High-voltage Cathode Research Articles

Lattice-Engineering modulated band structure facilitates enhanced stability of high-voltage LiCoO2 at 4.6 V

Lithium cobalt oxide (LCO) cathode materials could exceed 210 mAh g−1 with excellent volumetric energy density, when operated at voltages above 4.5 V. However, the progress in the advancement of high-voltage LCO cathodes is impeded by unstable lattice oxygen loss and rapid structural degradation. Herein, we propose a modification strategy to modulate the band structure and stabilize the crystal structure of LCO through Zr/Ti dual-doping. The modified Zr/Ti-LCO demonstrates stable cycling performance at elevated cut-off voltage of 4.6 V. Uniform co-doping with zirconium and titanium suppresses the severe H1-3/O1 deleterious phase transition of LCO. By fine-tuning TM-O interactions and modulated band structure mitigate oxygen release reactivity at high voltage, achieving a delicate balance between structural integrity and electrochemical stability. Consequently, the modified Zr/Ti-LCO half-cell achieves superb capacity retention of 87.7 % after 300 cycles at 3.0–4.6 V, while the Zr/Ti-LCO||graphite pouch full-cell retains up to 85.8 % capacity after 500 cycles at 3.0–4.5 V. This study offers critical perspectives for advancing the design of high-voltage LCO cathodes.

Strengthened High-Concentration Quasi-Solid Electrolytes for Lithium Metal with Ultralong Stable Cyclability.

The lithium metal batteries coupled with nickel-rich LiNixCoyMn1-x-yO2 (x > 0.7) cathodes hold promise for surpassing the current energy density limit of lithium-ion batteries. However, conventional electrolytes containing free active solvents are highly susceptible to decomposition, particularly at the interfaces of lithium anode and high-voltage cathode. Herein, we have developed a composite quasi-solid electrolyte (CQSE) utilizing sulfated Al2O3 (S-Al2O3)-bridged cellulose triacetate (CTA) to stabilize the interfaces between the electrolyte and electrodes. S-Al2O3 competitively dissociates Li+ through coordination interactions with anions, facilitating the formation of a distinctive solvation structure characterized by prevalent ion pairs and aggregates. In addition, coordination of S-Al2O3 with CTA forms S-Al2O3-bridged CTA molecular chain networks, enhancing the mechanical strength of the CQSE and immobilizing free liquid molecules. Consequently, the CQSE demonstrates an enhanced tensile strength of up to 7.4 MPa and a high ionic conductivity of 1.8 × 10-3 S cm-1 at room temperature. Furthermore, the CQSE not only suppresses electrode-electrolyte side reactions but also enables the formation of an inorganic-rich solid/cathode electrolyte interphase. As a result, the Li|CQSE|LiNi0.83Co0.11Mn0.06O2 (NCM83) batteries retain 84% capacity after 1000 cycles at 1 C, with the pouch cells demonstrating 80% capacity retention after 250 cycles at 0.5 C.

Integrated optimization design with inherent element behaviors for bulk and surface stability towards 4.7 V LiCoO2 cathode

LiCoO2 (LCO) cathode with higher energy density can be harvested through raising its upper cut-off voltage to 4.7 V (vs. Li+/Li). However, such high-voltage operation exacerbates the bulk and surface instability of LCO, which is responsible for its rapid capacity decay at high voltages. Consequently, to address these issues, an integrated optimization design is reasonably proposed, which involves Mg/F/PO43- cooperative modulation for LCO (LCO-MFP) based on the inherent behaviors of these elements. Specifically, our theoretical calculations reveal the distinct distribution of Mg/F/PO43- (Mg pillaring, F doping and PO43- coating), which is rooted in their innate occupancy propensity. Consistent with our theoretical results, it is experimentally discerned that Mg and F atoms prefer to enter Li layer and O framework of LCO, respectively, whereas PO43- gravitates towards enrichment on the surface, thereby stabilizing bulk structure, hampering the lattice O/Co evolution and enhancing surface stability. The resulting integrated optimized LCO-MFP cathode can achieve an excellent capacity retention of 81.0 % at 4.7 V after 200 cycles. This integrated optimization design is anticipated to pave the way for selecting appropriate modification elements with their intrinsic properties for high-voltage LCO cathode.

High Configuration Entropy Promises Electrochemical Stability of Chloride Electrolytes for High-Energy, Long-Life All-Solid-State Batteries.

