Irreversible Phase Transition Research Articles

A Universal Interfacial Reconstruction Strategy Based on Converting Residual Alkali for Sodium Layered Oxide Cathodes: Marvelous Air Stability, Reversible Anion Redox, and Practical Full Cell.

Mn-based layered oxide cathodes have attracted widespread attention due to high capacity and low cost, however, poor air stability, irreversible phase transitions, and slow kinetics inhibit their practical application. Here, we propose a universal interfacial reconstruction strategy based on converting residual alkali to tunnel phase Na0.44MnO2 for addressing the above mentioned issue simultaneously, using O3 NaNi0.4Fe0.2Mn0.4O2@2 mol % Na0.44MnO2 (NaNFM@NMO) as the prototype material. The optimized material exhibits an initial capacity and energy density comparable with lithium-ion batteries. The reversible anionic redox behavior and charge compensation mechanism of NaNFM@NMO were analyzed and verified by soft X-ray absorption spectrum and in situ X-ray absorption spectrum. Due to the intrinsic stability of the tunnel structure, excellent air stability and highly reversible structure evolution of the NaNFM@NMO cathode material are achieved, which are confirmed by contact angle test, rigorous aging test, and in situ X-ray diffraction. More importantly, the NaNFM@NMO cathode demonstrates a great match with the nonpresodiated hard carbon anode and shows excellent electrochemical performance of the full cell. Additionally, such a strategy could be also applied to modify P2-type cathodes, showing superior universality and good prospects in industrialized production. Overall, the proposed strategy could improve air stability while remaining interfacial and bulk stable simultaneously and will open up a whole new field for the optimization of other electrode materials.

Nickel Vanadate Cathode Induced In Situ Phase Transition for Improved Zinc Storage by Low Migration Barrier and Zn2+/H+ Co-Insertion Mechanism.

Designing cathode materials that exhibit excellent rate performance and extended cycle life is crucial for the commercial viability of aqueous zinc (Zn)-ion batteries (ZIBs). This report presents a hydrothermal synthesis of stable Ni0.22V2O5·1.22H2O (NVOH) cathode material, demonstrating high-rate performance and extended cycle life. A successful in situ phase transformation yields Zn3(OH)2V2O7·nH2O (ZVO), which undergoes an irreversible phase transition and exhibits exceptional energy storage properties. The procedure maintains the lattice structure of ZVO and ensures high structural stability throughout the phase transformation. The NVOH cathode material exhibits the discharge capacities of 399mA h g-1 at a rate of 1 A g-1 after 400 cycles and 303mA h g-1 at 10 A g-1 after 2000 cycles. Density functional theory calculations indicate that the material is protected by electrostatic forces and exhibits structural stability, with a Zn-ion migration barrier of 0.32eV across the host lattice and the electrode-electrolyte interface. Due to these properties, NVOH also exhibits high energy/power densities of 395Wh kg-1/406W kg-1 at 0.5 A g-1 and 288Wh kg-1/8830W kg-1 at 10 A g-1. Ex situ characterizations indicate structural modifications and irreversible phase changes of NVOH, highlighting the potential of H+ intercalation and in situ phase transitions for high-performance aqueous ZIBs.

Origin of the High Catalytic Activity of MoS2 in Na-S Batteries: Electrochemically Reconstructed Mo Single Atoms.

