Properties of the “Z”-Phase in Mn-Rich P2-Na0.67Ni0.1Mn0.8Fe0.1O2 as Sodium-Ion-Battery Cathodes

P₂ layered oxides have attracted more and more attention as cathode materials of high-power sodium-ion batteries (SIBs). During the charging process, the release of sodium ions leads to layer slip, which leads to the transformation of P₂ phase into O₂ phase, resulting in a sharp decline in capacity. However, many cathode materials do not undergo P₂-O₂ transition during charging and discharging, but form a “Z” phase. It is proved that the iron-containing compound Na_0.67Ni_0.1Mn_0.8Fe_0.1O₂ formed the “Z” phase of the symbiotic structure of the P phase and O phase during high-voltage charging through ex-XRD and HAADF-STEM. During the charging process, the cathode material undergoes a structural change of P₂-OP₄-O₂. With the increase of charging voltage, the O-type superposition mode increases to form an ordered OP4 phase, and the P₂-type superposition mode disappears after further charging to form a pure O₂ phase. ⁵⁷Fe-Mössbauer spectroscopy revealed that no migration of Fe ions is detected. The O–Ni–O–Mn–Fe–O bond formed in the transition metal MO₆ (M = Ni, Mn, Fe) octahedron can inhibit the elongation of the Mn–O bond and improve the electrochemical activity so that P2-Na_0.67Ni_0.1Mn_0.8Fe_0.1O₂ has an excellent capacity of 172.4 mAh g⁻¹ and a coulombic efficiency close to 99% at 0.1C.     

Synthesis and electrochemical properties of LiNi0.9Co0.1O2 cathode material for lithium secondary battery

Layered LiNi_0.9Co_0.1O₂ cathode material has been successfully synthesized with a calcination time of 0.5 h by a rheological phase reaction method. The obtained powder was characterized by X-ray diffraction (XRD), particle size and particle size distribution, scanning electronic microscope (SEM) and electrochemical measurements. The powder is confirmed to be α-NaFeO₂ structure. Cyclic voltammetry (CV) studies imply that the phase transitions from hexagonal to monoclinic exist during charge–discharge cycling. The LiNi_0.9Co_0.1O₂ cathode demonstrated a good electrochemical property with an initial discharge capacity of 193 mAh g^?1 and capacity retention of 88.6% after 15 cycles.     

LiNi0.9Co0.1O2正极材料的EDTA络合法合成及其性能研究

采用络合法制备了锂离子电池的活性正极材料LiNi_0.9Co_0.1O2粉体,实验表明合成的LiNi_0.9Co_0.1O₂粉体结晶良好,层状结构发育完善。电池充放电测试结果表明,其容量及循环性能与LiNi_0.9Co_0.1O₂粉体的合成温度有关,其中900℃合成得到的LiNi_0.9Co_0.1O₂材料具有最好的电化学性能,首次放电比容量高达120.5mAh/g,循环30次后可逆放电比容量仍高达118.8mAh/g,容量损失仅为1.4％。文中对容量退化的原因进行了分析。     

Correlating Rate-Dependent Transition Metal Dissolution between Structure Degradation in Li-Rich Layered Oxides

Understanding the mechanism of the rate-dependent electrochemical performance degradation in cathodes is crucial to developing fast charging/discharging cathodes for Li-ion batteries. Here, taking Li-rich layered oxide Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ as the model cathode, the mechanisms of performance degradation at low and high rates are comparatively investigated from two aspects, the transition metal (TM) dissolution and the structure change. Quantitative analyses combining spatial-resolved synchrotron X-ray fluorescence (XRF) imaging, synchrotron X–ray diffraction (XRD) and transmission electron microscopy (TEM) techniques reveal that low-rate cycling leads to gradient TM dissolution and severe bulk structure degradation within the individual secondary particles, and especially the latter causes lots of microcracks within secondary particles, and becomes the main reason for the fast capacity and voltage decay. In contrast, high-rate cycling leads to more TM dissolution than low-rate cycling, which concentrates at the particle surface and directly induces the more severe surface structure degradation to the electrochemically inactive rock-salt phase, eventually causing a faster capacity and voltage decay than low-rate cycling. These findings highlight the protection of the surface structure for developing fast charging/discharging cathodes for Li-ion batteries.     

