Reaction Of Anion Research Articles

Cellulose-based water-in-salt ZnBr2 hydrogels with multiple functions for energy storage devices

A new simple preparation method for water-in-salt-type cellulose hydrogels filled with ZnBr2 is reported. The ZnBr2 hydrogel electrolyte can be applied to zinc-ion hybrid supercapacitors and Zn-Br interfacial batteries. The water-in-salt ZnBr2 hydrogel serves as a stable electrolyte for good electrochemical performance in zinc-ion hybrid supercapacitors without redox reactions and can participate in the charging/discharging process of the Zn‒Br interfacial battery through the redox reaction of halogen anions. The assembled zinc-ion hybrid supercapacitor exhibits a specific capacitance of 241.8 F g-1 at 0.5 A g-1. Furthermore, after a 10000-cycle-long charging/discharging test at 5 A g-1, the coulombic efficiency is found at nearly 100%. The interfacial battery reaches the highest energy efficiency of 66% at a current density of 3 mA cm-2 at 0–1.8 V and displays a good cycle life with an 88% average coulombic efficiency at 3 mA cm-2. This work expands the application of hydrogels and provides new possibilities for optimizing the high performance of electrolytes.

Crystal Modulation of Mn-Based Layered Oxide toward Long-Enduring Anionic Redox with Fast Kinetics for Sodium-Ion Batteries.

Mn-based layered oxide cathodes for sodium-ion batteries with anionic redox reactions hold great potential for energy storage applications due to their ultra-high capacity and cost effectiveness. However, achieving high capacity requires overcoming challenges such as oxygen-redox failure, sluggish kinetics, and structural degradation. Herein, we employ an innovative crystal modulation strategy, using Mn-based Na0.72Li0.24Mn0.76O2 as a representative cathode material, which shows that the highly exposed {010} active facets enable an enhanced rate capability (119.6 mAh g-1 at 10C) with fast kinetics. Meanwhile, the reinforced Mn-O bond inhibits excessive oxidation of lattice oxygen and O-O cohesion loss, stabilizing and maintaining a long-enduring reversible oxygen-redox activity (100% high capacity retention after 100 cycles at 0.5C and 84.28% retention after 300 cycles at 5C). Time-resolved operando two-dimensional X-ray diffraction reveals the robust structural stability, zero-strain behavior, and suppressed phase transition with ultra-low volume variation during cycling at different rates (0.1C: 1.75%, 1C: 0.31%, 5C: 0.04%). Additionally, the full cell coupled with hard carbon achieves a high energy density of approximately 211 Wh kg-1 with superior performance. This work highlights the significance of crystal modulation and presents a universal approach in developing Mn-based oxide cathodes with stable anionic redox for high-performance sodium-ion batteries.

Crystal Modulation of Mn‐Based Layered Oxide toward Long‐Enduring Anionic Redox with Fast Kinetics for Sodium‐Ion Batteries

Mn‐based layered oxide cathodes for sodium‐ion batteries with anionic redox reactions hold great potential for energy storage applications due to their ultra‐high capacity and cost effectiveness. However, achieving high capacity requires overcoming challenges such as oxygen‐redox failure, sluggish kinetics, and structural degradation. Herein, we employ an innovative crystal modulation strategy, using Mn‐based Na0.72Li0.24Mn0.76O2 as a representative cathode material, which shows that the highly exposed {010} active facets enable an enhanced rate capability (119.6 mAh g−1 at 10C) with fast kinetics. Meanwhile, the reinforced Mn–O bond inhibits excessive oxidation of lattice oxygen and O–O cohesion loss, stabilizing and maintaining a long‐enduring reversible oxygen‐redox activity (100% high capacity retention after 100 cycles at 0.5C and 84.28% retention after 300 cycles at 5C). Time‐resolved operando two‐dimensional X‐ray diffraction reveals the robust structural stability, zero‐strain behavior, and suppressed phase transition with ultra‐low volume variation during cycling at different rates (0.1C: 1.75%, 1C: 0.31%, 5C: 0.04%). Additionally, the full cell coupled with hard carbon achieves a high energy density of approximately 211 Wh kg−1 with superior performance. This work highlights the significance of crystal modulation and presents a universal approach in developing Mn‐based oxide cathodes with stable anionic redox for high‐performance sodium‐ion batteries.