Solid-state electrolytes (SSEs) with high ionic conductivity, stability, and interface compatibility are indispensable for high-energy-density and long-life all-solid-state batteries (ASSBs), yet there are scarce SSEs with sufficient ionic conductivity and electrochemical stability. In this study, with a high-entropy SSE (HE-SSE, Li2.9In0.75Zr0.1Sc0.05Er0.05Y0.05Cl6), we show the high configuration entropy has a thermodynamically positive relationship with the high-voltage stability. As a result, the ASSBs with HE-SSE and high-voltage cathode materials exhibit superior high-voltage and long-cycle stability, achieving 250 cycles with 81.4 % capacity retention when charged to 4.8 V (vs. Li+/Li), and even 5000 cycles if charged to 4.6 V (vs. Li+/Li). Experimental characterizations and density functional theory calculations confirm that the HE-SSE greatly suppresses the high-voltage degradation of SSE at the interface, promoting the high-voltage stability coordinately through high entropy and interface stability. The high entropy design offers a general strategy to simultaneously improve the high-voltage stability and ionic conductivity of SSEs, creating an avenue to building high-energy and long-life ASSBs.

Surface Reconstruction Reduces Internal Stress of Ni-Rich Cathode Particles.

High-voltage Ni-rich layered cathode materials are undoubtedly a powerful driving force for high-energy density lithium batteries. However, residual lithium impurities on the surface of Ni-rich materials can cause more severe side reactions under high-voltage, leading to rapid decay. There is still no reliable mechanistic explanation for this phenomenon. It has been detected that residual alkali on the cathode surface under high voltage can cause obvious side reactions. This side reaction will affect the capacity retention of the material and increase the internal stress of the particles. In addition, the surface reconstruction of Ni-rich cathodes is achieved through simple chemical reactions, turning waste into treasure. The newly generated Ti-based layer not only repairs the structure of the nickel-rich material but also optimizes the material from a dynamic perspective. Removing residual lithium components on the cathode surface effectively reduces the hydrolysis and self-catalytic side reactions of PF6 - at the electrolyte cathode interface and suppresses gas generation during cycling, promoting the application of the next generation of high-energy density Ni-rich layered cathode-based lithium batteries with high-voltage.

Electrolyte Design Enables Stable and Energy-Dense Potassium-Ion Batteries.

Free from strategically important elements such as lithium, nickel, cobalt, and copper, potassium-ion batteries (PIBs) are heralded as promising low-cost and sustainable electrochemical energy storage systems that complement the existing lithium-ion batteries (LIBs). However, the reported electrochemical performance of PIBs is still suboptimal, especially under practically relevant battery manufacturing conditions. The primary challenge stems from the lack of electrolytes capable of concurrently supporting both the low-voltage anode and high-voltage cathode with satisfactory Coulombic efficiency (CE) and cycling stability. Herein, we report a promising electrolyte that facilitates the commercially mature graphite anode (>3 mAh cm-2) to achieve an initial CE of 91.14 % (with an average cycling CE around 99.94 %), fast redox kinetics, and negligible capacity fading for hundreds of cycles. Meanwhile, the electrolyte also demonstrates good compatibility with the 4.4 V (vs. K+/K) high-voltage K2Mn[Fe(CN)6] (KMF) cathode. Consequently, the KMF||graphite full-cell without precycling treatment of both electrodes can provide an average discharge voltage of 3.61 V with a specific energy of 316.5 Wh kg-1-(KMF+graphite), comparable to the LiFePO4||graphite LIBs, and maintain 71.01 % capacity retention after 2000 cycles.

Regulating Non-Equilibrium Solvation Structure in Locally Concentrated Ionic Liquid Electrolytes for Wide-Temperature and High-Voltage Lithium Metal Batteries.