Construction of MnO2 Artificial Leaf with Atomic Thickness as Highly Stable Battery Anodes

The leaf-like structure is a classic and robust structure and its unique vein support can reduce structural instability. However, biomimetic leaf structures on the atomic scale are rarely reported due to the difficulty in achieving a stable vein-like support in a mesophyll-like substrate. A breathable 2D MnO₂ artificial leaf is first reported with atomic thickness by using a simple and mild one-step wet chemical method. This homogeneous ultrathin leaf-like structure comprises of vein-like crystalline skeleton as support and amorphous microporous mesophyll-like nanosheet as substrate. When used as an anode material for lithium ion batteries, it first solves the irreversible capacity loss and poor cycling issue of pure MnO₂, which delivers high capacity of 1210 mAh g⁻¹ at 0.1 A g⁻¹ and extremely stable cycle life over 2500 cycles at 1.0 A g⁻¹. It exhibits the most outstanding cycle life of pure MnO₂ and even comparable to the most MnO₂-based composite electrode materials. This biomimetic design provides important guidelines for precise control of 2D artificial systems and gives a new idea for solving poor electrochemical stability of pure metal oxide electrode materials.     

Boosting Reaction Homogeneity in High-Energy Lithium-Ion Battery Cathode Materials

Conventional nickel-rich cathode materials suffer from reaction heterogeneity during electrochemical cycling particularly at high temperature, because of their polycrystalline properties and secondary particle morphology. Despite intensive research on the morphological evolution of polycrystalline nickel-rich materials, its practical investigation at the electrode and cell levels is still rarely discussed. Herein, an intrinsic limitation of polycrystalline nickel-rich cathode materials in high-energy full-cells is discovered under industrial electrode-fabrication conditions. Owing to their highly unstable chemo-mechanical properties, even after the first cycle, nickel-rich materials are degraded in the longitudinal direction of the high-energy electrode. This inhomogeneous degradation behavior of nickel-rich materials at the electrode level originates from the overutilization of active materials on the surface side, causing a severe non-uniform potential distribution during long-term cycling. In addition, this phenomenon continuously lowers the reversibility of lithium ions. Consequently, considering the degradation of polycrystalline nickel-rich materials, this study suggests the adoption of a robust single-crystalline LiNi_0.8Co_0.1Mn_0.1O₂ as a feasible alternative, to effectively suppress the localized overutilization of active materials. Such an adoption can stabilize the electrochemical performance of high-energy lithium-ion cells, in which superior capacity retention above ≈80% after 1000 cycles at 45 °C is demonstrated.     

Illumining phase transformation dynamics of vanadium oxide cathode by multimodal techniques under operando conditions

Subtle structural changes during electrochemical processes often relate to the degradation of electrode materials. Characterizing the minute-variations in complementary aspects such as crystal structure, chemical bonds, and electron/ion conductivity will give an in-depth understanding on the reaction mechanism of electrode materials, as well as revealing pathways for optimization. Here, vanadium pentoxide (V₂O₅), a typical cathode material suffering from severe capacity decay during cycling, is characterized by in-situ X-ray diffraction (XRD) and in-situ Raman spectroscopy combined with electrochemical tests. The phase transitions of V₂O₅ within the 0–1 Li/V ratio are characterized in detail. The V–O and V–V distances became more extended and shrank compared to the original ones after charge/discharge process, respectively. Combined with electrochemical tests, these variations are vital to the crystal structure cracking, which is linked with capacity fading. This work demonstrates that chemical bond changes between the transition metal and oxygen upon cycling serve as the origin of the capacity fading.