Reaction dynamics of the nonvalence bound states of the anions

Nonvalence bound state (NBS) is a unique anionic state where an excess electron is loosely bound to a neutral molecule in long-range potentials. Since Fermi and Teller first proposed that an electron could be bound in the dipolar field of a molecule, the physical and chemical properties of NBS in a variety of chemical systems have been investigated over recent decades. In this short review, recent notable studies aimed at thoroughly understanding the dynamics of NBS in various anionic chemical systems are elaborated. Photodetachment and photoelectron spectroscopic methods, particularly applied to cryogenically cooled anions, have been highly successful in providing detailed rovibronic structures of the NBS in many interesting chemical systems. Furthermore, real-time pump-probe photoelectron spectroscopy unraveled new dynamic aspects of anion physics and chemistry, offering deep insight into mode-specific autodetachment dynamics and the role of metastable NBS as a doorway into anionic chemical reactions. Autodetachment and/or nonvalence-to-valence (or vice versa) electron-transfer dynamics of NBS are found to be strongly mode-specific, presenting a challenge for theoretical explanations of their quantum-mechanical nature. The outlook for further exploration of NBS in various chemical or biological contexts as well as its potential exploitation in controlling chemical reaction is also provided.

Decoupling the Failure Mechanism of Li‐Rich Layered Oxide Cathode During High‐Temperature Storage in Pouch‐Type Full‐Cell: A Practical Concern on Anionic Redox Reaction

AbstractIn addressing the global climate crisis, the energy storage performance of Li‐ion batteries (LIBs) under extreme conditions, particularly for high‐energy‐density Li‐rich layered oxide (LRLO) cathode, is of the essence. Despite numerous researches into the mechanisms and optimization of LRLO cathodes under ideal moderate environment, there is a dearth of case studies on their practical/harsh working environments (e.g., pouch‐type full‐cell, high‐temperature storage), which is a critical aspect for the safety and commercial application. In this study, using pouch‐type full‐cells as prototype investigation target, the study finds the cell assembled with LRLO cathode present severer voltage decay than typical NCM layered cathode after high‐temperature storage. Further decoupling elucidates the primary failure mechanism is the over‐activation of lattice oxidized oxygen (aggravate by high‐temperature storage) and subsequent escape of oxidized oxygen species (On−), which disrupts transition metal (TM) coordination and exacerbates electrolyte decomposition, leading to severe TM dissolution, interfacial film reconstruction, and harmful shuttle effects. These chain behaviors upon high‐temperature storage significantly influence the stability of both electrodes, causing substantial voltage decay and lithium loss, which accelerates full‐cell failure. Although the anionic redox reaction can bring additional energy, but the escape of metastable On− species would introduce new concerns in practical cell working conditions.

Reactivity of Atomic Oxygen Radical Anions in Metal Oxide Clusters.

Atomic oxygen radical anion (O⋅-) represents an important type of reactive centre that exists in both chemical and biological systems. Gas-phase atomic clusters can be studied under isolated and well controlled conditions. Studies of O⋅--containing clusters in the gas-phase provide a unique strategy to interpret the chemistry of O⋅- radicals at a strictly molecular level. This review summarizes the research progresses made since 2013 for the reactivity of O⋅- radicals in the atomically precise metal oxide clusters including negatively charged, nanosized, and neutral heteronuclear metal clusters benefitting from the development of advanced experimental techniques. New electronic and geometric factors to control the reactivity and product selectivity of O⋅- radicals under dark and photo-irradiation conditions have been revealed. The detailed mechanisms of O⋅- generation have been discussed for the reaction systems of nanosized and heteroatom-doped metal oxide clusters. The catalytic reactions mediated by the O⋅- radicals in metal clusters have also been successfully established and the microscopic mechanisms about the dynamic generation and depletion of O⋅- radicals have been clearly understood. The studies of O⋅- containing metal oxide clusters in the gas-phase provided new insights into the chemistry of reactive oxygen species in related condensed-phase systems.

