Li-rich Mn-based Cathode Materials Research Articles

Constructing Targeted Strong Nb4d-O2p-Li2s Configurations to Obtain Excellent Energy Density and Long Life for Li-Rich Cathodes.

The Li-rich Mn-based cathode materials (LMRs) deliver excellent energy density and exhibit low cost, which are considered as the most promising cathode materials for the next generation lithium-ion batteries. However, the irreversible redox reaction of the oxygen atoms directly leads to release oxygen and intensifies phase transformation. Besides, the local stress and strain will be generated due to the unit-cell volume difference between R-3m and C2/m phases, which continuously aggravates the collapse of secondary particles. Herein, the strong Nb4d-O2p-Li2s configurations at the Li1 sites of the TM-layer in the C2/m phase and secondary particles with the radial arrangement of refined primary particles are designed to inhibit oxygen release and relieve lattice stress by Nb2O5 treatment. Meanwhile, the preferential growth of the active {010} planes is presented to obtain an excellent transmission rate of Li+. As a result, the designed LMR delivers remarkable electrochemical properties with high discharge capacity and initial coulomb efficiency of 276 mAh g-1 and 85 % at 0.1 C, outstanding cycling retention rate of 81 % after 300 cycles. This novel crystal structure combining oxygen coordination regulation and micro-nano scale design provides inspiration for the design of high-performance LMRs.

Constructing Targeted Strong Nb4d−O2p−Li2s Configurations to Obtain Excellent Energy Density and Long Life for Li‐Rich Cathodes

AbstractThe Li‐rich Mn‐based cathode materials (LMRs) deliver excellent energy density and exhibit low cost, which are considered as the most promising cathode materials for the next generation lithium‐ion batteries. However, the irreversible redox reaction of the oxygen atoms directly leads to release oxygen and intensifies phase transformation. Besides, the local stress and strain will be generated due to the unit‐cell volume difference between R‐3m and C2/m phases, which continuously aggravates the collapse of secondary particles. Herein, the strong Nb4d−O2p−Li2s configurations at the Li1 sites of the TM‐layer in the C2/m phase and secondary particles with the radial arrangement of refined primary particles are designed to inhibit oxygen release and relieve lattice stress by Nb2O5 treatment. Meanwhile, the preferential growth of the active {010} planes is presented to obtain an excellent transmission rate of Li+. As a result, the designed LMR delivers remarkable electrochemical properties with high discharge capacity and initial coulomb efficiency of 276 mAh g−1 and 85 % at 0.1 C, outstanding cycling retention rate of 81 % after 300 cycles. This novel crystal structure combining oxygen coordination regulation and micro‐nano scale design provides inspiration for the design of high‐performance LMRs.

Bulk/Interfacial Structure Design of Li-Rich Mn-Based Cathodes for All-Solid-State Lithium Batteries.

Li-rich Mn-based cathode materials (LRMO) are promising for enhancing energy density of all-solid-state batteries (ASSBs). Nonetheless, the development of efficient Li+/e- pathways is hindered by the poor electrical conductivity of LRMO cathodes and their incompatible interfaces with solid electrolytes (SEs). Herein, we propose a strategy of in-situ bulk/interfacial structure design to construct fast and stable Li+/e- pathways by introducing Li2WO4, which reduces the energy barrier for Li+ migration and enhances the stability of the surface oxygen structure. The reversibility of oxygen redox was improved, and the voltage decay of the LRMO cathode was addressed significantly. As a result, the bulk structure of the LRMO cathodes and the high-voltage solid-solid interfacial stability are improved. Therefore, the ASSBs achieve a high areal capacity (∼3.15 mAh/cm2) and outstanding cycle stability of ≥1200 cycles with 84.1% capacity retention at 1 C at 25 °C. This study offers new insights into LRMO cathode design strategies for ASSBs, focusing on ultrastable high-voltage interfaces and high-loading composite electrodes.

Retarding the capacity fading and voltage decay of Li-rich Mn-based cathode materials via a compatible layer coating for high-performance lithium-ion batteries.