     

Capacity stabilization of layered Li0.9Mn0.9Ni0.1O2 cathode material by employing ZnO coating

Li_0.9Mn_0.9Ni_0.1O₂ has been prepared by an ion-exchange process and evaluated as the positive electrode material for lithium-ion battery application. The particles of the oxide have been subjected to surface modification by coating a thin layer of ZnO. Both the ZnO coated and bare samples have been characterized by chemical analysis, powder X-ray diffraction, scanning electron microscopy, EDAX, EDS-dot mapping, cyclic voltammetry, charge–discharge cycling and AC impedance spectroscopy. The physicochemical studies suggest the formation of a layered structure in the oxide with a uniformly dispersed ZnO coating on fine particles. The electrochemical studies suggest a stable discharge capacity of 210 mA h g⁻¹ for ZnO coated oxide over about 50 cycles tested in the studies. By contrast, the capacity of bare oxide decreases rapidly on cycling. The enhanced performance of these electrodes is also reflected in AC impedance studies.     

A facile method to enhance electrochemical performance of high-nickel cathode material Li(Ni<Subscript>0.8</Subscript>Co<Subscript>0.1</Subscript>Mn<Subscript>0.1</Subscript>)O<Subscript>2</Subscript> via Ti doping

The cycle stability of Li(Ni_0.8Co_0.1Mn_0.1)O₂ is enhanced obviously by titanium doping via a facile solid-state method. The property of crystal structure is evaluated by XRD, which illustrates the samples possessed a layered α-NaFeO₂ structure with R-3m space group. According to the charge/discharge studies, the capacity retention of pristine sample is around 51% after 125 cycles at 5 C, and the sample with Ti dopant displays a good cyclic stability, after 125 cycles, the capacity retention increases to 75% under 5 C, suggesting it could be possibly applied in fast charge Lithium-ion battery area. The superb electrochemical performance might be attributed to the Ti⁴⁺ occupy the layer structure to broaden the Lithium-ion channel, which is benefit to lithium intercalation and deintercalation during cycling.     

LiNi0.8 Co0.15 A10.05 O2正极材料的表面包覆改性研究

LiNi_0.8 Co_0.15 A1_0.05 O₂正极材料具有容量高、价格低等优点,被认为是最具发展前景的锂离子电池正极材料之一.但LiNi 0.8Co 0.15A1 0.05O₂材料本身存在充放电过程中容量衰减较快、倍率性能差和储存性能差等缺陷,影响了其进一步发展.本文以 LiNi 0.8Co 0.15A1 0.05O₂为研究对象,采用共沉淀法制备氢氧化物前驱体,在前驱体的表面包覆一层Ni 1/3Co 1/3 Mn 1/3(OH)₂,制备成具有核壳结构的正极材料.通过XRD、SEM、EDX、电化学测试等分析手段,系统地研究了其结构、形貌以及电化学性能.分析表明:包覆改性后,LiNi 0.8Co 0.15Al 0.05O₂正极材料在0.1、0.2、0.5、1 C倍率下,材料的首次充放电比容量分别为167.6,160.1,0.4,8.5 mAhg -1.由0.1到1 C,包覆改性前后的正极材料的放电比容量衰减量由34.7 mAhg -1降为29.1 mAhg -1,容量衰减百分比由22.1%降低到17.4%.综合性能分析认为,包覆改性后电化学性能有一定的改善.     

Dually-functionalized Ni-rich layered oxides for high-capacity lithium-ion batteries

