High-voltage Cathode Materials Research Articles

A Unique Wide-Spacing Fence-Type Superstructure for Robust High-Voltage O3-Type Sodium Layered Cathode.

Enhancing the energy density of layered oxide cathode materials is of great significance for realizing high-performance sodium-ion batteries and promoting their commercial application. Lattice oxygen redox at high voltage usually enables a high capacity and energy density. But the structural degradation, severe voltage decay, and the resultant poor cycling performance caused by irreversible oxygen release seriously restrict the practical application. Herein we introduce a novel fence-type superstructure (2a × 3a type supercell) into O3-type layered cathode material Na0.9Li0.1Ni0.3Mn0.3Ti0.3O2 and achieve a stable cycling performance at a high voltage of 4.4 V. The fence-type superstructure effectively inhibits the formation of the vacancy clusters resulting from out-of-plane Li migration and in-plane transition metal migration at high voltage due to the wide d-spacing, thereby significantly reducing the irreversible release of lattice oxygen and greatly stabilizing the crystal structure. The cathode exhibits a high energy density of 545 Wh kg-1, a high rate capability (112.8 mAh g-1 at 5C) and a high cycling stability (85.8%@200 cycles with a high initial capacity of 148.6 mAh g-1 at 1C) accompanied by negligible voltage attenuation (98.5%@200 cycles). This strategy provides a distinct spacing effect of superstructure to design stable high-voltage layered cathode materials for Na-ion batteries.

New Insight into Bulk Structural Degradation of High-Voltage LiCoO2 at 4.55 V.

The aggravated mechanical and structural degradation of layered oxide cathode materials upon high-voltage charging invariably causes fast capacity fading, but the underlying degradation mechanisms remain elusive. Here we report a new type of mechanical degradation through the formation of a kink band in a Mg and Ti co-doped LiCoO2 cathode charged to 4.55 V (vs Li/Li+). The local stress accommodated by the kink band can impede crack propagation, improving the structural integrity in a highly delithiated state. Additionally, machine-learning-aided atomic-resolution imaging reveals that the formation of kink bands is often accompanied by the transformation from the O3 to O1 phase, which is energetically favorable as demonstrated by first-principles calculations. Our results provide new insights into the mechanical degradation mechanism of high-voltage LiCoO2 and the coupling between electrochemically triggered mechanical failures and structural transition, which may provide valuable guidance for enhancing the electrochemical performance of high-voltage layered oxide cathode materials for lithium-ion batteries.

Cathode|Electrolyte Interface Engineering by a Hydrogel Polymer Electrolyte for a 3D Porous High-Voltage Cathode Material in a Quasi-Solid-State Zinc Metal Battery by In Situ Polymerization.

This work highlights the development of a superior cathode|electrolyte interface for the quasi solid-state rechargeable zinc metal battery (QSS-RZMB) by a novel hydrogel polymer electrolyte using an ultraviolet (UV) light-assisted in situ polymerization strategy. By integrating the cathode with a thin layer of the hydrogel polymer electrolyte, this technique produces an integrated interface that ensures quick Zn2+ ion conduction. The coexistence of nanowires for direct electron routes and the enhanced electrolyte ion infiltration and diffusion by the 3D porous flower structure with a wide open surface of the Zn-MnO electrode complements the interface formation during the in situ polymerization process. The QSS-RZMB configured with an integrated cathode (i-Zn-MnO) and the hydrogel polymer electrolyte (PHPZ-30) as the separator yields a comparable specific energy density of 214.14Whkg-1 with that of its liquid counterpart (240.38Whkg-1, 0.5MZn(CF3SO3)2 aqueous electrolyte). Other noteworthy features of the presented QSS-RZMB system include its superior cycle life of over 1000 charge-discharge cycles and 85% capacity retention with 99% coulombic efficiency at the current density of 1.0Ag-1, compared to only 60% capacity retention over 500 charge-discharge cycles displayed by the liquid-state system under the same operating conditions.

Hybrid Surface Modification and Bulk Doping Enable Spent LiCoO2 Cathodes for High-Voltage Operation.