Li-rich Mn-based layered oxides have been considered as the most promising cathode candidate for high energy density lithium ion batteries. However, the practical application of Li-rich Mn-based layered oxides is hindered due to the capacity fading and voltage decay accompanied with structure transition from the layered structure to spinel phase during cycling. Herein, a facile surface structure repair via Ce modification is reported. The structural analysis of the bulk and coating layer was carried out using XRD, XPS, SEM and TEM, which confirmed the successful doping of Ce and formation of a Li2CeO3 coating on the surface. The modified sample LLO-2 delivers a discharge specific capacity of 263.5 mA h g-1 at 0.1C and capacity retention rate with 88.1% at 0.2C after 100 cycles compared to 250.2 mA h g-1 and 75.6% for the pristine sample. The enhanced performance could be because Ce doping enlarges the lattice parameter, which may contribute to accelerating the Li+ diffusion rate. Moreover, the newly formed Li2CeO3 coating with oxygen vacancies could inhibit the loss of lattice oxygen and protect the electrode surface by suppressing the attack from the electrolyte. This work provides an effective approach to design Li-rich Mn-based layered oxides with improved electrochemical performance.

Enhancing the electrochemical properties of Li-rich layered oxide cathodes by a facile Fe/Ti integrated modification strategy

Li-rich layered oxide cathodes have gained much attention due to their high specific capacity, high operating voltage, and environmental friendliness. However, poor rate performance, rapid capacity and voltage decay during cycling have hindered its commercial application. In this work, a Fe/Ti integrated modification strategy is proposed to construct a LiFeTiO4 spinel phase coating on the surface of Li1.2Mn0.54Ni0.13Co0.13O2, effectively reducing interfacial side reactions and suppressing the irreversible oxygen release, while doping with Fe3+ and Ti4+ ions can effectively broaden the lithium diffusion channel and enhance the structural stability. As a result, the modified sample with 2 wt% of Fe/Ti demonstrates excellent cycling stability with a superior capacity retention of 91% after 400 cycles at 1C and good rate performance with a high specific discharge capacity of 216 mAh g−1 at 2C. Moreover, the initial Coulombic efficiency of the modified sample is also improved. This integrated modification strategy offers a new design to promote the large-scale application of Li-rich Mn-based cathode materials.

In Situ Surface Reaction for the Preparation of High-Performance Li-Rich Mn-Based Cathode Materials with Integrated Surface Functionalization.

Li-rich Mn-based cathode materials (LLOs) are often faced with problems such as low initial Coulombic efficiency (ICE), limited rate performance, voltage decay, and structural instability. Addressing these problems with a single approach is challenging. To overcome these limitations, we developed an LLO with surface functionalization using a simple fabrication method. This two-step process involved a liquid-stage NaBF4 treatment followed by an in situ chemical reaction during sintering. This reaction led to the creation of oxygen vacancies (OV), spinel structures, and doping with Na at the Li site, B at the tetrahedral interstitial spaces of O in both the transition-metal (TM) layer and Li layers as well as the octahedral interstices in the TM layer, and F at the O site. We have carried out a thorough study and employed density functional theory calculations to reveal the hidden mechanisms. The treatment not only increases the electrical conductivity but also changes the oxygen charge environment and inhibits lattice oxygen activity. Surprisingly, the B-O bond is so strong that it prevents the migration of TM within the tetrahedral interstitial spaces of O in both the TM and Li layers, hence stabilizing its structure. This bonding interaction strengthens the transition of the TM 3d and O 2p states to lower energy levels, thus causing an increase in the redox potentials. Hence, a rise in the operating voltage occurs. Of special importance, this therapy dramatically increases the ICE to 90.29% and keeps a specified capacity of 203.3 mAh/g after 100 cycles at 1C, which is an excellent capacity retention of 89.94%. This study introduces ideas and methods to tackle the challenges associated with LLOs in batteries. It also provides compelling evidence for the development of high-energy-density Li-ion batteries.

