Fluorination-Enhanced Surface Stability of Cation-Disordered Rocksalt Cathodes for Li-Ion Batteries

Cation-disordered rocksalt (DRX) materials have emerged as a class of novel high-capacity cathodes for Li-ion batteries. However, the commercialization of DRX cathodes will require reducing their capacity decay, which has been associated with oxygen loss during cycling. Recent studies show that fluorination of DRX cathodes can effectively reduce oxygen loss and improve cycling stability; however, the underlying atomic-scale mechanisms remain elusive. Herein, using a combination of electrochemical measurements, scanning transmission electron microscopy, and electron energy loss spectroscopy, the correlation between the electrochemical properties and structural evolution in Mn-redox-based DRX cathodes, Li_1.2Ti_0.4–xMn_0.4+xO_2.0-xF_x (x = 0 and 0.2) is examined. It is found that fluorination strongly suppresses structural amorphization and void formation initiated from the particle surface, therefore greatly enhancing the cyclability of the cathode. A novel rocksalt-to-spinel-like structural transformation in the DRX bulk is further revealed, which surprisingly contributes to a gradual capacity increase during cycling. The results provide important insight for the design of novel DRX cathodes with high capacity and long cycle life.     

Decoupling the Voltage Hysteresis of Li-Rich Cathodes: Electrochemical Monitoring,Modulation Anionic Redox Chemistry and Theoretical Verifying

Cathodes in lithium-ion batteries with anionic redox can deliver extraordinarily high specific capacities but also present many issues such as oxygen release, voltage hysteresis, and sluggish kinetics. Identifying problems and developing solutions for these materials are vital for creating high-energy lithium-ion batteries. Herein, the electrochemical and structural monitoring is conducted on lithium-rich cathodes to directly probe the formation processes of larger voltage hysteresis. These results indicate that the charge-compensation properties, structural evolution, and transition metal (TM) ions migration vary from oxidation to reduction process. This leads to huge differences in charge and discharge voltage profile. Meanwhile, the anionic redox processes display a slow kinetics process with large hysteresis (≈0.5 V), compared to fast cationic redox processes without any hysteresis. More importantly, a simple yet effective strategy has been proposed where fine-modulating local oxygen environment by the lithium/oxygen (Li/O) ratio tunes the anionic redox chemistry. This effectively improves its electrochemical properties, including the operating voltage and kinetics. This is also verified by theoretical calculations that adjusting anionic redox chemistry by the Li/O ratio shifts the TM 3d—O 2p bands and the non-bonding O 2p band to a lower energy level, resulting in a higher redox reaction potential.     

Highly Reversible Anion Redox of Manganese-Based Cathode Material Realized by Electrochemical Ion Exchange for Lithium-Ion Batteries

Anion energy storage provides the possibility to achieve higher specific capacity in lithium-ion battery cathode materials, but the problems of capacity attenuation, voltage degradation, and inconsistent redox behavior are still inevitable. In this paper, a novel O2-type manganese-based layered cathode material Li_x[Li_0.2Mn_0.8]O₂ with a ribbon superlattice structure is prepared by electrochemical ion exchange, which realizes the highly reversible redox of anions and excellent cycle performance. Through low-voltage pre-cycling treatment, the specific capacity of the material can reach 230 mAh g⁻¹ without obvious voltage attenuation. During the electrochemical ion exchange, the precursor with P2 structure transforms into Li_x[Li_0.2Mn_0.8]O₂ with O2 structure through the slippage and shrink of adjacent slabs, and the special superlattice structure in Mn slab is still retained. Simultaneously, a certain degree of lattice mismatch and reversible distortion of the MnO₆ octahedron occur. In addition, the anion redox catalyzes the formation of the solid electrolyte interface, stabilizing the electrode/electrolyte interface and inhibiting the dissolution of Mn. The mechanism of electrochemical ion exchange is systematically studied by comprehensive structural and electrochemical characterization, opening an attractive path for the realization of highly reversible anion redox.     

