Cathode Material For Batteries Research Articles

High cycling stability of MnO2 cathode for aqueous Mg-ion batteries enabled by Fe doping

MnO2 has been widely investigated as a promising cathode material for aqueous magnesium-ion batteries, which, however, suffers from the severe capacity fading during charge/discharge cycling. In present work, we report that the doping of Fe in α-MnO2 enlarges the lattice and alleviates the Jahn–Teller distortions and thus accelerates the Mg2+ diffusion and strengthens the structural stability. Consequently, the capacity retention remarkably increases from 44.3 % to 85.2 % after 1000 cycles by Fe doping. Furthermore, it is found for the first time that Fe doping enables the co-insertion of H+ and Mg2+ in the tunnels of α-MnO2, which improves remarkably the specific capacity from 131.9 to 205.9 mA h g−1 at 0.1 A g−1.

Mitigating voltage decay of O3‐NaNi1/3Fe1/3Mn1/3O2 layered oxide cathode for sodium‐ion batteries by incorporation of 5d metal tantalum

AbstractThe cycling stability of O3‐type NaNi1/3Fe1/3Mn1/3O2 (NFM) as a commercial cathode material for sodium ion batteries (SIBs) is still a challenge. In this study, the Ni/Fe/Mn elements are replaced successfully with tantalum (Ta) in the NFM lattice, which generated additional delocalized electrons and enhanced the binding ability between the transition metal and oxygen, resulting in suppressed lattice distortion during charging and discharging. This caused significant mitigation of voltage decay and improved cycle stability within the potential range of 2.0–4.2 V. The optimized Na(Ni1/3Fe1/3Mn1/3)0.97Ta0.03O2 sample achieved a reversible capacity of 162.6 mAh g−1 at a current rate of 0.1 C and 73.2 mAh g−1 at a high rate of 10 C. Additionally, the average charge/discharge potential retention reached 98% after 100 cycles, significantly mitigating the voltage decay. This work demonstrates a significant contribution towards the practical utilization of NFM cathodes in the SIBs energy storage field.

Boosting the Electrochemi,cal Performance of Primary and Secondary Lithium Batteries with Mn-Doped All-Fluoride Cathodes.

Transition metal fluorides are potentially high specific energy cathode materials of next-generation lithium batteries, and strategies to address their low conductivity typically involve a large amount of carbon coating, which reduces the specific energy of the electrode. In this study, MnyFe1-yF3@CFx was generated by the all-fluoride strategy, converting most of the carbon in MnyFe1-yF3@C into electrochemical active CFx through a controllable NF3 gas phase fluorination method, while still retaining a tightly bound graphite layer to provide initial conductivity, which greatly improved the energy density of the composite. This synergistic effect of nonfluorinated residual carbon (∼11%) and Mn doping ensures the electrochemical kinetics of the composite. The loading mass of the active substance had been increased to 86%. The theoretical and actual discharge capacity of MnyFe1-yF3@CFx composite was up to 765 mAh g-1 (pure FeF3 is 712 mAh g-1) and 728 mAh g-1, respectively. The discharge capacity at the high-voltage (3.0 V) platform was more than three times higher than that of the non-Mn-doped composite (FeF3@CFx).

Exploring the potential of Mbenes in energy storage

MBene, a layered metal boride similar to MXene, has garnered significant attention in recent times. Nevertheless, there is still a lack of comprehensive understanding regarding their structure and properties, necessitating further research and investigation. In this study, theoretical calculations were employed first to study the binding energy, band structures and density of states of three MBenes, namely MoB, MgB2, and ZrB2, providing insights into their electronic characteristics. In addition, open circuit voltage (OCV) and adsorption energy were also conducted using the three MBenes as cathode materials for zinc ion batteries, indicating their low ion migration barrier and potential in energy storage application. Subsequently, MoB, MgB2, and ZrB2 were experimentally synthesized using etching or exfoliation method and utilized as cathode materials for zinc ion batteries. Results demonstrates that the specific capacity of MoB is 60 mAh g-1 at 0.1 A g-1. Systematic investigation including kinetics simulation and ex situ XRD suggests the cation insertion mechanism of the MoB electrodes. Building upon these findings, attempts were made to enhance the performance of MoB through the incorporation of 1 T-MoS2 composites, urea molecular intercalation. Notably, the modified composite exhibited a specific capacity exceeding 150 mAh g-1 at 0.1 A g-1, with a stable Coulombic efficiency of 100% after 100 cycles. This study provides novel directions and insights for the research of MBene in the context of aqueous zinc-ion batteries.