Layered lithium nickel-cobalt-manganese oxides(NCM)have been highlighted as advanced cathode materials for lithium-ion batteries(LIBs);however,their low interfacial stability must be overcome to ensure stable cycling performance of the cell.In this work,we propose a one-step surface modi-fication method that uses a task-specific precursor,N,N,N,N-tetraethylsulfamide(NTESA),to improve interfacial stability of Ni-rich NCM cathode materials.The unstable surface properties of Ni-rich NCM cathode material are improved by embedding an artificial cathode-electrolyte interphase(CEI)layer on the cathode surface by heat treatment of the Ni-rich NCM cathode material with an NTESA precursor at low temperature.Our material analyses indicate that this approach allows the formation of amine-and sulfone-functionalized CEI layers on the surface of Ni-rich NCM cathode material without changing the layered structure of the cathode material.NTESA-functionalized Ni-rich NCM cathode materials exhibit improved cycling retention after 100 cycles:for example,a cell cycled with a 3.0 NTESA-modified NCM811 cathode presents the highest retention ratio of 88.3％,whereas a cell cycled with a non-functionalized NCM811 cathode suffers from rapid fading of the cycling performance(68.4％).Our additional SEM,XPS,and EIS analyses indicate that electrolyte decomposition is suppressed during electrochemical cycling,thereby leading to smaller increases in the internal resistances.ICP-MS analyses of the cycled anodes also indicate that the NTESA-based artificial CEI layer inhibits the dissolution of transition metal components from the Ni-rich NCM cathode materials,thereby contributing to an improved overall electrochemical performance of the cell.     

Nanoscale Manipulation of Spinel Lithium Nickel Manganese Oxide Surface by Multisite Ti Occupation as High‐Performance Cathode

A novel two‐step surface modification method that includes atomic layer deposition (ALD) of TiO₂ followed by post‐annealing treatment on spinel LiNi_0.5Mn_1.5O₄ (LNMO) cathode material is developed to optimize the performance. The performance improvement can be attributed to the formation of a TiMn₂O₄ (TMO)‐like spinel phase resulting from the reaction of TiO₂ with the surface LNMO. The Ti incorporation into the tetrahedral sites helps to combat the impedance growth that stems from continuous irreversible structural transition. The TMO‐like spinel phase also alleviates the electrolyte decomposition during electrochemical cycling. 25 ALD cycles of TiO₂ growth are found to be the optimized parameter toward capacity, Coulombic efficiency, stability, and rate capability enhancement. A detailed understanding of this surface modification mechanism has been demonstrated. This work provides a new insight into the atomic‐scale surface structural modification using ALD and post‐treatment, which is of great importance for the future design of cathode materials.     

锂离子电池高镍LiNi0.8Mn0.2O2正极材料的微波合成及其Co、Al共改性

高镍正极材料由于较高的比容量和性价比而受到关注, 但在循环过程中稳定性较差且安全性能不佳, 限制了其更广泛的应用。本研究结合微波辅助共沉淀与高温固相法制备高镍正极LiNi_0.8Mn_0.2O₂二元材料, 再掺入不同比例的Co、Al对材料进行改性研究。结果表明, 改性后的材料性能明显改善, 特别是LiNi_0.8Mn_0.1Co_0.08Al_0.02O₂在2.75~4.35 V、1C下循环100次后容量保持率达到91.39%, 在5C下放电比容量仍有160.03 mAh∙g^-1, 并且掺杂后的材料具有较高的热稳定性, 安全性得到提升。其优异的循环保持率归因于Co、Al较好地抑制了循环过程中H2→H3相变的不可逆性对材料结构稳定性的破坏, 以及较弱的电极反应极化, 使电荷转移电阻降低。     

A highly stabilized Ni-rich NCA cathode for high-energy lithium-ion batteries

In this study, we have demonstrated that boron doping of Ni-rich Li[Ni_xCo_yAl_1−x−y]O₂ dramatically alters the microstructure of the material. Li[Ni_0.885Co_0.1Al_0.015]O₂ is composed of large equiaxed primary particles, whereas a boron-doped Li[Ni_0.878Co_0.097Al_0.015B_0.01]O₂ cathode consists of elongated particles that are highly oriented to produce a strong, crystallographic texture. Boron reduces the surface energy of the (0 0 3) planes, resulting in a preferential growth mode that maximizes the (0 0 3) facet. This microstructure modification greatly improves the cycling stability; the Li[Ni_0.878Co_0.097Al_0.015B_0.01]O₂ cathode maintains a remarkable 83% of the initial capacity after 1000 cycles even when it is cycled at 100% depth of discharge. By contrast, the Li[Ni_0.885Co_0.1Al_0.015]O₂ cathode retains only 49% of its initial capacity. The superior cycling stability clearly indicates the importance of the particle microstructure (i.e., particle size, particle shape, and crystallographic orientation) in mitigating the abrupt internal strain caused by phase transitions in the deeply charged state, which occurs in all Ni-rich layered cathodes. Microstructure engineering by surface energy modification, when combined with protective coatings and composition modification, may provide a long-sought method of harnessing the high capacity of Ni-rich layered cathodes without sacrificing the cycling stability.     