New Insights into Anionic Redox in P2-Type Oxide Cathodes for Sodium-Ion Batteries.

Manganese/nickel-based layered transition metal oxides have caught the attention of studies as promising cathodes for sodium-ion batteries (SIBs). It is reported that utilizing both cationic and anionic redox reactions is a promising method for higher energy density cathodes. However, the anionic redox reaction comes at the expense of irreversible oxygen release. Hence, a Li-Mg cosubstituted P2-Na0.67Li0.07Mg0.07Ni0.28Mn0.58O2 material with a honeycomb-ordered superstructure was designed. The Ni3+/Ni4+ redox couple and the anionic redox reaction are proven to have a competitive relationship. Density functional theory calculations reveal the effect of O 2p nonbonding states from Li and prove that Mg-O bonds can stabilize the Ni-O eg states. In situ electrochemical impedance spectroscopy measurements and galvanostatic charging/discharging derived dV/dQ, representing resistance changes with time, are obtained to reveal the mechanism of the anionic redox reaction. This study presents the effect and mechanism of the O 2p nonbonding state and Mg-O bonds of manganese/nickel-based layered oxides.

Unraveling the Anionic Redox Chemistry in Aqueous Zinc‐MnO2 Batteries

AbstractActivating anionic redox reaction (ARR) has attracted a great interest in Li/Na‐ion batteries owing to the fascinating extra‐capacity at high operating voltages. However, ARR has rarely been reported in aqueous zinc‐ion batteries (AZIBs) and its possibility in the popular MnO2‐based cathodes has not been explored. Herein, the novel manganese deficient MnO2 micro‐nano spheres with interlayer “Ca2+‐pillars” (CaMnO‐140) are prepared via a low‐temperature (140 °C) hydrothermal method, where the Mn vacancies can trigger ARR by creating non‐bonding O 2p states, the pre‐intercalated Ca2+ can reinforce the layered structure and suppress the lattice oxygen release by forming Ca−O configurations. The tailored CaMnO‐140 cathode demonstrates an unprecedentedly high rate capability (485.4 mAh g−1 at 0.1 A g−1 with 154.5 mAh g−1 at 10 A g−1) and a marvelous long‐term cycling durability (90.6 % capacity retention over 5000 cycles) in AZIBs. The reversible oxygen redox chemistry accompanied by CF3SO3− (from the electrolyte) uptake/release, and the manganese redox accompanied by H+/Zn2+ co‐insertion/extraction, are elucidated by advanced synchrotron characterizations and theoretical computations. Finally, pouch‐type CaMnO‐140//Zn batteries manifest bright application prospects with high energy, long life, wide‐temperature adaptability, and high operating safety. This study provides new perspectives for developing high‐energy cathodes for AZIBs by initiating anionic redox chemistry.

Gradient and De-Clustered Anionic Redox Enabled Undetectable O2 Formation in 4.5V Sodium Manganese Oxide Cathodes.

Anionic redox chemistry presents a promising approach to enhancing the energy density of oxide cathode materials. However, anionic redox reactions invariably lead to O2 formation, either as free gaseous O2 or trapped molecular O2, which destabilizes the material's structure. Here, this critical challenge is addressed by constructing a crystal structure with both gradient redox activity and de-clustered redox-active oxygen. This design strategy is directly validated by operando differential electrochemical mass spectrometry and ex situ 50K electron paramagnetic resonance, revealing no release of O2 or trapped O2 in the 4.5V P2-type sodium manganese-based layered oxide. Notably, the material exhibits a highly reversible capacity of 247mAhg-1 at 20mAg-1 and exceptional capacity retention of 91.4% after 300 cycles at 300mAg-1. In situ X-ray diffraction further suggests that the absence of O2 formation suppresses the typical P2-O2 phase transition, resulting in a minimal lattice volume change of only 0.5%. Ex situ neutron diffraction studies and theoretical calculations further elucidate that the locally ordered lattice is well-preserved, attributable to reduced cationic migrations during cycling.