Rational design of V2O5 nanorod anchored carbon microsphere cathode materials for improved-performance lithium-ion batteries

Rational design of V2O5 nanorod anchored carbon microsphere cathode materials for improved-performance lithium-ion batteries

Intercalation-Induced Localized Conversion Reaction in h-CuSe for Ultrafast-Rechargeable and Long-Cycling Sodium Metal Battery.

Cathode materials of sodium-based batteries with high specific capacity and fast charge/discharge mode, as well as ultralong reversible cycles at wide applied temperatures, are essential for future development of advanced energy storage system. Developing transition metal selenides with intercalation features provides a new strategy for realizing the above cathode materials. Herein, we report a storage mechanism of sodium ion in hexagonal CuSe (h-CuSe) based on the DFT guidance. We reveal that the two-dimensional ion intercalation triggers localized redox reaction in the h-CuSe bulk phase, termed intercalation-induced localized conversion (ILC) mechanism, to stabilize the sodium storage structure by forming localized Cu7Se4 transition phase and adjusting the near-edge coordination state of the Cu sites to achieve high reversible capacity and ultra-long cycling life, while allowing rapid charge/discharge cycling over a wide temperature range. This article is protected by copyright. All rights reserved.

First-principles study of high-entropy sulfides and their alkali metal-doped modification as cathode material for sodium-ion batteries.

High-entropy materials (HEMs) have been explored as high-capacity cathode materials for sodium-ion batteries (SIBs) due to their excellent structural stability and abundant metal redox sites. Among them, high-entropy sulfides (HESs) have greater potential and more extensive research than high-entropy oxides, as they exhibit higher charging voltage and theoretical capacity as cathodes. Furthermore, alkali metal doping of HESs can further enhance their performance and broaden their application fields. Inspired by the cocktail effect of HEMs, we performed the first theoretical calculation of the properties of Na(MnFeCoNi)1/2S and its Li-doped derivative, Na7/8Li1/8(MnFeCoNi)1/2S, to understand their potential as SIB cathode materials. Using density functional theory based on first principles, we investigated the structure and electronic characteristics of Na(MnFeCoNi)1/2S and Na7/8Li1/8(MnFeCoNi)1/2S, and calculated their theoretical voltage and capacity, respectively. Compared with Na(MnFeCoNi)1/2S, Na7/8Li1/8(MnFeCoNi)1/2S showed better electronic performance in reducing the band gap and increasing the density of states, ultimately providing a specific capacity of 160.3 mAh·g-1 and a charging voltage of 4.85 V in sodium-ion storage. Moreover, Na7/8Li1/8(MnFeCoNi)1/2S exhibited remarkable structural stability throughout the sodium-ion deintercalation process, thus it can be reasonably concluded that Na7/8Li1/8(MnFeCoNi)1/2S can serve as an excellent cathode material for future SIB applications.

Mn-HCF@Fe-HCF Core–Shell Architecture: Enhancing Structural Stability and Electrochemical Performance of Sodium-Ion Batteries

To overcome the structural failure of Manganese-based Prussian blue analogue (Mn-HCF) as a cathode material of sodium ion batteries caused by Mn ion dissolution induced by Jahn–Teller effect, we coated Mn-HCF with iron-based Prussian blue (Fe-HCF) to prepare the core–shell Mn-HCF@Fe-HCF cathode material for sodium ion batteries through co-precipitation method. The research results indicate that this structure effectively blocks the direct contact between Mn-HCF and electrolyte, thereby minimizing the dissolution of Mn[Formula: see text] in the electrolyte and significantly improving the cycling stability and rate performance. The discharge capacity of this material at a current density of 0.1[Formula: see text]C (14[Formula: see text]mA[Formula: see text]g[Formula: see text] is 129.7[Formula: see text]mAh[Formula: see text]g[Formula: see text]. It still has a capacity of 87.4[Formula: see text]mAh[Formula: see text]g[Formula: see text] at a current density of 2[Formula: see text]C (280[Formula: see text]mA[Formula: see text]g[Formula: see text], and still has a capacity retention rate of 84.3% (91[Formula: see text]mAh[Formula: see text]g[Formula: see text] after 100 cycles at a current density of 0.5[Formula: see text]C (70[Formula: see text]mA[Formula: see text]g[Formula: see text]. Compared with the capacity retention rate of 51.5% of Mn-HCF 100 cycles before coating, the cycle stability of Mn-HCF@Fe-HCF is greatly improved.