Enhancing lithium-rich manganese cathodes: Structural optimization and defect engineering via innovative thermal treatment for improved electrochemical durability and efficiency

Lattice oxygen release, which results in progressive structural disintegration and inevitable capacity fading, poses a significant challenge to the commercialization of Li-rich Mn-based cathode materials. To mitigate voltage capacity degradation and offer a feasible manufacturing process for commercial-scale production, this study developed a cost-effective thermal processing method for a Li-rich Mn-based cathode material Li1.2Ni0.13Co0.13Mn0.54O2 based on water-spray quenching. This method refines the physical phase structure, increases the specific capacity of the material, and creates a defect-tolerant dislocation substructure in the surface lattice. Furthermore, refining the nanoparticle size suppresses the occurrence of redox side reactions and mitigates electrolyte corrosion, resulting in a material with a specific capacity of 196.7 mAh g−1 after 200 cycles at a rate of 1C. This performance markedly exceeds that achieved with the untreated material, which exhibited a capacity of 104.2 mAh g−1 under the same conditions. In contrast to the conventional surface engineering and elemental modulation techniques, this study presents a practical solution for industrial applications, facilitating cost reductions and large-scale production.

Exceptional Rate Performances of Li-Rich Mn-Based Cathodes Enabled by Boron-Based Additives-Driven Self-Optimized Interface.

Li-rich Mn-based cathode material (LRM), as a promising cathode for high energy density lithium batteries, suffers from severe side reactions in conventional lithium hexafluorophosphate (LiPF6)-based carbonate electrolytes, leading to unstable interfaces and poor rate performances. Herein, a boron-based additives-driven self-optimized interface strategy is presented to dissolve low ionic conductivity LiF nanoparticles at the outer cathode electrolyte interface, leading to the optimized interfacial components, as well as the enhanced Li ion migration rate in electrolytes. Being attributed to these superiorities, the LRM||Li battery delivers a high-capacity retention of 92.19% at 1C after 200 cycles and a low voltage decay of 1.08 mV/cycle. This work provides a new perspective on the rational selection of functional additives with an interfacial self-optimized characteristic to achieve a long lifespan LRM with exceptional rate performances.

Stabilized Li-rich Mn-based oxide cathode particles with an artificial surface in-Situ-preprocessing

The heavy hybrid anion and cation redox contributes to high discharge capacity for Li-rich Mn-based cathode material, but also raises a number of issues including the low initial coulombic efficiency (ICE), rapid attenuation of capacity and voltage and so on, which have prevented its commercialization for more than a decade. Herein, solid-liquid impregnating is conducted to in-situ-build an artificial surface for Li1.2Mn0.54Ni0.13Co0.13O2 (FLLO) particles, which concurrently constructed a anion-redox-free LiMn1.5Ni0.5O4 (LNMO) shell during FLLO synthesis process that completely encloses the FLLO lattice (A-2%-LNMO-FLLO), presents as solid solution structure between FLLO and LNMO coating interface and exhibits stronger bonding between coatings and FLLO cathode material. DSC, TEM and industry computed tomography (ICT) evidence that LNMO coatings is effectiveness in stabilizing the crystal structure of FLLO from macro and micro aspects, leading to the excellent electrochemical properties, such as A-2%-LNMO-FLLO exhibits a discharge capacity of 278mAh/g under 0.1C, and the capacity retention is 98.5 % after 200 cycles under 1C. Furthermore, the enhancement mechanism on electrochemical properties is investigated from aspects of reaction process and crystal structure stability. This paper can provide a theoretical and experimental support for the practical application of FLLO cathode material.

Multiple-functional LiTi2(PO4)3 modification improving long-term performances of Li-rich Mn-based cathode material for advanced lithium-ion batteries