The development of high-voltage lithium metal batteries (LMBs) encounters significant challenges due to aggressive electrode chemistry. Recently, locally concentrated ionic liquid electrolytes (LCILEs) have garnered attention for their exceptional stability with both Li anodes and high-voltage cathodes. However, there remains a limited understanding of how diluents in LCILEs affect the thermodynamic stability of the solvation structure and transportation dynamics of Li+ ions. Herein, we propose a wide-temperature LCILEs with 1,3-dichloropropane (DCP13) diluent to construct a non-equilibrium solvation structure under external electric field, wherein the DCP13 diluent enters the Li+ ion solvation sheath to enhance Li+ ion transport and suppress oxidative side reactions at high-nickel cathode (LiNi0.9Co0.05Mn0.05O2, NCM90). Consequently, a Li/NCM90 cell utilizing this LCILE achieves a high capacity retention of 94 % after 240 cycles at 4.3 V, also operates stably at high cut-off voltages from 4.4 V to 4.6 V and over a wide temperature range from -20 °C to 60 °C. Additionally, an Ah-level pouch cell with this LCILE simultaneously achieves high-energy-density and stable cycling, manifesting the practical feasibility. This work redefines the role of diluents in LCILEs, providing inspiration for electrolyte design in developing high-energy-density batteries.

Improving Energy Density in Lithium-Ion Batteries Using Nanomaterials

Lithium-ion batteries are pivotal in modern energy storage, powering everything from consumer electronics to electric vehicles. Despite their advantages, current materials limit their energy density, particularly for electric vehicles. This paper explores the potential of nanomaterials to enhance lithium-ion battery performance, focusing on anodes, cathodes, and electrolytes. The study discusses the limitations of traditional graphite anodes and highlights nanostructured silicon and metal oxides as alternatives to significantly increase capacity and reduce volume expansion. For cathodes, it examines how nanomaterials like S-TiO2 yolk-shell structures and high-voltage cathode materials can improve energy density and stability. The role of nanostructured solid electrolytes in enhancing ionic conductivity and overall battery performance is also analyzed. The paper addresses the challenges of using nanomaterials, such as higher costs and the need for scalable production methods. It suggests future research directions, including optimizing nanostructures and developing cost-effective manufacturing processes. The findings underscore the potential of nanotechnology to overcome current limitations and significantly boost the energy density of lithium-ion batteries.

Challenges and Modification Strategies on High-Voltage Layered Oxide Cathode for Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) have attracted great attention due to their advantages on resource abundance, cost and safety. Layered oxide cathodes (LOCs) of SIBs possess high theoretical capacity, facile synthesis and low cost, and are promising candidates for large scale energy storage application. Increasing operating voltage is an effective strategy to achieve higher specific capacity and also high energy density of SIBs. However, at high operating voltages, LOCs will undergo a series of phase transitions in bulk phase, leading to huge change of volume and layer spacings accompanied by severe lattice stress and cracking formation. Degeneration of surface also occurs between LOCs and electrolytes, resulting in sustained growth of cathode electrolyte interphase (CEI) and release of O2 and CO2. These induce structural destruction and electrochemical performance degradation in high voltage regions. Recently, many strategies have been proposed to improve electrochemical performance of LOCs under high voltages, including bulk element doping, structural design, surface coating and gradient doping. This review describes pivotal challenges and occurrence mechanisms at high voltages, and summarizes strategies to improve stability of bulk and surface. Viewpoints will be provided to promote development of high energy density SIBs.

A Li-Rich Fluorinated Lithium Zirconium Chloride Solid Electrolyte for 4.8 V-Class All-Solid-State Batteries.

Chloride solid-state electrolytes (SEs) represent an important advance for applications in all-solid-state batteries (ASSBs). Among various chloride SEs, lithium zirconium chloride (Li2ZrCl6) is an attractive candidate considering the high natural abundance of Zr. However, Li2ZrCl6 meets the challenge in practical ASSBs because of its limited ionic conductivity and instability when paired with high-voltage cathodes. This is a major drawback, which can result in a high internal resistance, a low capacity utilization of cathode, and poor cycle stability, especially at high voltage. Existing methods cannot achieve simultaneous enhancement on both ionic conductivity and high-voltage stability due to a trade-off between lithium-ion migration and structural stability. Here a two-pronged strategy based on partial fluorination and incorporation of lithium ions in excess of stoichiometric ratios is introduced that enables high-voltage stability while increasing ionic conductivity concurrently. The Li-rich fluorinated halide SE (Li2.3ZrCl6.1F0.2) exhibits a significant advancement in performance, with an ionic conductivity that is double that of the pristine Li2ZrCl6 and much better high-voltage stability. By leveraging Li2.3ZrCl6.1F0.2 with the LiCoO2 cathode and the Li-In anode, the all-solid-state cell exhibits a remarkable initial specific capacity (198.0 mAh g-1 at 0.1 C) and a high capacity retention (78.5% after 150 cycles) within 3.0-4.8V.