Room-temperature sodium-sulfur (RT Na-S) batteries with high energy density and low cost are considered promising next-generation electrochemical energy storage systems. However, their practical feasibility is seriously impeded by the shuttle effect of sodium polysulfide (NaPSs) resulting from the sluggish reaction kinetics. Introducing a suitable catalyst to accelerate conversion of NaPSs is the most used strategy to inhibit the shuttle effect. Traditional catalytic approaches often want to avoid the irreversible phase transition of the catalyst at a deep discharge. On the contrary, here, we leverage the intrinsic structural tunability of the MoS2 catalyst in the opposite direction and innovatively propose a voltage modulation strategy for in situ generation of trace Mo single atoms (MoSAC) during the first charge-discharge process, leading to the formation of highly active catalytic phases (MoS2/MoSAC) through the self-reconstruction. Theoretical calculations reveal that the incorporation of MoSAC modulates the electronic structure of the Mo d-band center, which not only effectively promotes the d-p orbital hybridization but also accelerates the catalytic intermediate desorption by the bonding transition, the dynamic single-atom synergistic catalytic mechanism enhances the adsorption response between the metal active site and NaPSs, which significantly improves the sulfur redox reaction (SRR), and the initial capacity of the MoS2/MoSAC/CF@S cell at 0.2 A g-1 is increased by 46.58% compared to that of the MoS2/CF@S cell. The discovery of the MoS2/MoSAC/CF catalyst provides new insights into adjusting the structure and function of transition metal disulfide catalysts at the atomic scale, offering hope for the development of high-specific-energy RT Na-S batteries.

Enhancing the potassium-ion storage performance of potassium manganese oxide cathode by single-element doping strategies

Layered manganese-based oxides are considered as ideal cathode materials for potassium-ion batteries (PIBs) due to their ease of synthesis and relatively large interlayer spacing. Nevertheless, the Jahn-Teller effect of Mn3+ and the irreversible phase transitions in high-voltage regions of layered manganese-based oxide leads to slow diffusion kinetics of potassium ions and severe capacity fading. Herein, a series of single-element doped manganese-based oxide cathodes K0.5Mn0.98X0.02O2 (X = Fe, Mg, Cu, Ti and Zn) are designed and investigated. The results demonstrate that trace doping with these elements stabilizes the layered structure of KMnO2 cathode materials, improves the diffusion coefficient of K+, and effectively suppresses the P3-O3-P3 phase transition in high-voltage regions. Among the doping-samples, the K0.5Mn0.98Fe0.02O2 exhibits outstanding reversible specific capacity of 127 mAh g−1 at a current density of 20 mA g−1. Meanwhile, K0.5Mn0.98Ti0.02O2 demonstrates exceptional cycling stability and rate capability, retaining 83.8 % of its initial capacity after 300 cycles at 200 mA g−1, and maintaining a high specific capacity close to 40 mAh g−1 even at 1000 mA g−1. This study validates the feasibility of trace element doping in enhancing the electrochemical performance of layered Mn-based cathode materials for PIBs.

High-entropy doping for high-voltage LiCoO2 with enhanced electrochemical performances

Lithium cobalt oxide (LiCoO2), as a pioneering layered oxide cathode material for lithium-ion batteries (LIBs), possesses exceptional theoretical specific capacity and cycling stability, positioning it as a leading candidate for commercial LIB applications. Boosting the upper-limit of charge voltage of LiCoO2 is a promising strategy to increase the capacity of batteries, vital for advancing energy storage solutions from portable electronics to electric vehicles. Nevertheless, hybrid redox reactions at high voltages speed up oxygen evolution, electrolyte decomposition, and irreversible phase transitions, ultimately causing rapid capacity fading.To address these challenges, we present a novel approach to enhance the structural stability and electrochemical performances of LiCoO2 cathode via La-Al-Mg-Y high-entropy doping. This strategy significantly improves the high-voltage cycling stability of the cathode material by retaining 72.5 % of its initial capacity after 500 cycles at 5 C under 4.6 V. Furthermore, the structural change caused by the phase transition between the O3 and H1-3 phases is remarkably suppressed. This advancement in LIB cathode technology paves the way for the development of high performance batteries and it is crucial for meeting the growing demand for sustainable energy storage.

Improving the Cycle Stability of LiNiO2 through Al3+ Doping and LiAlO2 Coating.