Zn2+-storage mechanism in V6O13 with nanosheets for high-capacity and long-life aqueous zinc-metal batteries.

V6O13 with a nanosheet structure was employed as a cathode material for aqueous zinc metal batteries. V6O13 delivered a high specific capacity of 425 mA h g-1, outstanding rate performance and durable cycling with high capacity retention of 86% after 3000 cycles. Moreover, in situ X-ray diffractometer (XRD), ex situ X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES) were employed to ascertain the reaction mechanism of Zn2+ storage.

Comprehensive Study of Zr-Doped Ni-Rich Cathode Materials Upon Lithiation and Co-Precipitation Synthesis Steps.

Ni-rich layered oxides LiNi1-x-yMnxCoyO2 (NMC811, x = 0.1 and y = 0.1) are considered promising cathode materials in lithium-ion batteries (LiBs) due to their high energy density. However, those suffer a severe capacity loss upon cycling at high delithiated states. The loss of performance over time can be retarded by Zr doping. Herein, a small amount of Zr is added to NMC811 material via two alternative pathways: during the formation of the transition metal (TM) hydroxide precursor at the co-precipitation step (0.1%-Zr-cp) and during the lithiation at the solid-state synthesis step (0.1%-Zr-ss). In this work, the crystallographic Zr uptake in both 0.1%-Zr-ss and 0.1%-Zr-cp is determined and quantified through synchrotron X-ray diffraction and X-ray absorption spectroscopy. We prove that the inclusion of Zr in the TM site for 0.1%-Zr-cp leads to an improvement of both specific capacity (156 vs 149 mAh/g) and capacity retention (85 vs 82%) upon 100 cycles compared to 0.1%-Zr-ss where the Zr does not diffuse into the active material and forms only an extra phase separated from the NMC811 particles.

Ultrahigh‐Ni Cathode with Superior Structure Stability Enabled by a Covalent Bonding Strategy

Ultrahigh‐nickel layered oxide cathodes are the most promising cathode materials for high‐energy lithium‐ion batteries. However, the rapid structural degradation during cycling charge‐discharge process limits its commercial application. Herein, we report a covalent pinning strategy to enhance structure stability of ultrahigh‐Ni cathode LiNi0.9Co0.06Mn0.04O2 (NCM90). Zr is gradient diffused into the lattice of NCM90 and forms Zr‐O bonds during the sintering process, which can effectively alleviate the lattice distortion like introducing pinning centers due to the stronger bond energy, enhancing its structure stability during charge‐discharge process. In the meanwhile, the Zr‐O on the surface of NCM90 powder forms LixZryOz coating layer due to the reaction with lithium residue, which prevents from the edge reconstruction and mitigates the occurrence of side reactions, as well as ensuring a fast Li+ diffusion pathway crossing the interface. As a result, the Zr‐O modified NCM90 (Zr‐NCM) achieves 88.8% remarkable capacity retention at 1 C after 200 cycles over 2.8‐4.3V, which is superior to the pristine NCM90 with 71.2% retention. This work demonstrates that the Zr‐O bonding can provide an effective structure pinning for the ultrahigh‐Ni cathode, which will largely guide the development of high‐performance lithium‐ion battery cathode materials.