Boosting the electrochemical performance of LiNi0.8Co0.1Mn0.1O2 cathode materials with Zn3(PO4)2 surface coating

Ni-rich layered oxides have been demonstrated to be promising cathode materials for high-energy–density batteries. However, most of them suffer from sluggish kinetics and structural instability, severely impeding their practical applications. Herein, the surface of LiNi_0.8Co_0.1Mn_0.1O₂ cathode is modified with ionic, conducting zinc phosphate (Zn₃(PO₄)₂) nanolayers. The nanolayers are autogenously formed from the reaction of NH₄H₂PO₄ with ZnO assisted with citric acid. The as-prepared 3 wt% Zn₃(PO₄)₂ coated sample exhibits a first discharge capacity of 203.4 mAh g^-1and excellent capacity retention for 100 cycles. The surface Zn₃(PO₄)₂ nanolayers positively impact the cell performance by scavenging HF and H₂O in the electrolyte, leading to less formation of byproducts on the surface of the cathodes, which lowers the cell resistance and polarization voltage. Our study provides a simple and efficient strategy to design and optimize promising layer-structural cathodes for LIBs.     

Fast Capacitive Energy Storage and Long Cycle Life in a Deintercalation–Intercalation Cathode Material

Ni‐rich Li‐ion cathode materials promise high energy density, but are limited in power density and cycle life, resulting from their poor dynamic characteristics and quick degradation. On the other hand, capacitor electrode materials promise high power density and long cycle life but limited capacities. A joint energy storage mechanism of these two kinds is performed in the material‐compositional level in this paper. A valence coupling between carbon π‐electrons and O^2? is identified in the as‐prepared composite material, using a tracking X‐ray photoelectron spectroscopy strategy. Besides delivering capacity simultaneously from its LiNi_0.8Co_0.1Mn_0.1O₂ and capacitive carbon components with impressive amount and speed, this material shows robust cycling stability by preventing oxygen emission and phase transformation via the discovered valence coupling effect. Structural evolution of the composite shows a more flattened path compared to that of the pure LiNi_0.8Co_0.1Mn_0.1O₂, revealed by the in situ X‐ray diffraction strategy. Without obvious phase transformation and losing active contents in this composite material, long cycling can be achieved.     

Suppressing Cation Migration and Reducing Particle Cracks in a Layered Fe‐Based Cathode for Advanced Sodium‐Ion Batteries

Sodium‐ion batteries have huge potential in large‐scale energy storage applications. Layered Fe‐based oxides are one of the desirable cathode materials due to abundance in the earth crust and high activity in electrochemical processes. However, Fe‐ion migration to Na layers is one of the major hurdles leading to irreversible structural degradation. Herein, it is revealed that distinct Fe‐ion migration in cycling NaFeO₂ (NFO) should be mainly responsible for the strong local lattice strain and resulting particle cracks, all of which results in the deterioration of electrochemical performance. More importantly, a strategy of Ru doping could effectively suppress the Fe‐ion migration and then reduce the local lattice strain and the particle cracks, finally to greatly enhance the sodium storage performance. Atomic‐scale characterization shows that NFO electrode after cycling presents the intense lattice strain locally, accompanied by the remarkable particle cracks. Whereas, Ru‐doped NFO electrode maintains the well‐ordered layered structure by inhibiting the Fe–O distortion, so as to eliminate the resulting side effect. As a result, Ru‐doped NFO could greatly improve the comprehensive electrochemical performance by delivering a reversible capacity of 120 mA h g^?1, about 80% capacity retention after 100 cycles. The findings provide new insights for designing high‐performance electrodes for sodium‐ion batteries.     

