High-performance Cathode Materials Research Articles

A modification engineering to form two kinds of truncated octahedrons by in situ LaBO3 coating for high-performance LiMn2O4 cathode material

Rapid capacity fade of spinel LiMn2O4 cathode material limits the application of lithium-ion batteries. Herein, the introduction of La/B elements achieves the dual-modification of surface coating and single-crystal truncated morphology, ensuring the compatibility of rate capability and cycling stability. The La and B introduction enables the in situ formation of LaBO3 coating layer. Both the LaBO3 coating and truncated morphology prevent the direct exposure of the cathode to the electrolyte, decreasing the Mn dissolution and providing the additional Li+ diffusion channels. The increase of La and B modification partially restrains the development of {110} crystal planes. The refinement manifests that the La3+/B3+ doping partially replaces Mn3+ of the LiMn2O4, inhibiting the Jahn-Teller effect and stabilizing the [MnO6] skeleton. Consequently, the optimized LiMn2O4@0.04LaBO3 with the favorable LaBO3 coating thickness and two truncated octahedrons exhibits the excellent electrochemical properties at high current rate. The first discharge capacities of 109.1, 104.2 and 96.9 mAh⋅g−1 are obtained, whilst the capacity retentions of 64.8 % (after 2000 cycles), 65.8 % (after 2000 cycles) and 80.5 % (after 1000 cycles) can be maintained at 5 C, 10 C and 20 C, respectively. Even at 5 C and 55 °C, the high initial discharge capacity of 113.6 mAh⋅g−1 and good cycling lifespans can be achieved. This modification strategy provides valuable insight for preparing the advanced LiMn2O4 cathode materials for lithium-ion batteries.

Research on the Performance Improvement Method for Lithium-Ion Battery in High-Power Application Scenarios

With the development of technology, high-power lithium-ion batteries are increasingly moving towards high-speed discharge, long-term continuous output, instantaneous high-rate discharge, and miniaturization, and are being gradually developed towards the fields of electric tools, port machinery and robotics. Improving the power performance of batteries can be achieved from multiple dimensions, such as electrochemical systems and battery design. In order to improve the power performance of lithium-ion batteries, this paper proposes design methods from the perspective of electrochemical systems, which include increasing the high-rate discharge capacity and low impedance of the battery. This article also studies the preparation of high-power lithium-ion batteries. This article aims to improve the rate performance of batteries by studying high-performance cathode materials, excellent conductive networks, and high-performance electrolytes. This article successfully screened high-performance cathode materials by comparing the effects of different particle sizes of cathode materials on electrode conductivity and battery internal resistance. By comparing the effects of electrolyte additives under pulse cycling, high-quality electrolyte additive materials were selected. By comparing the effects of different types, contents, and ratios of conductive agents on electrode conductivity, battery internal resistance, high-quality conductive agents, and appropriate ratios were selected. Finally, a 10 Ah cylindrical high-power lithium-ion battery with a specific energy of 110 Wh/kg, pulse discharge specific power of 11.3 kW/kg, an AC internal resistance of ≤0.7 m Ω, a 10C full capacity discharge cycle of over 1700, a 30C full capacity discharge cycle of over 500, and a continuous discharge capacity of 10C–30C, and a pulse discharge capacity of over 100C was prepared.

Three dimensional CuCo2S4@CNT as cathode for sustainable aluminum batteries

It is a challenging and meaningful subject that developing high-performance cathode materials for aluminum batteries（ABs）. In this work, a three dimensional CuCo2S4@CNT (CNT refers to carbon nanotube) material was designed for ABs. The three-dimensional structure is constructed by combining CuCo2S4 microspheres with CNT scaffolds. CuCo2S4 microspheres are constructed from ultrathin nanosheets and CuCo2S4 microspheres uniformly distribute in these three dimensional all-carbon CNT architectures. The CNT framework improves material conductivity and inhibits aggregation of CuCo2S4 particles, and also acts as a buffer, eliminating volume changes and providing more stable contacts between particles. Compared with the pristine CuCo2S4 electrode, the CuCo2S4@CNT electrode exhibits superior electrochemical performance. At a current density of 100 mA/g, CuCo2S4@CNT electrode still provides a reversible capacity of 128 mAh/g after 200 cycles. Meanwhile, the coulombic efficiency remains above 96 %.