Li-rich layered oxides with high energy densities have become one kind of promising cathode for advanced lithium-ion batteries, however some issues are severely hindering their practical applications. To address these challenges, fast ion conductive LiTi2(PO4)3 (LTPO) is employed to modify the typical Li-rich cathode Li1·2Mn0·56Ni0·17Co0·07O2 (LMNCO) via a sol-gel process combined with a two-step annealing treatment in this work. Serving as a physical separator, LTPO coating effectively depresses the side reactions at cathode-electrolyte interface and the transition-metal dissolution from LMNCO active material under harsh electrochemical environment. Meanwhile, LTPO layer with high ion conductivity could facilitate the interfacial Li+ diffusion during charge/discharge process. In addition, partial Ti4+ ions doped into LMNCO effectively elevate the oxygen electronegativity and restrain the excessive oxidization of lattice oxygen, thus stabilizing the crystal structure and alleviating the stress-strain propagation upon cycling. Electrochemical characterization results demonstrate that the LTPO-modified LMNCO cathode exhibits a superior capacity retention of 86.5 % after 400 cycles at room temperature and that of 73.7 % even under an elevated temperature of 45 °C after 250 cycles under 1C. This study provides a facile strategy for the surface modification of Li-rich layered-structure oxides, which also sheds light in enhancing electrochemical performances for various cathode materials.

A cation and anion dual-doping strategy in novel Li-rich Mn-based cathode materials for high-performance Li metal batteries

Lithium (Li)-rich Manganese (Mn)-based cathode materials are considered to be the most hopeful cathode materials for next-generation high-energy-density Li metal batteries. However, the rapid capacity fading and voltage decaying derived from phase transformation still hinder their practical application. Herein, we developed a cation/anion dual-doping strategy by synchronically incorporating Zr4+ cation and F− anion to boost the structural stability of the Li-rich Mn-based cathode. The strengthened transition metal-oxygen bonds raised by doping effect can inhibit the release of oxygen for enhanced electrochemical reversibility and mitigate the anisotropic lattice distortion to stabilize the layered structure. Meanwhile, dual doping strategy expands the lattice distance and increases oxygen vacancy formation energy, thereby improving ion diffusion kinetics and structural stability. As a result, the obtained cathode presents an excellent initial discharge capacity of 268.5 mAh g−1 and a prolonged cycle lifespan beyond 300 cycles. A stable cycling performance can be obtained under a high areal capacity of 5.17 mAh cm−2 with a low negative/positive electrode capacity ratio of 1.93. Our dual-doping strategy provides a valuable new idea for improving the structural stability and electrochemical properties of Li-rich Mn-based cathode materials, further promoting the development of high-energy-density Li metal batteries.

Engineering Reversible Lattice Structure for High-Capacity Co-Free Li-Rich Cathodes with Negligible Capacity Degradation.

Co-free Li-rich Mn-based cathode materials are garnering great interest because of high capacity and low cost. However, their practical application is seriously hampered by the irreversible oxygen escape and the poor cycling stability. Herein, a reversible lattice adjustment strategy is proposed by integrating O vacancies and B doping. B incorporation increases TM─O (TM: transition metal) bonding orbitals whereas decreases the antibonding orbitals. Moreover, B doping and O vacancies synergistically increase the crystal orbital bond index values enhancing the overall covalent bonding strength, which makes TM─O octahedron more resistant to damage and enables the lattice to better accommodate the deformation and reaction without irreversible fracture. Furthermore, Mott-Hubbard splitting energy is decreased due to O vacancies, facilitating electron leaps, and enhancing the lattice reactivity and capacity. Such a reversible lattice, more amenable to deformation and forestalling fracturing, markedly improves the reversibility of lattice reactions and mitigates TM migration and the irreversible oxygen redox which enables the high cycling stability and high rate capability. The modified cathode demonstrates a specific capacity of 200 mAh g-1 at 1C, amazingly sustaining the capacity for 200 cycles without capacity degradation. This finding presents a promising avenue for solving the long-term cycling issue of Li-rich cathode.

Enabling Ultrastable Co-Free Li-Rich Oxides via TbF3 Treatment.