Toward Stable Cycling of a Cost-Effective Cation-Disordered Rocksalt Cathode via Fluorination

The recently developed Li-excess cation-disordered rock salts (DRXs) exhibit an excellent chemical diversity for the development of alternative Co/Ni-free high-energy cathodes. Herein, the synthesis of a highly fluorinated DRX cathode, Li_1.2Mn_0.6Ti_0.2O_1.8F_0.2, based on cost-effective and earth-abundant transition metals, via a solid-state reaction, is reported. The fluorinated DRX cathode using ammonium fluoride precursor exhibits more uniform particle size and delivers a specific discharge capacity of 233 mAh g⁻¹ and specific energy of 754 Wh kg⁻¹, with 206 mAh g⁻¹ retained after 200 cycles. The combined synchrotron X-ray absorption spectroscopy and resonant inelastic X-ray scattering spectroscopy analysis reveals that the remarkable cycling performance is attributed to the high fluorination and thus enhanced Mn content, enabling the utilization of more Mn redox than the oxide analog. This study demonstrates a great promise to develop next-generation cost-effective DRX cathodes with enhanced capacity retention for high-energy Li-ion batteries.     

Unveiling the Anionic Redox Chemistry in Phosphate Cathodes for Sodium-Ion Batteries

Anionic redox chemistry has aroused increasing attention in sodium-ion batteries (SIBs) by virtue of the appealing additional capacity. However, up to now, anionic redox reaction has not been reported in the mainstream phosphate cathodes for SIBs. Herein, the ultrathin VOPO₄ nanosheets are fabricated as promising cathodes for SIBs, where the oxygen redox reaction is first activated accompanied by reversible ClO₄⁻ (from the electrolyte) insertion/extraction. As a result, the VOPO₄ cathode harvests a record-high capacity (168 mAh g⁻¹ at 0.1 C) among its counterparts ever reported. Moreover, the ClO₄⁻ insertion efficiently expands the interlayer spacing of VOPO₄ and accelerates the ion diffusion, enabling an unprecedentedly high rate performance (69 mAh g⁻¹ at 30 C). Via systematic ex situ characterizations and theoretical computations, the anionic redox chemistry and charge storage mechanism upon cycling are thoroughly elucidated. This study opens up a new avenue toward high-energy phosphate cathodes for SIBs by triggering anionic redox reactions.     

The Role of Ni and Co in Suppressing O-Loss in Li-Rich Layered Cathodes

Lithium-rich transition metal cathodes can deliver higher capacities than stoichiometric materials by exploiting redox reactions on oxygen. However, oxidation of O²⁻ on charging often results in loss of oxygen from the lattice. In the case of Li₂MnO₃ all the capacity arises from oxygen loss, whereas doping with Ni and/or Co leads to the archetypal O-redox cathodes Li[Li_0.2Ni_0.2Mn_0.6]O₂ and Li[Li_0.2Ni_0.13Co_0.13Mn_0.54]O₂, which exhibit much reduced oxygen loss. Understanding the factors that determine the degree of reversible O-redox versus irreversible O-loss is important if Li-rich cathodes are to be exploited in next generation lithium-ion batteries. Here it is shown that the almost complete eradication of O-loss with Ni substitution is due to the presence of a less Li-rich, more Ni-rich (nearer stoichiometric) rocksalt shell at the surface of the particles compared with the bulk, which acts as a self-protecting layer against O-loss. In the case of Ni and Co co-substitution, a thinner rocksalt shell forms, and the O-loss is more abundant. In contrast, Co doping does not result in a surface shell yet it still suppresses O-loss, although less so than Ni and Ni/Co doping, indicating that doping without shell formation is effective and that two mechanisms exist for O-loss suppression.     

Local Electronic Structure Modulation Enables Fast-Charging Capability for Li-Rich Mn-Based Oxides Cathodes With Reversible Anionic Redox Activity