Unraveling the Anionic Redox Chemistry in Aqueous Zinc-MnO2 Batteries.

Activating anionic redox reaction (ARR) has attracted a great interest in Li/Na-ion batteries owing to the fascinating extra-capacity at high operating voltages. However, ARR has rarely been reported in aqueous zinc-ion batteries (AZIBs) and its possibility in the popular MnO2-based cathodes has not been explored. Herein, the novel manganese deficient MnO2 micro-nano spheres with interlayer "Ca2+-pillars" (CaMnO-140) are prepared via a low-temperature (140 °C) hydrothermal method, where the Mn vacancies can trigger ARR by creating non-bonding O 2p states, the pre-intercalated Ca2+ can reinforce the layered structure and suppress the lattice oxygen release by forming Ca-O configurations. The tailored CaMnO-140 cathode demonstrates an unprecedentedly high rate capability (485.4 mAh g-1 at 0.1 A g-1 with 154.5 mAh g-1 at 10 A g-1) and a marvelous long-term cycling durability (90.6 % capacity retention over 5000 cycles) in AZIBs. The reversible oxygen redox chemistry accompanied by CF3SO3 - (from the electrolyte) uptake/release, and the manganese redox accompanied by H+/Zn2+ co-insertion/extraction, are elucidated by advanced synchrotron characterizations and theoretical computations. Finally, pouch-type CaMnO-140//Zn batteries manifest bright application prospects with high energy, long life, wide-temperature adaptability, and high operating safety. This study provides new perspectives for developing high-energy cathodes for AZIBs by initiating anionic redox chemistry.

Synthesis and Reactivity of an Alumanyl-Tin Species to Form an Al,N-Heteroallene Derivative.

The molecular chemistry of metal-metal bonds is crucial for understanding the bonding and reactivity of metal-containing molecules as well as solid metals and their alloys, especially with respect to their application as catalysts for organic transformations and industrial processes. Despite the high efficiency of the recently developed nucleophilic alumanyl anions in the synthesis of diverse Al-metal bonds, the bonding between main group metals in a low oxidation state and the Al atom remains largely unexplored. This paper describes the reaction of an alumanyl anion with a chlorostannylene precursor to afford a compound with an unprecedented covalent Al-Sn bond. The lability of the covalent Al-Sn bond renders it reactive toward the insertion of carbodiimide, N2O, and phenylacetylene. Remarkably, the reaction with benzonitrile furnished an unprecedented Al,N-heteroallene species that contains a linear Al═N═C linkage.

The influence of P-toluenesulfonyl isocyanate on the solvation structure and solid electrolyte interphase formation on graphite anode under high temperatures

The formation and stability of the solid electrolyte interphase (SEI) play a crucial role in determining the performance and lifespan of lithium-ion batteries (LIBs) at evaluated temperatures. Electrolyte additives have emerged as promising candidates for modulating the formation kinetics and stability of the SEI layer. In this study, molecular dynamics (MD) and ab initio molecular dynamics (AIMD) simulations were employed to investigate the influences of P-toluenesulfonyl isocyanate (PTSI) as an electrolyte additive in the LiPF6/EC/DMC electrolyte on the SEI formation process on the graphite anode under high temperatures. MD simulations revealed that PTSI induces modifications in the solvation structure, resulting in two ethylene carbonate (EC) and two dimethyl carbonate (DMC) molecules in the first solvation shell of Li+. Furthermore, the PTSI additive suppressed the decomposition of solvent molecules and PF6 anions in the LiPF6/EC/DMC/PTSI electrolyte under high temperatures according to the AIMD simulations, contributing to a more stable SEI layer. Moreover, this suppression can be attributed to the reduced reactivity of solvent molecules and salt anions, as evidenced by the enhanced bond strength and decreased bond length. These microscopic insights provide a multi-faceted understanding of the functionality of PTSI additives, facilitating the rational design of novel additives.