Recycling of LiCoO2 from the cathode of a waste lithium battery via reduction in a molten salt

A new method for recycling and resynthesizing a lithium battery cathode material was developed. A LiCl-KCl molten salt was used as a medium. The raw materials were LiOH·H2O obtained by membrane electrolysis and Co2O3 obtained by carbothermal reduction, and the high-performance cathode material LiCoO2 was synthesized by molten salt method, and then placed into a battery for recycling. The specific reaction process and reaction kinetics for the LiCoO2 synthesis were studied by TG-DSC thermal analyses. The effects of different reaction conditions on the structure and morphology of the LiCoO2 were studied by XRD and SEM. The battery performance of the LiCoO2 was characterized with electrochemical analyses. The activation energies of the three endothermic reactions occurring in the synthetic process were calculated with the Kissinger method and were 34.212 kJ·mol−1, 168.53925 kJ·mol−1 and 221.26181 kJ·mol−1. The experimental battery prepared from a LiCoO2 sample calcined at 720 °C for 7 h showed first charge–discharge specific capacities of 150 mAh/g and 147 mAh/g, and the coulombic efficiency was 98%. The discharge specific capacity after 50 charge and discharge cycles was still 129 mAh/g. The battery showed good charge and discharge performance after rate cycling.

Recent Progress and Synthetic Methods for Single-crystalline Cathode in Lithium-ion Batteries

Ni-rich layered transition metal oxides have been regarded as the most feasible way for achieving high energy density of lithium-ion batteries. Conventional Ni-rich cathodes are composed of spherical secondary particles, consisting of numerous primary particles. Unfortunately, the grain boundaries in the polycrystalline structure are vulnerable to the pulverization, leading to microcracks during cycling. The newly exposed surface from the microcrack can induce undesirable side reactions with the electrolyte, which severely deteriorates the battery performance. On the other hand, single-crystalline Ni-rich cathodes have gained significant attention for industrial applications due to their robust mechanical strength, resulting from the elimination of grain boundaries. The improved mechanical properties of single-crystalline cathodes effectively mitigate the interfacial side reactions, thereby attaining superior structural, thermal, and electrochemical performance. Herein, we have introduced various synthetic methods of the single-crystalline cathode, encompassing not only high-temperature sintering and the molten-salt method for the Ni-rich cathode but also the other strategies for different single-crystalline cathode materials. This review aims to provide a comprehensive understanding of single-crystalline cathode synthesis, with implications for the development of high-performance cathode materials.

A new In Situ Oxidized 2D Layered MnBi2Te4 Cathode for High-Performance Aqueous Zinc-Ion Battery.

Recently, aqueous zinc ion batteries (AZIBs) with the superior theoretical capacity, high safety, low prices, and environmental protection, have emerged as a contender for advanced energy storage. However, challenges related to cathode materials, such as dissolution, instability, and structural collapse, have hindered the progress of AZIBs. Here, a novel AZIB is constructed using an oxidized 2D layered MnBi2Te4 cathode for the first time. The oxidized MnBi2Te4 cathode with large interlayer spacing and low energy barrier for zinc ion diffusion at 240°C, exhibited impressive characteristics, including a high reversibility capacity of 393.1mAhg-1 (0.4Ag-1), outstanding rate performance, and long cycle stability. Moreover, the corresponding aqueous button cell also exhibits excellent electrochemical performance. To demonstrate the application in practice in the realm of flexible wearable electronics, a quasi-solid-state micro ZIB (MZIB) is constructed and shows excellent flexibility and high-temperature stability (the capacity does not significantly degrade when the temperature reaches 100°C and the bending angle exceeds 150°). This research offers effective tactics for creating high-performance cathode materials for AZIBs.