Anionic and cationic redox chemistries boost ultrahigh specific capacities of Li-rich Mn-based oxides cathodes (LRMO). However, irreversible oxygen evolution and sluggish kinetics result in continuous capacity decay and poor rate performance, restricting the commercial fast-charging cathodes application for lithium ion batteries. Herein, the local electronic structure of LRMO is appropriately modulated to alleviate oxygen release, enhance anionic redox reversibility, and facilitate Li⁺ diffusion via facile surface defect engineering. Concretely, oxygen vacancies integrated on the surface of LRMO reduce the density of states of O 2p band and trigger much delocalized electrons to distribute around the transition metal, resulting in less oxygen release, enhancing reversible anionic redox and the MnO₆ octahedral distortion. Besides, partially reduced Mn and lattice vacancies synchronously stimulate the electrochemical activity and boost the electronic conductivity, Li⁺ diffusion rate, and fast charge transfer. Therefore, the modified LRMO exhibits enhanced cyclic stability and fast-charging capability: a high discharging capacity of 212.6 mAh·g⁻¹ with 86.98% capacity retention after 100 cycles at 1 C is obtained and to charge to its 80%, SOC is shortened to 9.4 min at 5 C charging rate. This work will draw attention to boosting the fast-charging capability of LRMO via the local electronic structure modulation.     

Anionic Redox in Rechargeable Batteries: Mechanism,Materials, and Characterization

Compared with conventional positive electrode materials in Li-ion batteries, Li-rich materials have a huge advantage of large specific capacities of >300 mAh g⁻¹. Anionic redox mechanism is proposed to explain the over-capacity, which means anions can participate in the redox process for charge compensation. The concept enriches the range and design considerations of high-energy-density positive electrode materials for both Li-ion and Na-ion batteries, which therefore arouses extensive attention. This review summarizes the progress of anionic redox in rechargeable batteries in recent years and discusses the fundamental mechanism that triggers anionic redox. Moreover, the state-of-the-art materials involving anionic redox are illustrated, accompanied by the challenges for practical applications. Furthermore, the common techniques for monitoring anionic redox are reviewed and compared for an advisable choice in future studies. Finally, the consideration and discussion for designing stable positive electrodes based on cationic and anionic redox are presented. The perspective is highlighted and this review provides a basic understanding of anionic redox in rechargeable batteries and paves the way to develop high-capacity positive electrodes for high-energy battery systems.     

Engineering Transition Metal Layers for Long Lasting Anionic Redox in Layered Sodium Manganese Oxide

Oxygen-redox-based-layered cathode materials are of great importance in realizing high-energy-density sodium-ion batteries (SIBs) that can satisfy the demands of next-generation energy storage technologies. However, Mn-based-layered materials (P2-type Na-poor Na_y[A_xMn_1−x]O₂, where A = alkali ions) still suffer from poor reversibility during oxygen-redox reactions and low conductivity. In this work, the dual Li and Co replacement is investigated in P2-type-layered Na_xMnO₂. Experimentally and theoretically, it is demonstrated that the efficacy of the dual Li and Co replacement in Na_0.6[Li_0.15Co_0.15Mn_0.7]O₂ is that it improves the structural and cycling stability despite the reversible Li migration from the transition metal layer during de-/sodiation. Operando X-ray diffraction and ex situ neutron diffraction analysis prove that the material maintains a P2-type structure during the entire range of Na⁺ extraction and insertion with a small volume change of ≈4.3%. In Na_0.6[Li_0.15Co_0.15Mn_0.7]O₂, the reversible electrochemical activity of Co³⁺/Co⁴⁺, Mn³⁺/Mn⁴⁺, and O^2-/(O₂)^n- redox is identified as a reliable mechanism for the remarkable stable electrochemical performance. From a broader perspective, this study highlights a possible design roadmap for developing cathode materials with optimized cationic and anionic activities and excellent structural stabilities for SIBs.     

Comprehensively Strengthened Metal-Oxygen Bonds for Reversible Anionic Redox Reaction

Introducing anionic redox in layered oxides is an effective approach to breaking the capacity limit of conventional cationic redox. However, the anionic redox reaction generally suffers from excessive oxidation of lattice oxygen to O₂ and O₂ release, resulting in local structural deterioration and rapid capacity/voltage decay. Here, a Na_0.71Li_0.22Al_0.05Mn_0.73O₂ (NLAM) cathode material is developed by introducing Al³⁺ into the transition metal (TM) sites. Thanks to the strong Al–O bonding strength and small Al³⁺ radius, the TMO₂ skeleton and the holistic TM–O bonds in NLAM are comprehensively strengthened, which inhibits the excessive lattice oxygen oxidation. The obtained NLAM exhibits a high reversible capacity of 194.4 mAh g^-1 at 20 mA g^-1 and decent cyclability with 98.6% capacity retention over 200 cycles at 200 mA g⁻¹. In situ characterizations reveal that the NLAM experiences phase transitions with an intermediate OP4 phase during the charge–discharge. Theoretical calculations further confirm that the Al substitution strategy is beneficial for improving the overlap between Mn 3d and O 2p orbitals. This finding sheds light on the design of layered oxide cathodes with highly reversible anionic redox for sodium storage.     

