation state Mn to be around +3.5 and above. Thus, the synthesis of a new series of spinel LiMn2- x - y Ce x Cu y O4 (0.01 ≤ x ≤ 0.05 and y = x) cathode materials are performed. An investigation of the electrical and electrochemical properties of the synthesized materials is performed.

Cation disorder dominates the defect chemistry of high-voltage LiMn1.5Ni0.5O4 (LMNO) spinel cathodes

Using first-principles calculations, a comprehensive intrinsic defect study on high-voltage spinel LiMn1.5Ni0.5O4 (LMNO) cathode shows that the defect chemistry of this material is dominated by cation antisites and their complexes.

Understanding the key role of {100} exposed crystal facets on the electrochemistry of the spinel LiMn2O4 cathode

The exposed {111} facets truncated by a portion of {100} facets reduce the Mn2+ dissolved into the electrolyte and improve the cycling stability of the spinel LiMn2O4 cathode.

Removing the Two-Phase Transition in Spinel LiMn2O4 through Cation Disorder

Removing the Two-Phase Transition in Spinel LiMn₂O₄ through Cation Disorder

(Digital Presentation) A Polymerized-Ionic-Liquid-Based Polymer Electrolyte for >4 V Class Solid-State Lithium Metal Batteries

Polymer solid electrolytes for solid-state batteries typically suffer from low ionic conductivity and low oxidative stability. We report a polymer electrolyte based on a polymerized ionic liquid and an ionic liquid plasticizer offering simultaneously a high room-temperature ionic conductivity of 0.8 mS cm-1 and a high oxidative stability > 5.0 V vs Li+/Li. The electrolyte is compatible with lithium metal, exhibits high thermal stability up to 300 °C, is non-flammable upon direct flame exposure, shows decent lithium-ion transference number of 0.44, and possesses a low gravimetric density of only 1.6 g cm-3, important when targeting batteries with high gravimetric energy density. In symmetric lithium metal cells, the electrolyte enables stable lithium plating and stripping at 0.1 mA cm−2 with a capacity of 1 mAh cm−2 per half cycle for over 1700 h at 25 °C. Cells with a lithium metal anode cycled against a state-of-the-art high-energy uncoated layered LiNi0.8Mn0.1Co0.1O2cathode achieve an initial capacity of 162 mA h g-1 and a capacity retention of 72% after 600 cycles to an upper cut-off voltage of 4.4 V at 0.1 mA cm-2 and 25 °C. Cells with a high-voltage spinel LiMn1.5Ni0.5O4 cathode reach an initial capacity of 132 mAh g-1 and a capacity retention of 76% after 300 cycles to an upper cut-off voltage of 5 V at 0.1 mA cm-2 and 25 °C, confirming the high oxidative stability and technological potential of this electrolyte for high-voltage solid-state lithium metal batteries.

(Digital Presentation) Regulating Anion Redox during Cycling of Spinel LiMn1.5Ni0.5O4 As Cathodes for Lithium Ion Batteries

In recent years, extensive research has been performed on high energy cathode materials for lithium ion batteries being used in electric vehicles to reduce carbon emissions. Compared to the commercial layered cathode materials, the absence of cobalt in the spinel LiMn1.5Ni0.5O4 (LMNO) makes this material more environmentally friendly and cheaper.1 Spinel LMNO cathodes also reveal attractive gravimetric and volumetric energy densities of 635Whkg−1 and 2820WhL−1, respectively.2 According to the distribution of transition metals (TM) within the cubic crystal structure, spinel LMNO can be categorized into either ordered or disordered. Normally, disordered LMNO materials are produced at temperatures higher than the theoretical oxygen release temperature of spinel LMNO (715 °C).3 The formation of O vacancies is accompanied by some Mn4+ atoms being reduced to Mn3+ to maintain the electroneutrality of spinel LMNO. Ordered LMNO can be obtained through calcination at temperatures lower than 715 °C or post-annealing disordered LMNO materials at 700 °C.4 The reversible extraction and insertion of O atoms accompanied with different distribution of TM during spinel LMNO preparation drive up a hypothesis that the oxygen activity during cycling of spinel LMNO may be affected by the distribution of TM atoms, especially since the operating voltage of spinel LMNO (> 4.7 V) is high enough to trigger oxygen redox in other lithium transition metal oxides.5 To explore the feasibility of oxygen activity during cycling of spinel LMNO, the normal, core-shell and sandwich designed synthesis are performed using special Mn0.75Ni0.25(OH)2 precursors to arrange different distributions of TM atoms in the obtained N-, CS- and SW-LMNO. As shown in Figure 1(a) – (c), the three materials show similar XRD patterns in the pristine state, yet different reflection peaks are observed in the three materials after charging to 4.9 V. The unclear phase transition of SW-LMNO indicates it show stable structure. The three materials also show different CV curves, see Figure 1(d). This indicates the extraction and insertion of Li atoms lead to different redox reactions in the three materials. Besides, differential electrochemical mass spectrometry (DEMS), in-situ transmission electron microscope (TEM) as well as hard and soft X-ray absorption spectroscopy (XAS) measurements are utilized to further investigate the oxygen activity during cycling of spinel LMNO.Reference1. Li, M. & Lu, J. Cobalt in lithium-ion batteries. Science 367, 979-980 (2020).2. Hagh, N. M. & Amatucci, G. G. A new solid-state process for synthesis of LiMn1. 5Ni0. 5O4−δ spinel. Journal of Power Sources 195, 5005-5012 (2010).3. Manthiram, A., Chemelewski, K. & Lee, E.-S. A perspective on the high-voltage LiMn1.5Ni0.5O4 spinel cathode for lithium-ion batteries. Energy & Environmental Science 7, 1339-1350 (2014).4. Chemelewski, K. R., Shin, D. W., Li, W. & Manthiram, A. Octahedral and truncated high-voltage spinel cathodes: the role of morphology and surface planes in electrochemical properties. Journal of Materials Chemistry A 1, 3347-3354 (2013).5. Seo, D.-H. et al. The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials. Nature chemistry 8, 692-697 (2016).Figure 1. Operando X-ray diffraction patterns of N- (a), CS- (b) and SW- (c) LiMn1.5Ni0.5O4 in the pristine states and at the charge states of 4.9 V and the corresponding cyclic voltammetry curves of the three materials (d) Figure 1