In this study, we addressed the poor cycling and rate performance of LiNiO2, a material with ultrahigh nickel content considered a strong contender for high-energy-density lithium-ion battery cathodes. We introduced nano-Al2O3 during the lithiation process to achieve dual modified material through bulk phase element doping and in situ LiAlO2 coating. Comparison revealed notable improvements in the modified materials. In particular, LiNi0.99Al0.01O2 maintained a capacity retention rate of 73.1% after 300 cycles in a long-cycle test at 0.5C current density, outperforming the undoped material. In rate performance tests, the doped samples consistently exhibited higher discharge-specific capacities than that of the undoped counterpart. Notably, at a high current density of 5C, LiNi0.99Al0.01O2 exhibited a discharge-specific capacity of 101.75 mAh g-1. The results indicate that an appropriate amount of Al doping can effectively stabilize the layered structure of the cathode material and delay the irreversible phase transition from H2 to H3. Further, Al doping facilitates the formation of a LiAlO2 coating on the surface of the particles. This coating acts as a fast-ion conductor, enhancing the transport of lithium ions and reducing the erosion of the active material by the electrolyte.

Engineering Interlayer Space and Composite of Square-Shaped V2O5 by PVP-Assisted Polyaniline Intercalation and Graphene for Aqueous Zinc-Ion Batteries.

V2O5 undergoes irreversible phase transition and collapse of layered structure during the Zn2+ insertion/extraction, which severely limits its application as a cathode for aqueous zinc-ion batteries (AZIBs). Herein, a synergistic strategy of conductive polyaniline insertion and graphene composite was proposed to boost the Zn2+ storage performance of the V2O5 cathode. A square-shaped polyaniline (PANI)-intercalated and graphene-composited vanadium oxide (GO/PANI-PVP/V2O5) structure was successfully synthesized via an in situ oxidation/insertion polymerization combined with a hydrothermal method. The results showed that PANI intercalation and the composite of graphene combined with layered V2O5, enabling reversible intercalation of Zn2+/H+. The insertion of conjugated PANI not only increases the lattice spacing of V2O5, providing a channel for rapid transport of Zn2+, but also increases the storage sites for charges through doping/dedoping processes and redox conversion reactions. GO/PANI-PVP/V2O5 delivers an excellent specific capacity (495 mA h g-1 at 0.1 A g-1), wonderful rate capability (208 mA h g-1 at 30 A g-1), and good cycling stability (93% after 4000 cycles). Our results provide a new approach for adjusting the valence states, interlayer spacing, and rational design of organic-inorganic compound materials for different functional materials.

Regulating solvated sheath with anion chelant enables 4.6 V ultra-stable commercial LiCoO2.

Increasing cut-off voltage of lithium cobalt oxide (LCO) (> 4.6 V) is an effective strategy to satisfy the ever-increasing demand for high energy density. However, the irreversible phase transition significantly destroys the structure of high-voltage LCO, especially the surface lattice. Considering that the structural stability of LCO is primarily dominated by the intrinsic merits of electrode-electrolyte interface (EEI), we explored and disclosed the operating mechanism of anion chelating agent tris(pentafluorophenyl) borane (TPFPB) and regulate the CEI layer on LCO electrode. Benefiting from the high HOMO energy level and preferential decomposition of TPFPB-PF6-, a robust LiF-rich CEI layer is constructed and greatly improves the stability of electrode/electrolyte interface. The well-designed electrolyte composed of 1 mol L-1 LiPF6 in EC/EMC with TPFPB additives endows Li/LCO half cells and 4 Ah Gr/LCO pouch cell with enhanced cycling stability under a high voltage condition. This work provides pave a new direction for the development of economical high-voltage LIBs.

Self-Adaptive Electrochemistry of Phosphate Cathodes toward Improved Calcium Storage.