The emerging market demand for high-energy-density of energy storage devices is pushing the disposal of end-of-life LiCoO2 (LCO) to shift toward sustainable upgrading into structurally stable high-voltage cathode materials. Herein, an integrated bulk and surface commodification strategy is proposed to render spent LCO (S-LCO) to operate at high voltages, involving bulk Mn doping, near surface P gradient doping, and Li3PO4/CoP (LPO/CP) coating on the LCO surface to yield upcycled LCO (defined as MP-LCO@LPO/CP). Benefiting from hybrid surface coating with Li+-conductive Li3PO4 (LPO) and electron conductive CoP (CP) coupled with Mn and P co-doping, the optimized MP-LCO@LPO/CP cathode exhibits enhanced high-voltage performance, delivering an initial discharge capacity of 218.8 mAh g-1 at 0.2 C with excellent capacity retention of 80.9% (0.5 C) after 200 cycles at a cut-off voltage of 4.6V, along with 96.3% of capacity retention over 100 cycles at 4.5V. These findings may afford meaningful construction for the upcycling of commercial S-LCO into next-generation upmarket cathode materials through the elaborate surface and bulk modification design.

Boosting interface compatibility of high-voltage LiNi0.5Mn1.5O4 cathode materials with an ionic-conductive Li0.33La0.56TiO3 coating

High voltage LiNi0.5Mn1.5O4 (LNMO) is a crucial cathode material for lithium-ion batteries (LIBs) aiming at high energy densities. However, its performance is hindered by the dissolution of transition metal ions and the instability of the cathode electrolyte interface (CEI) film at elevated voltages. To address these issues, we report a solvothermal method to prepare LNMO coated with Li+-conductor Li0.33La0.56TiO3 (LNMO@LLTO). Our study reveals that the LLTO coating not only enhances ion diffusion at the interface, minimizing the Li+ concentration gradient, and acts as a barrier against Mn-ion dissolution. This coating minimizes side reactions, mitigates structural degradation, and promotes the formation of a stable and balanced CEI film that incorporates LLTO, thus ensuring the long-term cycle stability. When compared to bulk LNMO, the LNMO@LLTO cathode demonstrates superior performance, maintaining reversible capacities of 111.4 and 102.2 mAh·g−1 after 500 cycles at 2 and 5C at 25 °C, respectively. Even at 60 °C, the LNMO@LLTO maintains a high capacity of 94.3 mAh·g−1 with minimal electrochemical polarization after 200 cycles at 2C. This simple preparation technique, together with its performance promotion, offers new insights into the development of high voltage cathode materials for high energy density LIBs.

Stabilizing NASICON-type Na4MnCr(PO4)3 by Ti-substitution toward a high-voltage cathode material for sodium ion batteries

The sodium superionic conductor Na4MnCr(PO4)3 gains increasing attention owing to its three-dimensional structure and the three-electron reaction. However, rapid structure degradation during cycling is the major challenge for its practical application. Herein, Ti4+ is utilized to replace a portion of Mn2+ in Na4MnCr(PO4)3. The low redox voltage and d0 electronic configuration of the Ti4+ ions are helpful to suppress the structure alteration and improve electronic conduction. Consequently, the as-prepared Na3.4Mn0.7Ti0.3Cr(PO4)3/C cathode exhibits a remarkable good 91.0% capacity retention after 500 cycles at 10C rate, with exceptional rate capacities of 99.5 mAh g−1 and 81.0 mAh g−1 at 5C and 10C rate, respectively. Furthermore, based on ≈2.86-electron reactions involving Mn2+/Mn3+ (3.5 V), Mn3+/Mn4+ (4.1 V), Cr3+/Cr4+ (4.3 V), and Ti3+/Ti4+ (2.1 V), the material can provide an energy density of approximately 541.6 Wh kg−1, slightly surpassing that of Na4MnCr(PO4)3. Ex-situ XRD investigation further elucidates that throughout the entire charge–discharge process, the Ti-substituted material experiences highly reversible solid-solution and two-phase reactions. Additionally, Ti substitution can greatly promote the interfacial charge transfer of the material and suppress the decomposition of the electrolyte during cycling. This work might open a new insight for designing sodium-ion battery cathode materials with good cycling stability and high energy density.

Exploring the impact of synergistic dual-additive electrolytes on 5 V-class LiNi0·5Mn1·5O4 cathodes