Thermodynamic Activation of Charge Transfer in Anionic Redox Process for Li‐Ion Batteries

Anionic redox processes are vital to realize high capacity in lithium‐rich electrodes of lithium‐ion batteries. However, the activation mechanism of these processes remains ambiguous, hampering further implementation in new electrode design. This study demonstrates that the electrochemical activity of inert cubic‐Li₂TiO₃ is triggered by Fe³⁺ substitution, to afford considerable oxygen redox activity. Coupled with first principles calculations, it is found that electron holes tend to be selectively generated on oxygen ions bonded to Fe rather than Ti. Subsequently, a thermodynamic threshold is unravelled dictated by the relative values of the Coulomb and exchange interactions (U) and charge‐transfer energy (Δ) for the anionic redox electron‐transfer process, which is further verified by extension to inactive layered Li₂TiS₃, in which the sulfur redox process is activated by Co substitution to form Li_1.2Ti_0.6Co_0.2S₂. This work establishes general guidance for the design of high‐capacity electrodes utilizing anionic redox processes.     

Prussian Blue Analogues Cathodes for Nonaqueous Potassium-Ion Batteries: Past,Present, and Future

Recently, potassium-ion batteries (PIBs) have emerged as a new energy storage system, offering a complementary solution to lithium-ion batteries due to their cost-effectiveness and significantly high theoretical energy density, making them suitable for large-scale grid energy storage applications. The critical challenge PIBs face is the scarcity of appropriate high-capacity cathode materials. Among the various contenders, Prussian blue analogs (PBAs) stand out. The appeal of PBAs arises from their simple synthesis, economic viability, and a stable, open framework conducive to the insertion/extraction of large-size K⁺. This review aims to provide an overview of current research progress on PBAs as cathode materials in nonaqueous PIBs. A comprehensive examination of the crystal structure and electrochemical reaction mechanisms of PBAs is undertaken, with a focus on prevalent optimization strategies in PIBs. Subsequent sections delve into designing and developing potassium-based full cells architectures incorporating PBAs. The discourse culminates in a discussion on the requirements for transitioning PBAs PIBs from a laboratory setting to commercial production, aiming to chart a course for the development of advanced PIBs.     

Ambilaterality of Redox Mediators towards 1O2 in Li-O2 Batteries: Trap and Quencher

Lithium oxygen batteries (LOBs) are considered promising next-generation lithium batteries owing to their high theoretical specific energy density. However, several issues must be addressed for realizing the practical applications of LOBs. Among them, the evolution of singlet oxygen (¹O₂)—which undergoes vigorous reactions that compromise the stability of the system—is a key challenge. The high overpotential induced by low-conductivity lithium peroxide necessitates the use of a redox mediator (RM) to facilitate the charging process; however, RMs can also be degraded by ¹O₂, which limits their efficacy in the long term. Recently, it was revealed that certain RMs play a role in suppressing the generation of ¹O₂. In this review, the relationship between the RM and ¹O₂ is described. Based on recent understandings, clear insight into RM reactions toward ¹O₂ and possible future research directions will be provided.     

Simultaneous Cationic and Anionic Redox Reactions Mechanism Enabling High‐Rate Long‐Life Aqueous Zinc‐Ion Battery

Rechargeable aqueous zinc‐ion batteries hold great promise for potential applications in large‐scale energy storage, but the reversible insertion of bivalent Zn²⁺ and fast reaction kinetics remain elusive goals. Hence, a highly reversible Zn/VN_x O_y battery is developed, which combines the insertion/extraction reaction and pseudo‐capacitance‐liked surface redox reaction mechanism. The energy storage is induced by a simultaneous reversible cationic (V³⁺ ? V²⁺) and anionic (N^3? ? N^2?) redox reaction, which are mainly responsible for the high reversibility and no structural degradation of VN_xO_y. As expected, a superior rate capability of 200 mA h g^?1 at 30 A g^?1 and high cycling stability up to 2000 cycles are achieved. This finding opens new opportunities for the design of high‐performance cathodes with fast Zn²⁺ reaction kinetics for advanced aqueous zinc‐ion batteries.     