Polyanion phosphates exhibit great potential as calcium-ion battery (CIB) cathodes, boasting high working voltage and rapid ion diffusion. Nevertheless, they frequently suffer from capacity decay with irreversible phase transitions; the underlying mechanisms remain elusive. Herein, we report an adaptively layerized structure evolution from discrete NaV2O2(PO4)2F nanoparticles (NPs) to interconnected VOPO4 nanosheets (NSs), triggered by electrochemical (de)calcification, leading to an improvement in Ca2+ storage performance. This electrochemistry-driven self-adapted layerization occurs over approximately 200 cycles, during which NPs undergo a "deform/merge-layerization" process, transitioning from a three-dimensional to a two-dimensional atomic structure, with a distinct 0.68 nm lattice spacing. The transition mechanism is demonstrated to be linked to the gradual separation of structural Na+ and F-. The resultant VOPO4 NSs exhibit exceptional Ca2+ diffusion kinetics (3.19 × 10-9 cm2 s-1, currently the optimal value among inorganic cathode materials for CIBs), enhanced capacity (∼100 mA h g-1), longevity (over 1000 cycles at 50 mA g-1), and high rate (84% retention rates when increasing current density from 50 to 200 mA g-1). Employing advanced electron microscopy, this study reveals an electrochemical activation-induced structure evolution at the atomic level, providing valuable insights into the design of high-performance CIB cathodes.

Boosting the Structural Reversibility of Layered Oxide Cathode for Realizing Long-Term Cycle Life Through Electronic Structure Regulation.

O3-type layered oxide cathode exhibits great application potential for practical sodium-ion batteries, due to its cost-effectiveness, abundant sodium and manganese resources, and high theoretical capacity. However, the irreversible phase transition, coupled with rapid capacity decay, which is primarily attributed to the Jahn-Teller effect of Mn3+, remains a significant bottleneck for commercial application. Additionally, the sluggish kinetics during the (de)sodiation process require urgent improvement. Herein, an electronic structure regulation strategy is proposed by low-valence Li/Cu co-substitution to address these issues. The roles of Li/Cu on the electronic structure, structural evolution, and electrochemical properties in the Na0.96Ni0.22Fe0.2Mn0.5Li0.04Cu0.04O2 (NFMLC) cathode are comprehensively explored through systematic in situ/ex situ characterization techniques and theoretical calculations. The results reveal that this strategy effectively activates more Ni2+/3+ and Fe3+/4+ redox reactions above 2.5V, while suppressing Mn3+/4+ redox activity below 2.5V, thereby achieving highly structural reversibility. Therefore, the NFMLC electrode displays excellent long-term cycling stability (81.5% capacity retention after 2000 cycles at 5 C), and significantly enhanced rate performance (from 45.5% to 80.4% under a ratio of 5 C to 0.5 C). This work provides a valuable perspective on the design of low-cost, long-life, and high-performance layered oxide cathodes for practical sodium-ion batteries.

Improving structure stability of single-crystalline Ni-rich cathode at high voltage by element gradient doping and interfacial modification

Single-crystalline Ni-rich cathodes can provide high energy density and capacity retention rates for lithium-ion batteries (LIBs). However, single-crystalline Ni-rich cathodes experience severe transition metal dissolution, irreversible phase transitions, and reduced structural stability during prolonged cycling at high voltage, which will significantly hinder their practical application. Herein, a Li4TeO5 surface coating along with bulk Te-gradient doping strategy is proposed and developed to solve these issues for single-crystalline Ni-rich LiNi0.90Co0.05Mn0.05O2 cathode (LTeO-1.0). It has been found that the bulk Te6+ gradient doping can lead to the formation of robust Te–O bonds that effectively inhibit H2-H3 phase transformations and reinforce the lattice framework, and the in-situ Li4TeO5 coating layer can act as a protective layer that suppresses the parasitic reactions and grain fragmentation. Besides, the modified material exhibits a higher Young’s modulus, which will be conducive to maintaining significant structural and electrochemical stability under high-voltage conditions. Especially, the LTeO-1.0 electrode shows the improved Li+ diffusion kinetics and thermodynamic stability as well as high capacity retention of 95.83% and 82.12% after 200 cycles at the cut-off voltage of 4.3 and 4.5 V. Therefore, the efficacious dual-modification strategy will definitely contribute to enhancing the structural and electrochemical stability of single-crystalline Ni-rich cathodes and developing their application in LIBs.