Co-free Li-rich Mn-based cathode materials (Co-free LRMOs) have become one of the most promising cathode materials in lithium-ion batteries for the next generation due to their low cost, high capacity, and environmental friendliness. Under high voltage, redox reactions involving anions can easily lead to various issues, including oxygen release, dissolution of transition metal elements (TMs), and structural collapse in these materials. The absence of the Co element further exacerbates this issue. Here, a simple one-step solid-phase reaction strategy is proposed to achieve nanoscale dual modification of the Co-free LRMOs with F and Tb doping. The dual modification has a relatively small impact on the cell parameters and Li+ diffusion ability of the LRMOs, leading to no significant improvement in its rate performance. The modified LRMOs only exhibited discharge capacities of 220.7, 200.1, 140.0, 115.5, and 90.9 mAh·g-1 at 0.1, 0.2, 1.0, 2.0, and 5.0 C, respectively. However, the modified Co-free LRMOs exhibit extremely strong structural stability and retain 95.1% of the initial capacity after 300 cycles, so far, the highest capacity retention rates among all Ni/Mn-based Li-rich materials. Mechanism studies have shown that the enhancement in structural stability of the Co-free LRMOs is attributed to the increased concentration of oxygen vacancies and Ni3+ ions through F doping. Furthermore, Tb doping not only hinders the release of O2 but also enhances the Li+ migration and electronic conductivity coefficient of the LRMOs.

Synergistic strategy of surface-induced spinel structure and F doping to improve the electrochemical performance of Li-rich cathodes

Li-rich Mn-based materials provide higher capacity than commercial NCM layered materials due to the synergistic redox effect of cations and anions. However, lattice straining and structural collapse caused by the irreversible oxygen release at high voltage range during cycling, which results in severe capacity and voltage decay. Herein, a synergistic strategy of surface-induced spinel structure and F doping is provided to improve the structural stability. The surface spinel structure helps to reduce the structural collapse caused by electrolyte corrosion on the cathode and effectively inhibits voltage decay resulted from structural evolution. The stronger Mn-F bonds are formed by F doping to inhibit migration of transition metal (TM) and induce the uniform deposition of LiF to form the thinner and more stable CEI on the cathode. Accordingly, the designed cathode (LMNO-NF) shows remarkable cycling performance with the capacity retention of 86.68 ​% and voltage retention of 96.6 ​% for 200 cycles at 1C, higher than pristine material (68.76 ​% and 85.75 ​%). Therefore, this simple dual-modification strategy of one-step synthesis is promising for solving the structural evolution and voltage decay of Li-rich Mn-based cathode materials effectively, achieving further commercialization.

Uniform amorphous MgxByOz coating combined with Vo for highly stable Li-Rich Mn-based cathode material

Li-rich Mn-based cathode materials (LRs) have attracted significant research interests owing to high energy density, but their commercial application is limited by capacity/voltage attenuation caused by irreversible lattice oxygen release, structural reconstruction, interface reactions, as well as the dissolution of transition metals (TM). This work proposed a synergistic modification strategy of surface coating by magnesium borate (MgxByOz) cooperated with defect construction of enriched oxygen vacancy (Vo) for Li1.2Mn0.54Ni0.13Co0.13O2 cathode material, and the interior and exterior modification has been achieved in one step through the interaction between reducing agent of BH4- and oxygen at surface. The amorphous MgxByOz coating with good mechanical strength and toughness provides lasting protection and prevents phase degradation from layered to rock-salt phase. The constructed Vo reduce irreversible oxygen release and subsequently slows down capacity decay and voltage degradation. The modified MBO2-LR exhibits superior rate capacity with a specific capacity of 140.6 mAh g−1 at a high current density of 10C and an satisfactory capacity retention of 83.6% after 200 high-voltage cycles at 1C, much higher than the values of the pristine sample. This work offers a viable modifying route for the promising cathode materials with high energy density.

PO43--doped layer @ spinel @ rGO sandwich-structured lithium-rich manganese-based cathode material with enhancing rate capability and cycle stability for Li-ion battery

The Li-rich Mn-based cathode (LRM) material faces challenges like low initial coulombic efficiency (ICE) and reduced capacity retention, which limit their commercial viability in high energy density lithium-ion batteries (LIBs). These challenges primarily arise from the irreversible migration of transition metal ions (TMn+) and the escape of lattice oxygen. Herein, this study proposes a novel approach to enhance Li-rich cathodes by implementing a PO43--doped layer @ spinel @ rGO sandwich structure, which effectively addresses the aforementioned challenges. Through the synergistic effects of PO43- doping and rGO surface modification, the modified samples demonstrate remarkable electrochemical properties. These include an impressive initial coulombic efficiency (ICE) of 87.54%, and a superior capacity of 187.12 mAhg−1 and 149.44 mAhg−1 at 25°C and 45°C, respectively, following 200 cycles at 1 C. Additionally, they exhibit an outstanding rate capability of 82.3 mAhg−1 at 10 C and a minimal voltage decrease of 0.504 V after 200 cycles. The synergetic strategy presented in this work serves as an inspiring source for the exploration of high energy density and long-cycle cathode materials.