LaCoO3@Fe3O4 as peroxymonosulfate activator derived from spent lithium battery cathode materials for degradation of sulfamethoxazole in water

To reduce the various hazards of SMX to aquatic ecosystems, in this study, magnetically separable LaCoO3@Fe3O4 catalysts for the degradation of sulfamethoxazole (SMX) in water by activated peroxymonosulfate (PMS) were successfully prepared by using cobalt oxalate recovered from spent batteries using sol–gel, hydrothermal, and high-temperature calcination methods. The main factors influencing the reaction and the effect of coexisting ions on the degradation efficiency of SMX were investigated. The results showed that under optimal conditions ([SMX] = 30 mg, [LaCoO3@Fe3O4] = 10 mg/L, [PMS] = 30 mg/L, pH (initial) = 7.02), the LaCoO3@Fe3O4/PMS system degraded SMX up to 93 % in 15 min. The degradation of SMX in the LaCoO3@Fe3O4/PMS system was shown to be achieved by a combination of radical (SO4•-/•OH/•O2–) and non-radical (1O2) pathways by quenching experiments and electron paramagnetic resonance spectroscopy (EPR) analysis. Then, three possible degradation pathways were proposed using LC-MS, and Ecological Constitutive Relationship (ECOSAR) analysis showed that the toxicity of the intermediate products was all lower than that of SMX, indicating that the system is feasible for SMX degradation. This study provides a new idea for activating PMS for the degradation of antibiotics in water by preparing catalysts using precious metals from recycled batteries.

Revealing the Nature of Binary-Phase on Structural Stability of Sodium Layered Oxide Cathodes.

The emergence of layered sodium transition metal oxides featuring a multiphase structure presents a promising approach for cathode materials in sodium-ion batteries (SIBs), showcasing notably improved energy storage capacity. However, the advancement of cathodes with multiphase structures faces obstacles due to the limited understanding of the integrated structural effects. Herein, we comprehend the integrated structural effects by an in-depth structure-chemistry analysis in the developed layered cathode system NaxCu0.1Co0.1Ni0.25Mn0.4Ti0.15O2 with purposely designed P2/O3 phase integration. Our results affirmed that integrated phase ratio plays a pivotal role in electrochemical/structural stability, particularly at high voltage and with the incorporation of anionic redox. In contrast to previous reports advocating solely for the enhanced electrochemical performance in biphasic structures, we demonstrated an inappropriate composite structure is more destructive than a single-phase design. The in situ X-ray diffraction (XRD) results, coupled with density functional theory (DFT) computations further confirm the biphasic structure with P2:O3 = 4:6 shows suppressed irreversible phase transition at high desodiated states and thus exhibits optimized electrochemical performance. These fundamental discoveries provide clues to the design of high-performance layered oxide cathodes for next-generation SIBs. This article is protected by copyright. All rights reserved.

Regulating Interfacial Compositions to Build a Stable Superlattice Structure of Layered Oxide Cathode Materials for Sodium-Ion Batteries

Regulating Interfacial Compositions to Build a Stable Superlattice Structure of Layered Oxide Cathode Materials for Sodium-Ion Batteries

Predominant P3-Type Solid-Solution Phase Transition Enables High-Stability O3-Type Na-Ion Cathodes.

Layered O3-type oxides are one of the most promising cathode materials for Na-ion batteries owing to their high capacity and straightforward synthesis. However, these materials often experience irreversible structure transitions at elevated cutoff voltages, resulting in compromised cycling stability and rate performance. To address such issues, understanding the interplay of the composition, structure, and properties is crucial. Here, we successfully introduced a P-type characteristic into the O3-type layered structure, achieving a P3-dominated solid-solution phase transition upon cycling. This modification facilitated a reversible transformation of the O3-P3-P3' structure with minimal and gradual volume changes. Consequently, the Na0.75Ni0.25Cu0.10Fe0.05Mn0.15Ti0.45O2 cathode exhibited a specific capacity of approximately 113 mAh/g, coupled with exceptional cycling performance (maintaining over 70% capacity retention after 900 cycles). These findings shed light on the composition-structure-property relationships of Na-ion layered oxides, offering valuable insights for the advancement of Na-ion batteries.

Crystalline MnCO3@Amorphous MnOx Composite as Cathode Material for High-Performance Aqueous Zinc-Ion Batteries.