A three-in-one strategy of high-entropy, single-crystal, and biphasic approaches to design O3-type layered cathodes for sodium-ion batteries

O3-type layered oxides are promising cathodes for sodium-ion batteries (SIBs). However, severe volume changes, irreversible phase transitions, and sluggish Na+ ion transport kinetics lead to structural collapse and severe capacity loss. Herein, a three-in-one strategy “high entropy, single crystal, and biphase” is proposed to design O3-type layered cathodes for SIBs, which achieves enhanced structural stability and Na+ transport kinetics by the combination effect of multimetal high-entropy, the single crystal, and Li substitution. The as-prepared high-entropy oxide (HEO) cathode, Na(Fe1/6Co1/6Ni1/6Mn1/6Ti1/6)Li1/6O2, exhibits a high reversible capacity of 140.3 mAh g−1, robust cycling stability, exceptional rate capability (86 mAh g−1 at rates of 15C), excellent air-stability, and water-resistance ability. In situ X-ray diffraction reveals that the HEO cathode has highly reversible phase transitions and small volume change (ΔV=3.28 %). Ex situ X-ray absorption spectroscopy reveals that reversible Ni2+/Ni4+, Fe3+/Fe3.6+, and Co3+/Co3.6+ redox couples provide charge compensation for the high-entropy cathode at 2.0∼4.2 V. Notably, the full-cell battery based on the high-entropy cathode and hard carbon anode delivers a specific capacity of 134.3 mAh g−1 and an energy density of 390.8 Wh kg−1. This work provides valuable insights into the design of novel high-performance high-entropy cathodes for SIBs, highlighting a promising avenue for advancing rechargeable battery technology.

Study on the impact of cutoff voltage on structural and electrochemical stability of sodium-ion layered cathodes

NaNi1/3Fe1/3Mn1/3O2 is recognized for its relatively high theoretical specific capacity and operating voltage, rendering it a sodium-ion cathode material with significant commercial potential. A higher cutoff voltage typically enables more sodium ion deintercalation, thereby achieving higher capacity. However, this increased deintercalation can introduce challenges such as structural instability and side reactions with the electrolyte, leading to electrochemical performance degradation. This study focuses on the migration process of transition metal ions under conditions of high charging cutoff voltage and high sodium removal. At a voltage of 4.3 V, the migration of Ni ions facilitates more charge compensation but is accompanied by irreversible Ni migration, inducing an irreversible phase transition to the O’ phase. Conversely, at a cutoff voltage of 4.1 V, the P3 and O3 phases with high sodium removal demonstrate excellent cycling stability. The specific capacities before and after 150 cycles (at 0.5C) are 142.3 and 113.7 mAh/g, respectively, indicating a tolerable internal structural stress within these high sodium removal phases. This contrasts with the differentiated internal structural stresses generated by the P3, O3, and O’ phases during phase transitions at a cutoff voltage of 4.3 V. The research underscores the importance of regulating reversible crystal phases within the tolerance range of internal stress and avoiding irreversible crystal phases to enhance the cycling stability of cathode materials. These findings provide crucial insights for optimizing NNFMO cathode materials and hold significant implications for the design of high-performance, long-life sodium-ion batteries.

Near-surface reconstruction strategy stabilizing high-voltage redox reactions in single crystal Li-rich Mn-based oxides

Li-rich Mn-based oxides (LRMO) greatly increase its output energy density due to its additional oxygen redox activity. However, the inherent oxygen loss and irreversible phase transition induce low initial coulombic efficiency and serious voltage decay, further seriously impeding its industrial application. Herein, a near-surface in-situ reconstruction strategy has been proposed, which constructs the oxygen vacancies and spinel phase coating on the surface of single-crystal Li-rich Mn-based oxide (SC-LRMO) concurrently to improve Li+ storage performance via the oxalic acid induction method. Intensive exploration based on structure characterizations demonstrates that such a near-surface in-situ reconstruction strategy not only accelerates the transmission of Li+, but also stabilizes high-voltage redox reactions by trapping the escaping On− within the newly formed spinel phase coating. Impressively, the modified sample exhibit 91.1% capacity retention ratio after 300 cycles, superior to the SC-LRMO (74.5% capacity retention ratio after 300 cycles). Additionally, even at a high cut-off voltage of 5 V, the acid etched sample exhibits significantly enhanced cycling stability, delivering 200 mAh g−1 with a 94% capacity retention ratio after 300 cycles. This surface self-reconstruction strategy provides profound insights into regulating the surface structure of LRMO for high-energy-density lithium-ion batteries.