Local electronic structure modulation via S substitution enables fast-discharging capability for Li-rich Mn-based oxides cathodes

Anionic and cationic redox reaction contribute to the ultrahigh specific capacities of Li-rich Mn-based oxides cathodes (LMNC). However, the irreversible oxygen evolution and sluggish kinetics result in the continuous capacity decay and poor rate performance, which limited its application as cathode material in lithium-ion batteries. Herein, the local electronic structure of LMNC is appropriately modulated via S2− doping to alleviate oxygen release, stabilize the crystal structure stability, and facilitate Li+ diffusion via facile surface defect engineering. The effect of S2− doping site on the systematically energy is investigated by DFT. Under the guidance of this result, LNMC-S is prepared by co-precipitation and high-temperature solid-phase reaction method. The effect of doping concentration on electrochemical property of LMNC was systematically investigated. The results exhibit that S2− doping can effectively suppress the electronic insulation of Li2MnO3, enhance the transport dynamics of lithium ion and inhibit the phase transition of LMNC sample during charge-discharge process. Thereby, the modified sample exhibits superior electrochemical property, such as the 200th discharge capacity is 184.3 mAh·g−1 under 1C, with a capacity retention rate of 87.6 %. This paper is beneficial for enriching the existing theoretical findings and discoveries, providing theoretical guidance for the preparation of high-performance material.

Cone Angles Quantify and Predict the Affinity and Reactivity of Anion Complexes between Trifluoroborates and Rigid Macrocycles.

Steric manipulation is a known concept in molecular recognition but there is currently no linear free energy relationship correlating sterics to the stability of receptor-anion complexes nor to the reactivity of the bound anion. By analogy to Tolman cone angles in cation coordination chemistry, we explore how to define and correlate cone angles of organo-trifluoroborates (R-BF3 -) to the affinities observed for cyanostar-anion binding. We extend the analogy to a rare investigation of the anion's reactivity and how it changes upon binding. The substituent on the anion is used to define the cone angle, θ. A series of 10 anions were studied including versions with ethynyl, ethylene, and ethyl substituents to tune steric bulk across the sp, sp2 and sp3 hybridized α-carbons bearing 0, 1 and 2 hydrogen atoms. A linear relationship between affinity and cone angle is observed for anions bearing substituents larger than the -BF3 - headgroup. This correlation predicted affinities of two new anions to within ±5 %. We explored how complexation affects the reactivity of fluoride exchange. The yield of fluoride transfer from R-BF3 - to Lewis acid triphenylborane is correlated with cone angle. We predict that other rigid macrocycles, like commercially available bambusuril, could follow these trends.

Durable high voltage solid-state sodium batteries with Pseudocapacitive P2 layered oxide cathode

Solid-state sodium batteries (SSBs) have attracted great interests due to their high energy density, good safety and low cost, but their performance including operation voltage, cycling stability and rate capability are far from satisfactory. In this study, a P2-Na0.68Li0.10Ni0.25Mn0.63Ca0.01Ti0.01O2 (NM-L10CT) layered cathode material were successfully fabricated, which possesses a high pseudocapacitance over 92 %, low volume strain of 0.8 %, high Na-ion diffusion coefficient and very good reversibility of anionic redox reaction. Moreover, room temperature solid-state sodium batteries with NM-L10CT and Na3Zr2Si2PO12 (NZSP) solid electrolyte are demonstrated, displaying much improved structural stability and cycling performance compared with that in liquid electrolyte batteries. The NM-L10CT/NZSP/Na SSBs exhibit very excellent electrochemical performance under high cut-off voltage, with high retention rates of 81.2 % after 500 cycles (2.0–4.2 V) and 74.2 % after 300 cycles (2.0–4.3 V), respectively. It has an outstanding rate performance with a high capacity of 115.4 mAh g-1 at 1 C and 74.5 mAh g-1 even at 10 C rate. This is due to the significantly reduced interface resistance and improved structural stability in solid state. This work demonstrates the successful application of high voltage layered cathode in SSBs and provides the insightful understanding of such material in liquid electrolyte and solid state battery.