Three Electron Reversible Redox Reaction in Sodium Vanadium Chromium Phosphate as a High‐Energy‐Density Cathode for Sodium‐Ion Batteries

A sodium‐ion battery operating at room temperature is of great interest for large‐scale stationary energy storage because of its intrinsic cost advantage. However, the development of a high capacity cathode with high energy density remains a great challenge. In this work, sodium super ionic conductor‐structured Na₃V_2?xCr_x(PO₄)₃ is achieved through the sol–gel method; Na₃V_1.5Cr_0.5(PO₄)₃ is demonstrated to have a capacity of 150 mAh g^?1 with reversible three‐electron redox reactions after insertion of a Na⁺, consistent with the redox couples of V²⁺/³⁺, V³⁺/⁴⁺, and V⁴⁺/⁵⁺. Moreover, a symmetric sodium‐ion full cell utilizing Na₃V_1.5Cr_0.5(PO₄)₃ as both the cathode and anode exhibits an excellent rate capability and cyclability with a capacity of 70 mAh g^?1 at 1 A g^?1. Ex situ X‐ray diffraction analysis and in situ impedance measurements are performed to reveal the sodium storage mechanism and the structural evolution during cycling.     

Lattice Oxygen Redox Reversibility Modulation in Enhancing the Cycling Stability of Li-Rich Cathode Materials

The practical application of lithium-rich layered oxides is prohibited by the drawbacks such as severe capacity and voltage degradation resulting from unstable oxygen redox environment and the accompanied irreversible oxygen release. Herein, a facile and effective strategy is proposed to regulate the oxygen redox chemistry via foreign Fe doping and its induced intrinsic transition metal (TM) doping as well as the in situ constructed spinel surface layer. The Fe doping, together with the induced intrinsic TM dual doping, can stabilize the lattice oxygen in the bulk due to the formed stronger Fe O bond, and restrain the irreversible TM migration and then the undesirable phase transformation. More importantly, thermodynamical energy barrier of oxygen activation is dramatically decreased by the O 2p–Fe 3d charge-transfer, allowing stable oxygen redox activity. And the pre-constructed spinel layer can effectively stabilize the surface lattice oxygen and suppress harmful interfacial side-reactions. Such a simple optimizing method make the modified cathode exhibit a high specific capacity of 298 mAh g⁻¹ at 0.2 C, outstanding cycling stability with a superior capacity and voltage retentions of 92.5% and 90.8%, respectively, after 400 cycles at 1 C. This study provides a new direction for developing advanced Li-ion batteries.     

A Materials Perspective on Direct Recycling of Lithium-Ion Batteries: Principles,Challenges and Opportunities

As the dominant means of energy storage technology today, the widespread deployment of lithium-ion batteries (LIBs) would inevitably generate countless spent batteries at their end of life. From the perspectives of environmental protection and resource sustainability, recycling is a necessary strategy to manage end-of-life LIBs. Compared with traditional hydrometallurgical and pyrometallurgical recycling methods, the emerging direct recycling technology, rejuvenating spent electrode materials via a non-destructive way, has attracted rising attention due to its energy efficient processes along with increased economic return and reduced CO₂ footprint. This review investigates the state-of-the-art direct recycling technologies based on effective relithiation through solid-state, aqueous, eutectic solution and ionic liquid mediums and thoroughly discusses the underlying regeneration mechanism of each method regarding different battery chemistries. It is concluded that direct regeneration can be a more energy-efficient, cost-effective, and sustainable way to recycle spent LIBs compared with traditional approaches. Additionally, it is also identified that the direct recycling technology is still in its infancy with several fundamental and technological hurdles such as efficient separation, binder removal and electrolyte recovery. In addressing these remaining challenges, this review proposes an outlook on potential technical avenues to accelerate the development of direct recycling toward industrial applications.     