Achieving rapid sodiation/desodiation kinetics in NASICON-structured Na3MnTi(PO4)3 via Cr doping

Na3MnTi(PO4)3 is one of the most promising cathode candidates for sodium-ion batteries owing to its low cost, high operating voltage, and large reversible capacity. However, its electrochemical performance is significantly impeded by its deteriorative structure and sluggish Na+ diffusion kinetics. Herein, Cr-doping is introduced to tailor the structure of Na3MnTi(PO4)3, which helps to lengthen the Na2-O bond and expand the Na ion diffusion channels. X-ray diffraction, cyclic voltammetry, galvanostatic intermittent titration technique, and first principle calculations confirm the broadened diffusion channel for Na+ and facilitated Na+ diffusion rate after Cr-doping. As a result, the Na3.1MnTi0.9Cr0.1(PO4)3 electrode exhibits superior electrochemical performance with high discharge capacity (167.5 mAh g–1 at 0.1 C), outstanding rate capability (127.5 mAh g–1 at 10 C), and remarkable cyclability (70.56 % retention after 1400 cycles at 5 C). We believe that the results are useful for the design of high-performance NASICON-structured cathode materials for practical sodium-ion batteries.

Application of lattice expansion effect in SrCoO3 based cathodes by Ba doping with elevated electrochemical performances for low-temperature solid oxide fuel cells

Developing excellent-performance cathode materials is an inevitable and challenging obstacle in the process of developing practical solid oxide fuel cells, especially in low temperature range. In this paper, we introduce barium into the premium SrCoO3-based cathodes and research its consequent effect in the oxygen reduction reaction process. It is observed that the barium dopant could expand the lattice, produce more oxygen vacancies and at some extent reduce the thermal expansion coefficient of parent perovskite, which results from the expanded free space for oxygen migration and weakened Co–O bond by Ba doping. The polarization resistances of single cells with Sr1-xBaxCo0.8Sc0.1Nb0.05Ti0.05O3-δ cathodes (x = 0, 0.2 and 0.5, defined as SCSNTi, SB0.2CSNTi and SB0.5CSNTi, correspondingly) are 0.038, 0.025 and 0.016 Ω cm2 at 600 °C, respectively, and corresponding peak power density of 0.852, 1.054 and 1.217 W cm−2. The SB0.5CSNTi cathode is selected and it stably operates for 200 h at 550 °C. And it also exhibits excellent performance when CH4 is used as fuel and good stability for 100 h at 600 °C. First principle calculations prove that the Ba doping effectively reduces the oxygen vacancy formation energy and oxygen migration barrier. This work proves that the lattice expansion effect is an effective strategy for accelerating the oxygen exchange rate and designing high-performance cathode materials.

Low over-potential cathode synthesized using a binary metal self-templated molybdenum reinforced method for highly efficient hydrogen evolution

To solve the problem of renewable energy generation fluctuation, water splitting for hydrogen generation is proposed, which can store renewable energy as hydrogen energy. Low overpotential cathode materials can effectively reduce the cost of hydrogen production. Here, a new NiMo/NMF electrode was prepared using a hydrothermal coupled H2 reduction method. Three-dimensional NiMo nanorod arrays were constructed by modulating the ion dissolution and surface epitaxial growth process of the electrode substrate. The influence of different hydrothermal reaction and H2 reduction conditions on the electrochemical performance of the electrode was investigated. Under optimum preparation conditions, the NiMo/NMF electrode exhibits a extremely low overpotentials of 158 mV at 500 mA cm-2 (30% wt. KOH alkaline medium), which can serve for preparing high efficiency and economy electrodes by in-situ integration of high active components on metal foam substrate. The NiMo/NMF electrode is a high-performance electrocatalytic cathode material with great prospects for industrial applications.