Superlattice cathodes endow cation and anion co-intercalation for high-energy-density aluminium batteries

Conventionally, rocking-chair batteries capacity primarily depends on cation shuttling. However, intrinsically high-charge-density metal-ions, such as Al3+, inevitably cause strong Coulombic ion-lattice interactions, resulting in low practical energy density and inferior long-term stability towards rechargeable aluminium batteries (RABs). Herein, we introduce tunable quantum confinement effects and tailor a family of anion/cation co-(de)intercalation superlattice cathodes, achieving high-voltage anion charge compensation, with extra-capacity, in RABs. The optimized superlattice cathode with adjustable van der Waals not only enables facile traditional cation (de)intercalation, but also activates O2– compensation with an extra anion reaction. Furthermore, the constructed cathode delivers high energy-density (466 Wh kg–1 at 107 W kg−1) and one of the best cycle stability (225 mAh g–1 over 3000 cycles at 2.0 A g–1) in RABs. Overall, the anion-involving redox mechanism overcomes the bottlenecks of conventional electrodes, thereby heralding a promising advance in energy-storage-systems.

Achieving Stable Cycling Performance in a P2-Type Layered Oxide Cathode through a Synergic Li/Zn Doping for Sodium-Ion Batteries.

It has been suggested that sodium layered transition metal oxides could potentially serve as excellent cathodes for sodium-ion batteries (SIBs) because of their appropriate operating potentials and high capacities. However, the growing reliance on energy requirements has necessitated a higher energy density of SIBs. It has been demonstrated that activating oxygen-related activities for SIBs is a viable method to improve energy density. Herein, we suggest applying the synergy of Li and Zn codoping to activate the anionic redox reactions (ARRs) and improve their reversibility in Na0.75Ni0.3Mn0.7O2. The dual ion doping alleviates the phase transition and inhibits the Na+/vacancy arrangements, consequently improving the rate capacity and cyclic stability. The Na0.75Li0.15Ni0.1Zn0.05Mn0.7O2 delivers a discharge capacity of 134 mA h g-1 and no significant capacity loss at 100 mA g-1 between 2 and 4.5 V after 200 cycles. More importantly, the density functional theory (DFT) calculation proves that the codoping strategy triggers more ARRs compared to single-element doping, thereby providing enhanced capacity. The codoping induced oxygen redox strategies will create a new path for rational design of cathodes to enhance the energy density for SIBs.

Enhancing Reversibility and Kinetics of Anionic Redox in O3‐NaLi1/3Mn2/3O2 through Controlled P2 Intergrowth

AbstractAnionic redox chemistry can surpass theoretical limits of conventional layered oxide cathodes in energy density. A recent model system of sodium‐ion batteries, O3‐NaLi1/3Mn2/3O2, demonstrated full anionic redox capacity but is limited in reversibility and kinetics due to irreversible structural rearrangement and oxygen loss. Solutions to these issues are missing due to the challenging synthesis. Here, we harness the unique structural richness of sodium layered oxides and realize a controlled ratio of P2 structural intergrowth in this model compound with the overall composition maintained. The resulted O3 with 27 % P2 intergrowth structure delivers an excellent initial Coulombic efficiency of 87 %, comparable to the state‐of‐the‐art Li‐rich NMCs. This improvement is attributed to the effective suppression of irreversible oxygen release and structural changes, evidenced by operando Differential Electrochemical Mass Spectroscopy and X‐ray Diffraction. The as‐prepared intergrowth material, based on the environmentally benign Mn, exhibits a reversible capacity of 226 mAh g−1 at C/20 rate with excellent cycling stability stemming from the redox reactions of oxygen and manganese. Our work isolates the role of P2 structural intergrowth and thereby introduces a novel strategy to enhance the reversibility and kinetics of anionic redox reactions in sodium layered cathodes without compromising capacity.