Modulating Interfacial Solvation via Ion Dipole Interactions for Low-Temperature and High-Voltage Lithium Batteries.

Extending the stability of ether solvents is pivotal for developing low-temperature and high-voltage lithium batteries. Herein, we elucidate the oxidation behavior of tetrahydrofuran with ternary BF4-, PF6- and difluoro(oxalato)borate anions and the evolution of interfacial solvation environment. Combined in-situ analyses and computations illustrate that the ion dipole interactions and the subsequent formation of ether-Li+-anion complexes in electrolyte rearrange the oxidation order of solvated species, which enhances the electrochemical stability of ether solvent. Furthermore, preferential absorption of anions on the surface of high-voltage cathode favors the formation of a solvent-deficient electric double layer and an anti-oxidation cathode electrolyte interphase, inhibiting the decomposition of tetrahydrofuran. Remarkably, the formulated electrolyte based on ternary anion and tetrahydrofuran solvent endows the LiNi0.8Co0.1Mn0.1O2 cathode with considerable rate capability of 5.0 C and high capacity retention of 93.12% after 200 cycles. At a charging voltage of 4.5 V, the Li||LiNi0.8Co0.1Mn0.1O2 cells deliver Coulombic efficiency above 99% at both 25 and -30 °C.

Deciphering and overcoming the high-voltage limitations of halide and sulfide-based all-solid-state lithium batteries

Adopting high-voltage Ni-rich cathodes in halide and sulfide-based all-solid-state lithium batteries (ASSLBs) holds great promise for breaking through the 400 Wh kg−1 bottleneck. However, both cell configurations are confronted with intricate interfacial challenges in high-voltage regines (≥4.5 V), resulting in inadequate cathode utilization and premature cell degradation. Moreover, contrary to previous studies, coupled with LiNi0.85Co0.1Mn0.05O2 cathodes, typical halide (Li2ZrCl6)-based cells at 4.5 V feature unlimited interfacial degradation and poor long cycle stability, while typical sulfide (Li6PS5Cl)-based cells feature self-limited interfacial degradation and poor initial cycle stability. Herein, this work addresses the high-voltage limitations of Li2ZrCl6 and Li6PS5Cl catholyte-based cells by manipulating electrode mass fraction and tailoring interfacial composition, thereby effectively improving interfacial charge-transfer kinetics and (electro)chemical stability within cathodes. After appropriate interface design, both optimized cells at 4.5 V demonstrate remarkably increased initial discharge capacities (>195 mA h g−1 at 0.1 C), improved cycle stabilities (>80% after 600 cycles at 0.5 C), and enhanced rate performances (>115 mA h g−1 at 1.0 C). This work deepens our understanding of high-voltage applications for halide/sulfide electrolytes and provides generalized interfacial design strategies for advancing high-voltage ASSLBs.

Evaluation of high-entropy (Cr, Mn, Fe, Co, Ni)-oxide nanofibers and nanoparticles as passive fillers for solid composite electrolytes

Solid-state electrolytes (SSEs) could represent the key to solve safety issues of lithium-ion batteries (LIBs). Among them, those obtained by homogenously dispersing inorganic nanofillers into a polymer matrix combine advantages of all SSE typologies. In this work, high-entropy (Cr,Mn,Fe,Co,Ni) oxide (HEO) with different morphology (nanoparticles or nanofibers) are evaluated as passive fillers for the preparation of composite polyethylene oxide (PEO)-based SSEs. By varying their preparation conditions (calcination at 400 or 800°C for 0.5 or 2 h, followed by rapid cooling) different size and crystallization degree of the oxide grains are obtained. The results of the electrochemical testing of the PEO/HEO composites evidence the crucial role of the filler microstructure and morphology. The best results in terms of electrolyte resistance (22.5 Ω), electrochemical stability window (4.7 V), Li+ transference number (0.37) and ionic conductivity (3.0⋅10−4 S cm−1 at 65°C) are obtained by using well crystallized HEO nanofibers with highly defective surface. The suitability of the most promising composite for practical applications is validated by successfully using it in full cell with commercial high-voltage cathode materials.

Self-Templated 3D Sulfide-Based Solid Composite Electrolyte for Solid-State Sodium Metal Batteries.