Prussian Blue Nanoplates for Potassium Ion Battery Cathode with High Capacity and High Energy Density

Prussian blue analogues represent as a class of materials with an open framework structure and have been explored as the potential active materials for alkaline‐ion batteries. Here, we present the synthesis of Prussian blue nanoplates (PBN) designed for use as high performance cathode materials in potassium‐ion batteries (KIBs). PBNs were synthesized through a facile solution precipitation, yielding potassium‐rich PBNs with horizontal crystals growth. The PBNs characterized with a larger particle size of 600 nm and a reduced specific surface area of 6.8 m2 g‐1, compared to conventional prepare Prussian blue hexahedrons. Half‐cell tests demonstrated that the PBNs exhibited a high gravimetric capacity of 152.5 mAh g‐1 with a nominal voltage 3.952 V at a C‐rate of 0.1 C, yielding an energy density of 602.7 Wh kg‐1. Cycling tests demonstrated a capacity of 122.7 mAh g‐1 and a nominal voltage of 3.923 V after 200 cycles at 0.2 C. In a full‐cell configuration with graphite anodes, a gravimetric capacity changed from 134.1 mAh g‐1 to 108.9 mAh g‐1 after 100 cycles at 0.2 C, demonstrating a good cycling stability. This work provides a new insight into the electrochemical properties of PBNs and highlights their potential as high‐performing cathode materials for KIBs.

Interfacial Engineering of P2-Type Ni/Mn-Based Layered Oxides by a Facile Water-Washing Method for Superior Sodium-Ion Batteries.

Owing to the strong basicity and reactivity, residual sodium compounds (RSCs) on the surface of Na-based layered oxides for sodium-ion batteries (SIBs) cause the deterioration of the electrochemical performance and processability of the oxide cathode materials. Herein, considering P2-type Na0.66Ni0.26Zn0.07Mn0.67O2 as the model material, the water-washing treatment is proven to be a facile, economic, and highly efficient method to improve the electrochemical performance of P2-type Ni/Mn-based layered oxides. Experimental results show that RSCs on material surfaces can be effectively removed by water washing without causing severe damage to the bulk structure. Notably, water washing triggers the formation of an ultrathin (2-3 nm thick) Na-poor disordered interfacial layer on the surface of Na0.66Ni0.26Zn0.07Mn0.67O2. This layer plays a passivating role in further enhancing the material's resistance to water and reduces the reactivity of the material surface with the electrolyte. These compositional and structural optimizations for P2-type Na0.66Ni0.26Zn0.07Mn0.67O2 effectively suppress the release of gaseous CO2, formation of thick cathode-electrolyte interphase films, and consumption of active Na+, enabling good Na+ transport kinetics during cycling. The water-washed Na0.66Ni0.26Zn0.07Mn0.67O2 exhibits significantly improved cycling stability with a capacity retention of 89.1% at 100 mA g-1 after 100 cycles and rate capability with a discharge capacity of 76.3 mA g-1 at 2000 mA g-1; these values are higher than those of the unwashed Na0.66Ni0.26Zn0.07Mn0.67O2 (83.3%, 71.4 mA h g-1). This work provides fundamental insights into the detrimental effect of RSCs on the electrochemical performance of layered oxides and highlights the importance of regulating interfacial compositions for developing high-performance layered-oxide cathode materials for SIBs.

Designing ultrastable P2/O3-type layered oxides for sodium ion batteries by regulating Na distribution and oxygen redox chemistry