Synthesis and characterization of LiNi<Subscript>0.9</Subscript>Co<Subscript>0.1</Subscript>O<Subscript>2</Subscript> for lithium batteries

LiNi_0.9Co_0.1O₂ cathode material is prepared from LiOH·H₂O and Ni_0.9Co_0.1(OH)₂ by co-precipitation and subsequent two-stage heat treatment in flowing oxygen based on the results of thermogravimetric. The structural and electrochemical properties of the samples are characterized by means of inductively coupled plasma-atomic emission spectrometer (ICP-AES), X-ray diffraction (XRD), scanning electron microscope (SEM), cyclic voltammogram (CV) and charge–discharge studies. All the samples sintered at different temperatures have a typical layered structure with space group R3-m and good electrochemical performances. The sintering temperature has a remarkable effect on the electrochemical performance of the samples. The sample sintered at 730 °C shows the largest initial discharge capacity 191.1 mAh g⁻¹ (50 mA g⁻¹, 3.0–4.3 V) and the best cycling performance. The initial discharge capacity rises to above 200 mAh g⁻¹ with the voltage range 3.0–4.5 V.     

Understanding the Insight Mechanism of Chemical-Mechanical Degradation of Layered Co-Free Ni-Rich Cathode Materials: A Review

Layered Cobalt (Co)-free Nickel (Ni)-rich cathode materials have attracted much attention due to their high energy density and low cost. Still, their further development is hampered by material instability caused by the chemical/mechanical degradation of the material. Although there are numerous doping and modification approaches to improve the stability of layered cathode materials, these approaches are still in the laboratory stage and require further research before commercial application. To fully exploit the potential of layered cathode materials, a more comprehensive theoretical understanding of the underlying issues is necessary, along with active exploration of previously unrevealed mechanisms. This paper presents the phase transition mechanism of Co-free Ni-rich cathode materials, the existing problems, and the state-of-the-art characterization tools employed to study the phase transition. The causes of crystal structure degradation, interfacial instability, and mechanical degradation are elaborated, from the material's crystal structure to its phase transition and atomic orbital splitting. By organizing and summarizing these mechanisms, this paper aims to establish connections among common research problems and to identify future research priorities, thereby facilitating the rapid development of Co-free Ni-rich materials.     

Enhancing Ionic Transport and Structural Stability of Lithium-Rich Layered Oxide Cathodes via Local Structure Regulation

Lithium-rich manganese-based layered oxides (LRM) have garnered considerable attention as cathode materials due to their superior performance. However, the inherent structural degradation and obstruction of ion transport during cycling lead to capacity and voltage decay, impeding their practical applications. Herein, an Sb-doped LRM material with local spinel phase is reported, which has good compatibility with the layered structure and provides 3D Li⁺ diffusion channels to accelerate Li⁺ transport. Additionally, the strong Sb-O bond enhances the stability of the layered structure. Differential electrochemical mass spectrometry indicates that highly electronegative Sb doping effectively suppresses the release of oxygen in the crystal structure and mitigates successive electrolyte decomposition, thereby reducing structural degradation of the material. As a result of this dual-functional design, the 0.5 Sb-doped material with local spinel phases exhibits favorable cycling stability, retaining 81.7% capacity after 300 cycles at 1C, and an average discharge voltage of 1.87 mV per cycle, which is far superior to untreated material with retention values of 28.8% and 3.43 mV, respectively. This study systematically introduces Sb doping and regulates local spinel phases to facilitate ion transport and alleviate structural degradation of LRM, thereby suppressing capacity and voltage fading, and improving the electrochemical performance of batteries.