Tuning Anionic Redox Activity and Reversibility for a High‐Capacity Li‐Rich Mn‐Based Oxide Cathode via an Integrated Strategy

When fabricating Li‐rich layered oxide cathode materials, anionic redox chemistry plays a critical role in achieving a large specific capacity. Unfortunately, the release of lattice oxygen at the surface impedes the reversibility of the anionic redox reaction, which induces a large irreversible capacity loss, inferior thermal stability, and voltage decay. Therefore, methods for improving the anionic redox constitute a major challenge for the application of high‐energy‐density Li‐rich Mn‐based cathode materials. Herein, to enhance the oxygen redox activity and reversibility in Co‐free Li‐rich Mn‐based Li_1.2Mn_0.6Ni_0.2O₂ cathode materials by using an integrated strategy of Li₂SnO₃ coating‐induced Sn doping and spinel phase formation during synchronous lithiation is proposed. As an Li⁺ conductor, a Li₂SnO₃ nanocoating layer protects the lattice oxygen from exposure at the surface, thereby avoiding irreversible oxidation. The synergy of the formed spinel phase and Sn dopant not only improves the anionic redox activity, reversibility, and Li⁺ migration rate but also decreases Li/Ni mixing. The 1% Li₂SnO₃‐coated Li_1.2Mn_0.6Ni_0.2O₂ delivers a capacity of more than 300 mAh g^?1 with 92% Coulombic efficiency. Moreover, improved thermal stability and voltage retention are also observed. This synergic strategy may provide insights for understanding and designing new high‐performance materials with enhanced reversible anionic redox and stabilized surface lattice oxygen.     

Biological Redox Mediation in Electron Transport Chain of Bacteria for Oxygen Reduction Reaction Catalysts in Lithium–Oxygen Batteries

Governing the fundamental reaction in lithium–oxygen batteries is vital to realizing their potentially high energy density. Here, novel oxygen reduction reaction (ORR) catalysts capable of mediating the lithium and oxygen reaction within a solution‐driven discharge, which promotes the solution‐phase formation of lithium peroxide (Li₂O₂), are reported, thus enhancing the discharge capacity. The new catalysts are derived from mimicking the biological redox mediation in the electron transport chain in Escherichia coli, where vitamin K2 mediates the oxidation of flavin mononucleotide and the reduction of cytochrome b in the cell membrane. The redox potential of vitamin K2 is demonstrated to coincide with the suitable ORR potential range of lithium–oxygen batteries in aprotic solvent, thereby enabling its successful functioning as a redox mediator (RM) triggering the solution‐based discharge. The use of vitamin K2 prevents the growth of film‐like Li₂O₂ even in an ether‐based electrolyte, which has been reported to induce surface‐driven discharge and early passivation of the electrode, thus boosting the discharge capacity by ≈30 times. The similarity of the redox mediation in the biological cell and lithium–oxygen “cell” inspires the exploration of redox active bio‐organic compounds for potential high‐performance RMs toward achieving high specific energies for lithium–oxygen batteries.     

Electrochemical Mg2+ Displacement Driven Reversible Copper Extrusion/Intrusion Reactions for High-Rate Rechargeable Magnesium Batteries

Rechargeable magnesium batteries (RMBs) based on metal Mg anodes have shown great potential owing to the abundant natural resources, high volumetric capacity, and low safety hazard. Nevertheless, the development of RMBs is hampered by the sluggish kinetics of Mg²⁺ diffusion and the limited cyclability of cathode materials. Herein, nonstoichiometric copper selenide (Cu_2–xSe) are synthesized via a solution-based method and exploited as a durable cathode material based on ionic displacement mechanism for RMBs. The copper ions in the Se²⁻ based sub-lattices are reversibly exchanged by Mg²⁺ ions without causing lattice collapse. Owing to the same face-centered cubic Se²⁻ sub-lattices and similar unit cell size of Cu_2–xSe and MgSe, the energy barrier for lattice reconstruction during cycling processes is very low, significantly improving the rate performance, structural stability, and cycle life of the Cu_2–xSe cathode. Moreover, metal Cu is in situ generated during discharging, thus greatly facilitating electron transport. Comprehensive characterizations confirm that the Cu_2–xSe cathode undergoes reversible copper ion extrusion/reinjection during the discharge−charge steps. This work suggests the great potential for exploring high-performance electrode materials based on ionic displacement mechanism for advanced multivalent-ion secondary batteries.