Enhancing Reversibility and Kinetics of Anionic Redox in O3-NaLi1/3Mn2/3O2 through Controlled P2 Intergrowth.

Anionic redox chemistry can surpass theoretical limits of conventional layered oxide cathodes in energy density. A recent model system of sodium-ion batteries, O3-NaLi1/3Mn2/3O2, demonstrated full anionic redox capacity but is limited in reversibility and kinetics due to irreversible structural rearrangement and oxygen loss. Solutions to these issues are missing due to the challenging synthesis. Here, we harness the unique structural richness of sodium layered oxides and realize a controlled ratio of P2 structural intergrowth in this model compound with the overall composition maintained. The resulted O3 with 27 % P2 intergrowth structure delivers an excellent initial Coulombic efficiency of 87 %, comparable to the state-of-the-art Li-rich NMCs. This improvement is attributed to the effective suppression of irreversible oxygen release and structural changes, evidenced by operando Differential Electrochemical Mass Spectroscopy and X-ray Diffraction. The as-prepared intergrowth material, based on the environmentally benign Mn, exhibits a reversible capacity of 226 mAh g-1 at C/20 rate with excellent cycling stability stemming from the redox reactions of oxygen and manganese. Our work isolates the role of P2 structural intergrowth and thereby introduces a novel strategy to enhance the reversibility and kinetics of anionic redox reactions in sodium layered cathodes without compromising capacity.

Origin of enhanced electrochemical performance in lithium-rich cathode materials via the fast ion conductor Li2O-B2O3-LiBr

Lithium-rich cathode materials have garnered significant attention in the energy sector due to their high specific capacity. However, severe capacity degradation impedes their large-scale application. The employment of fast ion conductors for coating has shown potential in improving their electrochemical performance, yet the structural and chemical mechanisms underlying this improvement remain unclear. In this study, we systematically analyze, through first-principles calculations, the mechanism by which Li2O-B2O3-LiBr (Hereafter referred to as LBB) coating enhances the electrochemical performance of the lithium-rich layered cathode material 0.5Li2MnO3·0.5LiNi1/3Co1/3Mn1/3O2 (Hereafter referred to as OLO). Our calculations reveal that the LBB coating introduces a more negative valence charge (average −0.14 e) around the oxygen atoms surrounding transition metals, thereby strengthening metal-oxygen interactions. This interaction mitigates irreversible oxygen oxidation caused by anionic redox reactions under high voltages, reducing irreversible structural changes during battery operation. Furthermore, while the migration barrier for Li+ in OLO is 0.61 eV, the LBB coating acts as a rapid conduit during the Li+ deintercalation process, reducing the migration barrier to 0.32 eV and slightly lowering the internal migration barrier within OLO to 0.43 eV. Calculations of binding energies to electrolyte byproducts HF before and after coating (at −7.421 and −3.253 eV, respectively) demonstrate that the LBB coating effectively resists HF corrosion. Subsequent electrochemical performance studies corroborated these findings. The OLO cathode with a 2% LBB coating exhibited a discharge capacity of 157.12 mAh g−1 after 100 cycles, with a capacity retention rate of 80.38%, whereas the uncoated OLO displayed only 141.67 mAh g−1 and a 72.45% capacity retention. At a 2 C rate, with the 2 wt% LBB-coated sample maintaining a discharge capacity of 140.22 mAh g−1 compared to only 107.02 mAh g−1 for the uncoated OLO.