P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries (SIBs) owing to their high energy density. However, exploring effective ways to enhance the synergy between the P2 and O3 phases remains a necessity. Herein, we design a P2/O3-type Na0.76Ni0.31Zn0.07Mn0.50Ti0.12O2 (NNZMT) with high chemical/electrochemical stability by enhancing the coupling between the two phases. For the first time, a unique Na+ extraction is observed from a Na-rich O3 phase by a Na-poor P2 phase and systematically investigated. This process is facilitated by Zn2+/Ti4+ dual doping and calcination condition regulation, allowing a higher Na+ content in the P2 phase with larger Na+ transport channels and enhancing Na+ transport kinetics. Because of reduced Na+ in the O3 phase, which increases the difficulty of H+/Na+ exchange, the hydrostability of the O3 phase in NNZMT is considerably improved. Furthermore, Zn2+/Ti4+ presence in NNZMT synergistically regulates oxygen redox chemistry, which effectively suppresses O2/CO2 gas release and electrolyte decomposition, and completely inhibits phase transitions above 4.0 V. As a result, NNZMT achieves a high discharge capacity of 144.8 mA h g−1 with a median voltage of 3.42 V at 20 mA g−1 and exhibits excellent cycling performance with a capacity retention of 77.3% for 1000 cycles at 2000 mA g−1. This study provides an effective strategy and new insights into the design of high-performance layered-oxide cathode materials with enhanced structure/interface stability for SIBs.

High-Rate and Ultra-Stable aqueous Zinc-Ion batteries enabled by Potassium-Infused ammonium vanadate nanosheets

Aqueous zinc-ion batteries (AZIBs), defined by low expenses, superior safety, and plentiful reserves, demonstrate tremendous development potential in energy storage systems at the grid scale. Whereas the cathode instability and the limited diffusion of Zn2+ have impeded the development of AZIBs. Herein, a high-performance K-NH4V4O10 (K-NVO) cathode with K+ doping synthesized successfully through one-step hydrothermal approach. Experiments and density functional theory (DFT) calculations indicate that K-NVO has Zn2+ diffusion pathways with lower barriers for smoother transport, and lower formation energy. The combination of the rapid Zn2+ diffusion and the stable structure results in outstanding electrochemical performance of K-NVO as demonstrated in tests. K-NVO cathode achieves a specific capacity of 406 mAh g−1 at 0.2 A g−1, maintains satisfactory cyclic stability with 81.6 % capacity retention after 1000 cycles at 5 A g−1, and possesses a high energy density of 350.9 Wh kg−1. Furthermore, confirmation of the zinc storage mechanism in K-NVO was carried out through Ex situ tests, such as XRD and XPS. This research contributes a unique perspective to the formulation of high-performance cathode materials for AZIBs.

Polymer-mediated vacancy defects of graphene sheets as high-performance cathode materials for aqueous zinc-ion hybrid supercapacitors

The electrochemical behavior of graphene sheets in energy storage system is closely related to its electronic structures. Specifically, structural vacancy defects can expose more active sites and enhance the electrochemical performance. However, it is still a challenging problem to realize valid defect regulation on improving the reaction kinetics of electrode materials. Herein, vacancy-defective graphene sheets were constructed through the thermal mediated method via intercalation of polyacrylonitrile nanofibers. The vacancy defects were generated from the NH3 gas resulting from polymer decomposition at gradient carbonization temperature. The obtained composites of the graphene sheets and carbon nanofibers demonstrate that the vacancy defects benefit to charge transport, allowing more electrons to pass through the interlayered structure, and enhance the adsorption capacitance during the reversible electrochemical process. In addition, the as-assembled Zn ion hybrid supercapacitors exhibit a high energy density of 129.9 Wh kg−1 and outstanding cyclic stability (99.8 % after 10,000 cycling). The confined polymer-mediated thermal modification strategy can afford abundant vacancy defective sites and exhibit promising outlook for constructing high-performance graphene-based electrode materials for Zn ion hybrid supercapacitors.