Rechargeable solid-state sodium metal batteries (SSMBs) experience growing attention owing to the increased energy density (vs Na-ion batteries) and cost-effective materials. Inorganic sulfide-based Na-ion conductors also possess significant potential as promising solid electrolytes (SEs) in SSMBs. Nevertheless, due to the highly reactive Na metal, poor interface compatibility is the biggest obstacle for inorganic sulfide solid electrolytes such as Na3SbS4 to achieve high performance in SSMBs. To address such electrochemical instability at the interface, new design of sulfide SE nanostructures and interface engineering are highly essential. In this work, a facile and straightforward approach is reported to prepare 3D sulfide-based solid composite electrolytes (SCEs), which utilize porous Na3SbS4 (NSS) as a self-templated framework and fill with a phase transition polymer. The 3D structured SCEs display obviously improved interface stability toward Na metal than pristine sulfide. The assembled SSMBs (with TiS2 or FeS2 as cathodes) deliver outstanding electrochemical cycling performance. Moreover, the cycling of high-voltage oxide cathode Na0.67Ni0.33Mn0.67O2 (NNMO) is also demonstrated in SSMBs using 3D sulfide-based SCEs. This study presents a novel design on the self-templated nanostructure of SCEs, paving the way for the advancement of high-energy sodium metal batteries.

Effect of carbon coating on improved electrical and electrochemical performance of Li3Co2SbO6

Abstract We reported a novel high voltage cathode having layered structure and manifold improvement (144%) in electrochemical performance on carbon coating Li3Co2SbO6. The carbon-coated Li3Co2SbO6 has been prepared using a high temperature solid-state method in an air medium with appropriate stoichiometry of the oxide and carbon source (sucrose). The x-ray diffraction and high-resolution transmission electron microscopy results have confirmed homogeneous carbon coating on oxide (Li3Co2SbO6) surface without disturbing phase, structure and morphology. The immediate effect of carbon coating resulted in electrical conductivity enhancement of the carbon coated Li3Co2SbO6 by four order of magnitudes ∼2.79 × 10−4 Scm−1 at room temperature vis-a-vis pristine Li3Co2SbO6. The electrochemical performance of the carbon coated Li3Co2SbO6 has shown sustainable improvement indicating redox activity by more than one Li+ transaction. The carbon coated Li3Co2SbO6 cathode exhibited an initial discharge capacity of 110 mAhg−1 compared to 45 mAhg−1 for its pristine counterpart. The improvement in electrochemical capacity on carbon coating, as reported in this work, is the highest ever compared to prior literature reports on Li3Co2SbO6.

A High-Voltage n-type Organic Cathode Materials Enabled by Tetraalkylammonium Complexing Agents for Aqueous Zinc-Ion Batteries.

Tetrabutylammonium (TBA) salt of hexacyano-substituted cyclopropane dianion (Cp(CN)6 2 -) is prepared through a facile two-step synthetic protocol from commercially available materials and fully characterized as a high-voltage n-type organic cathode in rechargeable aqueous zinc-ion batteries (AZIBs). The addition of tetrabutylammonium triflate (TBAOTf)to the electrolyte mitigates dissolution issues, leading to enhanced cycling stability. Remarkably, the Cp(CN)6 2 - cathode demonstrates a high discharge voltage of 1.43V in AZIBs and retains 85% of its capacity after 1000 cycles at a high loading of 10mg cm- 2 and a cycling rate of 10C. These results, combined with spectroscopic analyses, elucidate a reversible two-electron redox process of Cp(CN)6 2 - facilitated by the insertion/de-insertion of TBA cation. These findings underscore the potential of Cp(CN)6 2 - as a conversion-based n-type cathode in energy storage applications.

Boosting electrochemical performance by regulating rigid-flexible microphase separation of multiblock copolymers

The growth of lithium dendrites and associated safety issues hinder the further development of liquid lithium metal batteries. A novel rigid-flexible multiblock copolymer PBC-mb-PBS was successfully synthesized based on molecular design. Incorporating crystalline rigid phase polybutylene succinate (PBS) into PBC-mb-PBS significantly enhances its tensile strength and low-temperature toughness through physical crosslinking. The flexible polydibutyl 2-(2-cyanoethyl)malonate (PBC) phase with side-chain cyano groups facilitate ionic conduction, forming a LiN-rich stabilized interfacial layer, thereby improving oxidative stability and high-voltage cathode compatibility. A series of multiblock copolymers with varying segment lengths were synthesized to balance mechanical properties and ionic conductivity by adjusting microphase separation. The quasi-solid-state polymer electrolyte (QSPE), derived from PBC-mb-PBS with the molar block ratio of 0.42, exhibits optimal electrochemical performance with ionic conductivity of 6.20 × 10−5 S cm−1 at 30°C and 4.22 × 10−4 S cm−1 at 60°C. Due to its bicontinuous microphase structure, it also shows excellent mechanical strength and promotes uniform lithium deposition at high current densities. Li//LiFePO4 and Li//LiNi0.83Co0.05Mn0.12O2 cells demonstrate high capacity retention, confirming the potential of this polymer electrolyte in high-voltage applications. This design strategy offers insights for developing quasi-solid-state lithium metal batteries with superior overall performance.