The Correlation between Structure, Surface, and Performance in Fe- and Mg-Substituted LiNi0.5Mn1.5O4 Cathodes

A need for lithium-ion cathodes that have a reduced dependence on scarce elements, such as cobalt, has been prompted by surge in eco-consciousness over the past decade. The spinel-type LiNi0.5Mn1.5O4 (LNMO) cathodes, with high operating voltages (ca. 4.7V vs Li+/Li) and energy densities (ca. 650 Wh kg-1), have received particular attention for this reason.1 Poor cycling stability, however, which arises from structural instabilities, electrolyte degradation, surface densification and loss of active material through transition metal dissolution, limits their widespread adoption.2 Elemental substitution has been employed to overcome such limitations, in which improved cycling stability has been observed. In such samples, the segregation of substituents to the cathode surface has been reported, yet the effect of surface segregation on the local atomic structure and surficial reactivity of the cathodes is under-researched.3 To further explore these areas, Fe- and Mg-substituted LNMO samples have been synthesised. Despite lower initial capacity, Mg-substituted LNMO exhibits significantly improved cycling stability over 300 cycles at 50°C. A combination of x-ray and neutron diffraction, neutron pair distribution function analysis, and x-ray absorption and photoelectron spectroscopy are used to explore the complex relationships between bulk structure, local structure, surface reactivity and performance in Fe- and Mg-substituted LNMO cathodes. References Liang, G., Peterson, V.K., See, K.W., Guo, Z., and Pang, W.K. (2020). Developing high-voltage spinel LiNi 0.5 Mn 1.5 O 4 cathodes for high-energy-density lithium-ion batteries: current achievements and future prospects . J. Mater. Chem. A.Ma, J., Hu, P., Cui, G., and Chen, L. (2016). Surface and Interface Issues in Spinel LiNi0.5Mn1.5O4: Insights into a Potential Cathode Material for High Energy Density Lithium Ion Batteries. Chem. Mater. 28, 3578–3606.Shin, D.W., Bridges, C.A., Huq, A., Paranthaman, M.P., and Manthiram, A. (2012). Role of Cation Ordering and Surface Segregation in High-Voltage Spinel LiMn LiMn 1.5Ni 0.5-xM xO 4(M = Cr, Fe, and Ga) Cathodes for Lithium-Ion Batteries. Chem. Mater. 24, 3720–3731. Figure 1

A Polymerized‐Ionic‐Liquid‐Based Polymer Electrolyte with High Oxidative Stability for 4 and 5 V Class Solid‐State Lithium Metal Batteries

AbstractPolymer solid electrolytes for solid‐state batteries typically suffer from low ionic conductivity and low oxidative stability. Herein, a polymer electrolyte based on a polymerized ionic liquid and an ionic liquid plasticizer offering simultaneously a high room‐temperature ionic conductivity of 0.8 mS cm−1 and a high oxidative stability >5.0 V versus Li+/Li, is reported. The electrolyte is compatible with lithium metal and non‐flammable upon direct flame exposure. In symmetric lithium metal cells, the electrolyte enables stable lithium plating and stripping at 0.1 mA cm−2 with a capacity of 1 mAh cm−2 per half cycle for over 1700 h at 25 °C. Cells with a lithium metal anode cycled against a state‐of‐the‐art high‐energy uncoated layered LiNi0.8Mn0.1Co0.1O2 cathode achieve an initial capacity of 162 mA h g−1 and a capacity retention of 72% after 600 cycles to an upper cut‐off voltage of 4.4 V at 25 °C. Cells with a high‐voltage spinel LiMn1.5Ni0.5O4 cathode reach an initial capacity of 132 mAh g−1 and a capacity retention of 76% after 300 cycles to an upper cut‐off voltage of 5 V at 25 °C, confirming the high oxidative stability and technological potential of this electrolyte for high‐voltage solid‐state lithium metal batteries.