Ti-Doped Co-Free Li1.2Mn0.6Ni0.2O2 Cathode Materials with Enhanced Electrochemical Performance for Lithium-Ion Batteries

Cobalt-free manganese-based lithium-rich layered oxides (LLOs) have garnered research attention as prospective lithium-ion cathode materials owing to their large specific capacity and low price. However, their large-scale application is hindered by their low Coulombic efficiency, poor cycling performance, voltage attenuation, and structural phase transition. To address these issues, the LLO structure is modified via Ti doping at the manganese site herein. Ti-doped Li1.2Mn0.6−xTixNi0.2O2 (x = 0, 0.03, 0.05, 0.10, and 0.15) is prepared using the high-temperature solid-state method. The Ti-doped Li1.2Mn0.6Ni0.2O2 is calculated via first principles. The results show that Ti4+ doping improves the cycle stability and rate performance of Li1.2Mn0.6Ni0.2O2. Electrochemical test results show that the sample exhibits enhanced electrochemical performance when the Ti doping amount is 0.05. The discharge specific capacity at 0.1C is 210.4 mAh·g−1, which reaches 191.1 mAh·g−1 after 100 cycles, with a capacity retention rate of 90.7%. This study proves the feasibility of using cheap cobalt-free LLOs as cathode materials for LIBs and provides a novel system for exploiting low-cost and high-performance cathode materials.

Solid-phase construction of high-performance sodium-ion battery cathode materials with three-dimensional porous structure: Na4MnCr(PO4)3/C

Na4MnCr(PO4)3 is a promising cathode material with high redox potential and high energy density, but the intrinsic poor electronic conductivity and substandard structural stability restrict its practical application. Herein, porous Na4MnCr(PO4)3/C with conductive networks and improved electrochemical properties is synthesized by a facile modified solid-state process using citric acid as a multifunctional additive. The results reveal that citric acid can be used as a grinding aid to make the raw materials mix more evenly and speed up the efficiency of ball milling. Besides, 3D conductive network and porous structure originated from polycondensation and carbonization of citric acid can promote the electrochemical properties of Na4MnCr(PO4)3/C by enhancing the electronic/ionic conductivity and (de)intercalation reaction kinetics. As expected, the optimal Na4MnCr(PO4)3/C delivers a high reversible capacity of 130.5 mAh g−1 at 0.1C rate, and exhibits a capacity retention of 82.62% at 10C rate after 500 cycles. In addition, the reversible biphasic reaction of the cathode is confirmed by the constant galvanostatic intermittent titration technique and ex-situ XRD, which shows great potential of the synthesized Na4MnCr(PO4)3/C for practical applications.

Resource recovery and regeneration strategies for spent lithium-ion batteries: Toward sustainable high-value cathode materials

Traditional cathode recycling methods have become outdated amid growing concerns for high-value output and environmental friendliness in spent Li-ion battery (LIB) recycling. Our study presents a closed-loop approach that involves selective sulfurization roasting, water leaching, and regeneration, efficiently transforming spent ternary Li batteries (i.e., NCM) into high-performance cathode materials. By combining experimental investigations with density functional theory (DFT) calculations, we elucidate the mechanisms within the NCM-C-S roasting system, providing a theoretical foundation for selective sulfidation. Utilizing in situ X-ray diffraction techniques and a series of consecutive experiments, the study meticulously tracks the evolution of regenerating cathode materials that use transition metal sulfides as their primary raw materials. The Li-rich regenerated NCM exhibits exceptional electrochemical performance, including long-term cycling, high-rate capabilities, reversibility, and stability. The closed-loop approach highlights the sustainability and environmental friendliness of this recycling process, with potential applications in other cathode materials, such as LiCoO2 and LiMn2O4. Compared with traditional methods, this short process approach avoids the complexity of leaching, solvent extraction, and reverse extraction, significantly increasing metal utilization and Li recovery rates while reducing pollution and resource waste.

Unraveling the modified mechanism of ruthenium substitution on Na3V2(PO4)3 with superior rate capability and ultralong cyclic performance