Interlayer substitution enables air-stable and long-life O3-type cathode for sodium-ion batteries

The O3-type oxides (NaNi0.4Fe0.2Mn0.4O2 (NFM)) have been considered as the most commercially cathode material for high-energy-density sodium-ion batteries owing to their low price, good safety performance, and high energy density. However, their further development is seriously limited due to the complex phase transition, sluggish kinetics of Na+, and intrinsic air instability. Herein, an interlayer substituted NFM (IS-NFM) is constructed by a simple solid-state method with the introduction of alkaline-earth metal. The interlayer substitution will lead to the increase of oxygen content in the internal lattice, which will effectively suppress the irreversible phase transition during cycling and exposure to the air. In addition, the interlayer substitution effectively activated the charge compensation, leading to the mobilized cationic redox process and boosted de-/sodiated kinetic. Consequently, IS-NFM exhibits excellent capacity retention of 83.44 % at 1 C after 200 cycles and remarkable stability even at high voltage. After 15 days of exposure to the air, IS-NFM also delivers superior capacity retention (86.53 %, compared with 0.1 C) and cycling performance (82.70 % at 1 C after 200 cycles). Undoubtedly, the interlayer substitution strategy will expand a novel avenue for constructing air-stable and long-life O3-type oxides for commercial application.

Surface Catalytic Repair for the Efficient Regeneration of Spent Layered Oxide Cathodes.

Direct recycling is considered to be the next-generation recycling technology for spent lithium-ion batteries due to its potential economic benefits and environmental friendliness. For the spent layered oxide cathode materials, an irreversible phase transition to a rock-salt structure near the particle surface impedes the reintercalation of lithium ions, thereby hindering the lithium compensation process from fully restoring composition defects and repairing failed structures. We introduced a transition-metal hydroxide precursor, utilizing its surface catalytic activity produced during annealing to convert the rock-salt structure into a layered structure that provides fast migration pathways for lithium ions. The material repair and synthesis processes share the same heating program, enabling the spent cathode and added precursor to undergo a topological transformation to form the targeted layered oxide. This regenerated material exhibits a performance superior to that of commercial cathodes and maintains 88.4% of its initial capacity after 1000 cycles in a 1.3 Ah pouch cell. Techno-economic analysis highlights the environmental and economic advantages of surface catalytic repair over pyrometallurgical and hydrometallurgical methods, indicating its potential for practical application.

Surface Reconstruction Enhanced Li-Rich Cathode Materials for Durable Lithium-Ion Batteries.

Regulating the distribution of surface elements in lithium-rich cathode materials can effectively change the electrochemical performance of cathode materials. Considering that the enrichment of Mn element on the surface is the main reason for the irreversible phase transition and dissolution of its surface structure, which in turn is the main reason for performance degradation. Based on the molten salt-assisted sintering method, a lithium rich cathode material with surface rich Ni and Co is designed and prepared. The surface enrichment of Ni and Co effectively reduces the dissolution of Mn, promotes the occurrence of irreversible collapse of surface structure from layered phase to rock salt phase on the material surface, improves the stability of surface crystal phase structure, and improves the cycling stability of positive electrode materials. Notably, after 500 cycles at 1 C current density, the discharge-specific capacity attained 189.8 mAh g -1, with a capacity retention rate of 88.9%, indicating a 42.1% improvement in capacity retention. Molten salt treatment is widely used in the modification of positive electrode materials. The research work will provide new ideas for improving the stability of lithium rich materials and promoting their commercial applications.