Rechargeable aqueous zinc-ion batteries (RAZIBs) have received extensive attention because of their advantages of low cost, high safety, and nontoxicity. However, problems such as dissolution of the active cathode material, dendrites/passivation of the zinc anode, and slow reaction kinetics hindered their further applications. In this work, a crystalline/amorphous composite-type material composed of crystalline MnCO3 and amorphous MnOx was prepared and used as the cathode material for RAZIBs. The MnCO3@amorphous MnOx (MnCO3@A-MnOx) composite possesses the merits of both the pure crystalline phase of MnCO3 and the amorphous phase of MnOx, which can deliver better electrochemical performance than the corresponding single component in repeated cycles. In addition, crystalline MnCO3 undergoes a complex phase transition to the active MnO2 during the first charge process, providing the composite with a stable structure and additional electrochemical capacity. The electrochemical measurement results indicate that the MnCO3@A-MnOx electrode can display high reversible discharge capacity at 0.1 A g-1, excellent rate performance at 5.0 A g-1, and long cycling stability over 2000 cycles, showing great potential as a cathode material for high-performance RAZIBs.

Surface Pinning of Mn by Oxidation State Control for the Synthesis of Cobalt-Free, Ni-Rich, Core/Shell Structured Cathode Materials.

Motivated by the increasing cost, environmental concerns, and limited availability of Co, researchers are actively seeking alternative cathode materials for lithium-ion batteries. A promising strategy involves structure-modified materials, such as a NiMn core/shell system. This design leverages the high energy density of a Ni-rich core while employing an Mn-rich shell to enhance interfacial stability by suppressing unwanted reactions with the electrolyte. This approach offers improved cycling stability and reduced reliance on Co. However, the interdiffusion of Mn ions between the core and shell remains a significant challenge during synthesis. This work presents a facile approach to address the issue of Mn interdiffusion in core/shell cathode materials. The study demonstrates that partial oxidation of the precursor during the drying stage effectively enhances the Mn oxidation state. This strategy successfully suppresses Mn interdiffusion during subsequent calcination, leading to the preservation of the core/shell architecture in the final cathode material. This optimized structure mitigates interfacial reactions, enhances chemomechanical properties, and reduces crosstalk, a major contributor to rollover failure. This work presents a novel approach for synthesizing high-performance core/shell cathode materials for next-generation lithium-ion batteries.

Four-Electron Redox Reaction in Prussian Blue Analogue Cathode Material for High-Performance Sodium-Ion Batteries

Four-Electron Redox Reaction in Prussian Blue Analogue Cathode Material for High-Performance Sodium-Ion Batteries

Revisit of Polyaniline as a High-Capacity Organic Cathode Material for Li-Ion Batteries.

Polyaniline (PANI) has long been explored as a promising organic cathode for Li-ion batteries. However, its poor electrochemical utilization and cycling instability cast doubt on its potential for practical applications. In this work, we revisit the electrochemical performance of PANI in nonaqueous electrolytes, and reveal an unprecedented reversible capacity of 197.2 mAh g-1 (244.8 F g-1) when cycled in a wide potential range of 1.5 to 4.4 V vs. Li+/Li. This ultra-high capacity derives from 70% -NH- transformed to =NH+- during deep charging/discharging process. This material also demonstrates a high average coulombic efficiency of 98%, an excellent rate performance with 73.5 mAh g-1 at 1800 mA g-1, and retains 76% of initial value after 100 cycles, which are among the best reported values for PANI electrodes in battery applications.

Exploring the Molecular-Scale Structures at Solid/Liquid Interfaces of Li-Ion Battery Materials: A Force Spectroscopy Analysis with Sparse Modeling.

In this study, we clarify the liquid structure formed at the interface between LiCoO2 (LCO), the cathode material of Li-ion batteries, and propylene carbonate (PC), which is used as a solvent in the electrolyte, on a molecular scale. We apply sparse modeling-based modal analysis to force spectroscopy data measured by frequency modulation atomic force microscopy (FM-AFM) and show that each component in the FM-AFM force curve, such as oscillatory solvation force, background, and noise, can be automatically decomposed. Moreover, by combining detailed force curve analysis with solid/liquid interface simulations based on first-principles calculation, we have identified that there are distinct damped vibrational modes in the force curves at the LCO/PC interface with a period of about 0.57 nm and those with shorter periods, which likely correspond to the solvation forces associated with bulk-state PC molecules and those with PC molecules in "lying down" orientations.