Na3V2(PO4)3(NVP) is an ideal cathode material for sodium ion battery due to its stable three-dimensional frame structure and high operating voltage. However, the low intrinsic conductivity and serious structural collapse limit its further application. In this work, a simultaneous optimized Na3V1.96Ru0.04(PO4)3/C@CNTs cathode material is synthesized by a simple sol–gel method. Specifically, the ionic radius of Ru3+ is slightly larger than that of V3+ (0.68 Å vs 0.64 Å), which not only ensures the feasibility of Ru3+ replacing V3+ site, but also appropriately expands the migration channel of sodium ions in NVP and stabilizes the structure, effectively improving the diffusion efficiency of sodium ions. Moreover, CNTs construct a three-dimensional conductive network between the grains, reducing the impedance at the interface and effectively improving the electronic conductivity. Ex-situ XRD analysis at different SOC were performed to determine the change in the crystal structure of Ru3+doped Na3V2(PO4)3, and the refinement results simultaneously demonstrate the relatively low volume shrinkage value of less than 3 % during the de-intercalation process, further verifying the stabilized crystal construction after Ru3+ substitution. Furthermore, the ex-situ XRD/SEM/CV/EIS after cycling indicate the significantly improved kinetic characteristics and enhanced structural stability. Notably, the modified Na3V1.96Ru0.04(PO4)3/C@CNTs reveals superior rate capability and ultralong cyclic performance. It submits high capacities of 82.3/80.9 mAh g−1 at 80/120C and maintains 71.3/59.6 mAh g−1 after 14800/6250 cycles, indicating excellent retention ratios of 86.6 % and 73.6 %, respectively. This work provides a multi-modification strategy for the realization of high-performance cathode materials, which can be widely applied in the optimization of various materials.

Achieving structurally stable O3-type layered oxide cathodes through site-specific cation-anion co-substitution for sodium-ion batteries

O3-type layered oxides have garnered great attention as cathode materials for sodium-ion batteries because of their abundant reserves and high theoretical capacity. However, challenges persist in the form of uncontrollable phase transitions and intricate Na+ diffusion pathways during cycling, resulting in compromised structural stability and reduced capacity over cycles. This study introduces a special approach employing site-specific Ca/F co-substitution within the layered structure of O3-NaNi0.5Mn0.5O2 to effectively address these issues. Herein, the strategically site-specific doping of Ca into Na sites and F into O sites not only expands the Na+ diffusion pathways but also orchestrates a mild phase transition by suppressing the Na+/vacancy ordering and providing strong metal–oxygen bonding strength, respectively. The as-synthesized Na0.95Ca0.05Ni0.5Mn0.5O1.95F0.05 (NNMO-CaF) exhibits a mild O3 → O3 + O'3 → P3 phase transition with minimized interlayer distance variation, leading to enhanced structural integrity and stability over extended cycles. As a result, NNMO-CaF delivers a high specific capacity of 119.5 mA h g−1 at a current density of 120 mA g−1 with a capacity retention of 87.1% after 100 cycles. This study presents a promising strategy to mitigate the challenges posed by multiple phase transitions and augment Na+ diffusion kinetics, thus paving the way for high-performance layered cathode materials in sodium-ion batteries.

Synergistic π-Conjugation Organic Cathode for Ultra-Stable Aqueous Aluminum Batteries.

Rechargeable aqueous aluminum batteries (AABs) are promising energy storage technologies owing to their high safety and ultra-high energy-to-price ratio. However, either the strong electrostatic forces between high-charge-density Al3+ and host lattice, or sluggish large carrier-ion diffusion toward the conventional inorganic cathodes generates inferior cycling stability and low rate-capacity. To overcome these inherent confinements, a series of promising redox-active organic materials (ROMs) are investigated and a π-conjugated structure ROMs with synergistic C═O and C═N groups is optimized as the new cathode in AABs. Benefiting from the joint utilization of multi-redox centers and rich π-π intermolecular interactions, the optimized ROMs with unique ion coordination storage mechanism facilely accommodate complex active ions with mitigated coulombic repulsion and robust lattice structure, which is further validated via theoretical simulations. Thus, the cathode achieves enhanced rate performance (153.9mAhg-1 at 2.0Ag-1 ) and one of the best long-term stabilities (125.7mAhg-1 after 4,000 cycles at 1.0Ag-1 ) in AABs. Via molecular exploitation, this work paves the new direction toward high-performance cathode materials in aqueous multivalent-ion battery systems.