Revealing the role of B-site cations in the antiferroelectricity of NaNbO3-based perovskites

The promising prospects of antiferroelectric perovskite oxides in the realm of energy storage applications hinge on the unique field-induced phase transitions. Once the transition is triggered by the application of an electric field, characteristic double polarization loops appear. However, NaNbO3-based materials that exhibit a reversible phase transition are still rare, which hinders the practical applications of lead-free antiferroelectrics. Here, the impact of materials chemistry on the competition between antiferroelectric and ferroelectric states is demonstrated in a series of NaNbO3-based solid solutions with varying perovskite B-site cations, while the A-site is fixed as strontium. The crystal structure is analyzed on the basis of Rietveld refinement of high-energy X-ray diffraction data. The phase transition behavior as well as the antiferroelectric and ferroelectric properties are probed by a series of electrical measurements. The antiferroelectric phase is universally observed for all investigated materials in the virgin state. The SrTiO3-substituted system shows an irreversible phase transition similar to that of pure NaNbO3. In contrast, double polarization hysteresis loops are observed in the SrHfO3-, SrZrO3-, and SrSnO3-substituted systems. It is confirmed that compounds that can reduce the tolerance factor of the system contribute to the stabilization of the antiferroelectric order, while those that can reduce the electronegativity difference lead to more pronounced double loops. The competition between antiferroelectricity and ferroelectricity is linked to the competition between covalent and ionic bonding in perovskites.

Enhancing the Cycling and Rate Performance of NaNi1/3Fe1/3Mn1/3O2 Cathodes by La/Al Codoping.

O3-type layered oxides hold significant promise as the material for cathodes in sodium-ion batteries for their favorable electrochemical properties, while irreversible structural degradation and harmful phase transitions during cyclic operation limit the practical application of these materials. In this work, we proposed a La3+/Al3+ codoping strategy in O3-Na(Ni1/3Mn1/3Fe1/3)O2 cathode materials and found that batteries with the Na (Ni1/3Mn1/3Fe1/3)0.998La0.001Al0.001O2 (NFM-La/Al) cathodes exhibited not only promoted capacity from 135.80 to 170.42 mAh g-1 at 0.2 C but also significantly enhanced cycling stability, with a 10% improvement in capacity retention compared with NFM cathodes after 300 cycles. Particularly, their rate performance was significantly improved as well. XRD and XPS tests indicated that La could expand the c-axis of NFM due to its larger ionic radius and thus significantly increased Na+ ion diffusion efficiency, and in addition, Al doping could effectively increase the content of Ni2+ and Mn4+ and thus greatly alleviated the negative Jahn-Teller effect caused by Mn3+. Moreover, consistent with XRD analyses, DFT calculations further substantiated the effectiveness of the La/Al codoping strategy by demonstrating the detailed atom substitution mechanism in the NFM crystal lattice. The boosted structure stability and Na+ diffusion kinetics may enhance the potential for practical applications of O3-type oxide cathodes.

Improved Stability of Single‐Crystal LiCoO2 Cathodes at 4.8 V through Solvation Structure Regulation

AbstractIncreasing the charging cut‐off voltage can significantly improve the capacity of LiCoO2 cathode. However, when the cut‐off voltage exceeds 4.5 V (vs Li/Li+), LiCoO2 undergoes irreversible phase transitions, leading to particle cracking and structural failure. Additionally, the decomposition of the electrolyte compromises the stability of the cathode/electrolyte interface, resulting in diminished battery capacity. Herein, the elements Al, Mg, and Zr are doped into single‐crystal LiCoO2 to enhance the structural stability of LiCoO2. Moreover, a 3 Å zeolite film is used to regulate the solvation structure to enhance the oxidation resistance of the electrolyte. This design enables a more stable cathode/electrolyte interface during high‐voltage cycling. At a cut‐off voltage of 4.8 V, the Li||LiCoO2 battery exhibits an initial discharge capacity of 236.2 mAh g−1 at 0.1 C and maintains 86.6% capacity retention after 100 cycles at 1 C. The pouch full cell, which utilizes a graphite anode and LiCoO2 cathode, operating within a charge–discharge range of 2.8–4.65 V, achieves a specific energy of 276 Wh kg−1 with 81% capacity retention after 200 cycles. This work introduces a desolvated electrolyte into the LiCoO2 battery system, providing a professional approach to addressing the challenges of high‐voltage LiCoO2.