3D LiMn2 O4 Thin Film Deposited by ALD: A Road toward High-Capacity Electrode for 3D Li-Ion Microbatteries.

Miniaturized electronics suffer from a lack of energy autonomy. In that context, the fabrication of lithium-ion solid-state microbatteries with high performance is mandatory for powering the next generation of portable electronic devices. Here, the fabrication of a thin film positive electrode for 3D Li-ion microbatteries made by the atomic layer deposition (ALD) method and in situ lithiation step is demonstrated. The 3D electrodes based on spinel LiMn2 O4 films operate at high working potential (4.1 V vs Li/Li+ ) and are capable of delivering a remarkable surface capacity (≈180 μAh cm-2 ) at low C-rate while maintaining more than 40 μAh cm-2 at C/2 (time constant = 2 h). Both the thickness of the electrode material and the 3D gain of the template are carefully tuned to maximize the electrode performance. Advanced characterization techniques such as transmission electron and X-ray transmission microscopies are proposed as perfect tools to study the conformality of the deposited films and the interfaces between each layer: no interdiffusion or segregation are observed. This work represents a major issue towards the fabrication of 3D-lithiated electrode by ALD-without any prelithiation step by electrochemical technique-making it an attractive solution for the fabrication of 3D Li-ion solid-state microbatteries with semiconductor processing methods.

Microwave-assisted hydrothermal synthesis of a high-voltage microcube LiMn1.5Ni0.5O4−δ spinel cathode material

• High-quality LiMn 1.5 Ni 0.5 O 4−δ was synthesized by microwave-assisted hydrothermal method. • Microwave-treated LiMn 1.5 Ni 0.5 O 4−δ offers higher battery performance than LiMn 2 O 4. • Microwave irradiation modulates content of Mn 3+ and O vacancy improving performance. • Material with longer irradiation shows higher discharge capacity but less stability. • Improving intrinsic stability is required before practical use in Li-ion batteries. Electric vehicles (EVs) require high operating voltages as well as high-capacity batteries. One candidate material that has received a great deal of attention is the nickel-substituted “high-voltage” spinel LiMn 1.5 Ni 0.5 O 4 , which offers the advantages of both higher capacity and higher operating voltage than spinel LiMn 2 O 4 . These features, along with the relatively benign constituent elements, have made this material a top choice for the next generation of high-power batteries. In this study, LiMn 1.5 Ni 0.5 O 4−δ materials were synthesized by a microwave-assisted hydrothermal method. Analyses show that microwave irradiation enables the tuning of the Mn 3+ concentration, which is related to the degree of disorder and enhances the electrochemical performance. However, with increasing synthesis time, the material limit of the elastic strain was exceeded, and the structure became morphologically unstable, which deteriorated the electrochemical performance. Thus, further efforts are necessary to improve its intrinsic stability. The LiMn 1.5 Ni 0.5 O 4−δ cathode active material may be suitable for the rapid charging of electric vehicle batteries.

Defect-Engineered β-MnO2-δ Precursors Control the Structure-Property Relationships in High-Voltage Spinel LiMn1.5Ni0.5O4-δ.

This study examines the role of defects in structure–property relationships in spinel LiMn1.5Ni0.5O4 (LMNO) cathode materials, especially in terms of Mn3+ content, degree of disorder, and impurity phase, without the use of the traditional high-temperature annealing (≥700 °C used for making disordered LMNO). Two different phases of LMNO (i.e., highly P4332-ordered and highly Fd3̅m-disordered) have been prepared from two different β-MnO2−δ precursors obtained from an argon-rich atmosphere (β-MnO2−δ (Ar)) and a hydrogen-rich atmosphere [β-MnO2−δ (H2)]. The LMNO samples and their corresponding β-MnO2−δ precursors are thoroughly characterized using different techniques including high-resolution transmission electron microscopy, field-emission scanning electron microscopy, Raman spectroscopy, powder neutron diffraction, X-ray photoelectron spectroscopy, synchrotron X-ray diffraction, X-ray absorption near-edge spectroscopy, and electrochemistry. LMNO from β-MnO2−δ (H2) exhibits higher defects (oxygen vacancy content) than the one from the β-MnO2−δ (Ar). For the first time, defective β-MnO2−δ has been adopted as precursors for LMNO cathode materials with controlled oxygen vacancy, disordered phase, Mn3+ content, and impurity contents without the need for conventional methods of doping with metal ions, high synthetic temperature, use of organic compounds, postannealing, microwave, or modification of the temperature-cooling profiles. The results show that the oxygen vacancy changes concurrently with the degree of disorder and Mn3+ content, and the best electrochemical performance is only obtained at 850 °C for LMNO-(Ar). The findings in this work present unique opportunities that allow the use of β-MnO2−δ as viable precursors for manipulating the structure–property relationships in LMNO spinel materials for potential development of high-performance high-voltage lithium-ion batteries.