Simultaneous dual modification of Li-rich Mn-based cathode in restraining oxygen release and structure distortion

Li-rich Mn-based cathode material is modified by a dual modification approach involving Ce, B co-doping, which regulates energy band and induces surface structure reorganization to suppress lattice oxygen precipitation and electrolyte corrosion, thereby improving the cell performance.

Design of a new Li-rich Mn-based ternary cathode material based on the Ni, Co, and Mn action mechanism.

Rechargeable lithium-ion batteries, as the most advanced energy storage devices currently available, urgently require the development of cathode materials with high capacity, large specific energy, and fast charge/discharge performance to satisfy the continuous technological innovation. Here, a Li-rich Mn-based ternary cathode material Li7/6Nil/6Co1/6Mn1/2O2 is designed, and the geometrical structure, electronic properties, and thermodynamic properties of this material are investigated employing the first-principles method. Six layered structure models are established by adjusting the ratio of Ni, Co, and Mn elements, and the effects of various elements on the material properties are evaluated. Based on the performance of Ni, Co, and Mn in the structure, Li1.2Ni0.15Co0.1Mn0.55O2 features favorable electrical conductivity, thermal conductivity, and excellent stability. This material obtained through co-precipitation using a high temperature solid phase synthesis presents a high actual capacity (245 mA h g-1) and superior cycling performance (the capacity retention rate of the material is 84% after 60 cycles at 0.2C). This effort discusses the Li-rich Mn-based cathode materials in terms of the structural basis, reaction mechanism, and application exploration, which are valuable for guiding their theoretical design, optimization modification, and industrial application.

Li-Rich Mn-Based Cathode Materials for Li-Ion Batteries: Progress and Perspective

The development of cathode materials with high specific capacity is the key to obtaining high-performance lithium-ion batteries, which are crucial for the efficient utilization of clean energy and the realization of carbon neutralization goals. Li-rich Mn-based cathode materials (LRM) exhibit high specific capacity because of both cationic and anionic redox activity and are expected to be developed and applied as cathode materials for a new generation of high-energy density lithium-ion batteries. Nevertheless, the difficulty of regulating anionic redox reactions poses significant challenges to LRM, such as low initial Coulombic efficiency, poor rate capability, and fast cycling capacity and voltage decay. To address the existing challenges of LRM, this review introduces their basic physicochemical characteristics in detail, analyzes the original causes of these challenges, focuses on the recent progress of the modification strategies, and then especially discusses the development prospects of LRM from different aspects.

Concentration-gradient of Li-rich Mn-based cathode materials with enhanced cycling retention

Lithium-rich layered Mn-based materials have attracted much attention because of their high specific capacity and high energy density, but they have the characteristics of irreversible capacity loss, low initial coulombic efficiency, and poor cycling performance. In this study, a core-shell structure, including Mn0.75Ni0.25C2O4 precursor as core and Li-rich Mn-based oxides (LRMO, Li1.2Mn0.54Ni0.13Co0.13O2) as shell layer respectively, was synthesized by co-precipitation and sol-gel method. After sintering at high temperatures, the element concentration-gradient oxides material (LRMO-G) was formed. The material was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) and its electrochemical performance was investigated by various electrochemical methods. The LRMO-G material exhibits a high initial discharge specific capacity of 268 mAh/g at 0.1 C, and extremely superior capacity retention (95.4 %) after 100 cycles at 1 C. The initial coulomb efficiency of the LRMO-G material increases to 85 %, which is 12 % higher than that of LRMO.