Comparative Study of High Voltage Spinel∥Lithium Titanate Lithium‐ion Batteries in Ethylene Carbonate Free Electrolytes

AbstractA persistent obstacle towards the realization of high voltage cathodes is electrolyte instability where oxidation and transition metal dissolution manifest in rapid capacity failure with both issues connected to the presence of ethylene carbonate in the electrolyte. Here, alternative electrolyte co‐solvents are investigated and compared, where the cyclic carbonate is replaced with sulfones ethyl methyl sulfone (EMS) and tetra methylene sulfone (TMS) and fluoroethylene carbonate (FEC). The best full cell performance was observed for cells cycled in a FEC/EMC (3/7) and FEC/EMC (1/1) electrolytes which exhibited 84–85 % capacity retention after 500 cycles. TMS/EMC (3/7), was determined to be the best performing sulfone electrolyte and maintained 71 % capacity after 500 cycles. Post‐mortem XPS analysis indicated different film forming mechanisms for the respective co‐solvent. A thicker cathode electrolyte interphase (CEI) on the LNMO was observed for the FEC containing electrolytes (relative to when TMS was used as the co‐solvent) indicating more effective passivation of the reactive cathode surface which correlated well with the enhanced cycling stability observed. For LTO, more evidence of transition metal migration and a thicker solid electrolyte interphase (SEI) layer was observed for the sulfone electrolyte suggesting more parasitic anode‐electrolyte interactions and an inability to mitigate Mn2+/Ni2+ crosstalk.

Dielectric additive induced weak Li solvation towards stabilized solid electrolyte interface for 4.6V lithium metal batteries

Developing stable electrode-electrolyte interphases on Li metal anode (LMA) and high voltage cathode is crucial for producing durable Li metal batteries. Electrolyte engineering has been regarded as an efficient way to in-situ construct stable and robust interphase. Herein, a dielectric electrolyte system is proposed by introducing LiNbO3 nanoparticles to liquid carbonate-based electrolyte for regulating Li+ solvation structure, and thus inducing stable inorganic-rich solid electrolyte interphase. Moreover, these dielectric nano LiNbO3 additives can regulate the Li+ flux through their build-in electric field to guide dendrite free Li deposition. These multi-functional features of LiNbO3 allow for exceptional cyclic performance in both symmetric cell configuration (3300 h at 0.5 mA cm−2 and 1 mA h cm−2) and Li||LiNi0.8Co0.1Mn0.1O2 half-cell charged at 4.6 V with capacity retention of 80% over 200 cycles. These results demonstrate great potential of dielectric electrolyte on improving the performance of lithium metal batteries.

Understanding and Controlling Structural Defects and Disordering in LiNi0.5Mn1.5O4 Cathodes for Direct Recycling.

Despite significant progress in recycling spent lithium-ion batteries (LIBs), nondestructive, direct recycling methods still face untenable discrepancies in multiple cathode chemistries, which primarily originate from a variety of structure stabilities during the recycling process. Through systematic investigation of the microstructure evolution during the relithiation treatment, we observed the inevitably induced defects and Li/Mn disordering in the LiNi0.5Mn1.5O4 cathode, contributing to the sluggish Li+ transport and irreversible capacity loss. Employing a defect engineering approach to achieve twin boundaries and preferred grain orientation, we show the regenerated cathodes demonstrate a substantial enhancement of Li+ diffusion and cycling stability, retaining 97.4% capacity after 100 cycles and 87.96% after 200 cycles at C/3. This work not only elaborates on a systematic investigation of defect inducement and structural restoration mechanism but also provides an effective approach to directly recycle high-voltage spinel-type cathodes, contributing to the sustainability of next-generation LIBs.