Tris (trimethylsilyl) phosphate (TMSP) and tris(2,2,2-trifluoroethyl) phosphate (TTFP) was added to carbonate solvent-based electrolytes as dual-additives to enhance the performance of LiNi0·5Mn1·5O4 (LNMO). The X-ray photoelectron spectroscopy results revealed that both TMSP with high oxidation ability and TTFP with high oxidation resistance participated in the formation of cathode–electrolyte interphase (CEI) films. Electrochemical impedance spectroscopy confirmed that the constructed CEI films had excellent electronic insulation and ionic conductivity, reducing the interfacial impedance of the LNMO electrode, and improving the electrochemical performance of LNMO/Li half-cells and LNMO/Li4Ti5O12 full-cells. As measured by the nuclear magnetic resonance, the incorporation of TMSP and TTFP significantly reduced the HF content in the electrolytes. Therefore, both LNMO/Li half-cells (500 cycles with 95.7% capacity retention) and LNMO/Li4Ti5O12 full-cells (200 cycles with 79.9% capacity retention) displayed higher cycling stabilities at 5 C owing to the synergistic effect of TMSP and TTFP. In comparison, capacity retentions of ∼76.5% after 500 cycles and ∼37.2% after 200 cycles were respectively achieved for the LNMO/Li half-cells and LNMO/Li4Ti5O12 full-cells with the standard electrolyte at 5 C. This study provides strong evidence that additive combinations can improve the electrochemical performance of high-energy and high-voltage cathode materials.

High-Voltage Spinel Cathode Materials: Navigating the Structural Evolution for Lithium-Ion Batteries.

High-voltage LiNi0.5Mn1.5O4 (LNMO) spinel oxides are highly promising cobalt-free cathode materials to cater to the surging demand for lithium-ion batteries (LIBs). However, commercial application of LNMOs is still challenging despite decades of research. To address the challenge, the understanding of their crystallography and structural evolutions during synthesis and electrochemical operation is critical. This review aims to illustrate and to update the fundamentals of crystallography, phase transition mechanisms, and electrochemical behaviors of LNMOs. First, the research history of LNMO and its development into a LIB cathode material is outlined. Then the structural basics of LNMOs including the classic and updated views of the crystal polymorphism, interconversion between the polymorphs, and structure-composition relationship is reviewed. Afterward, the phase transition mechanisms of LNMOs that connect structural and electrochemical properties are comprehensively discussed from fundamental thermodynamics to operando dynamics at intra- and inter-particle levels. In addition, phase evolutions during overlithiation as well as thermal-/electrochemical-driven phase transformations of LNMOs are also discussed. Finally, recommendations are offered for the further development of LNMOs as well as other complex materials to unlock their full potential for future sustainable and powerful batteries.

Sustainable upcycling of mixed spent cathodes to a high-voltage polyanionic cathode material

Sustainable battery recycling is essential for achieving resource conservation and alleviating environmental issues. Many open/closed-loop strategies for critical metal recycling or direct recovery aim at a single component, and the reuse of mixed cathode materials is a significant challenge. To address this barrier, here we propose an upcycling strategy for spent LiFePO4 and Mn-rich cathodes by structural design and transition metal replacement, for which uses a green deep eutectic solvent to regenerate a high-voltage polyanionic cathode material. This process ensures the complete recycling of all the elements in mixed cathodes and the deep eutectic solvent can be reused. The regenerated LiFe0.5Mn0.5PO4 has an increased mean voltage (3.68 V versus Li/Li+) and energy density (559 Wh kg–1) compared with a commercial LiFePO4 (3.38 V and 524 Wh kg–1). The proposed upcycling strategy can expand at a gram-grade scale and was also applicable for LiFe0.5Mn0.5PO4 recovery, thus achieving a closed-loop recycling between the mixed spent cathodes and the next generation cathode materials. Techno-economic analysis shows that this strategy has potentially high environmental and economic benefits, while providing a sustainable approach for the value-added utilization of waste battery materials.

Exploration of Mixed Polyanionic Compound for Potential High-Voltage Cathode Materials in Sodium-Ion Batteries

Exploration of Mixed Polyanionic Compound for Potential High-Voltage Cathode Materials in Sodium-Ion Batteries

Manipulating Local Chemistry and Coherent Structures for High-Rate and Long-Life Sodium-Ion Battery Cathodes.

Layered sodium transition-metal (TM) oxides generally suffer from severe capacity decay and poor rate performance during cycling, especially at a high state of charge (SoC). Herein, an insight into failure mechanisms within high-voltage layered cathodes is unveiled, while a two-in-one tactic of charge localization and coherent structures is devised to improve structural integrity and Na+ transport kinetics, elucidated by density functional theory calculations. Elevated Jahn-Teller [Mn3+O6] concentration on the particle surface during sodiation, coupled with intense interlayer repulsion and adverse oxygen instability, leads to irreversible damage to the near-surface structure, as demonstrated by X-ray absorption spectroscopy and in situ characterization techniques. It is further validated that the structural skeleton is substantially strengthened through the electronic structure modulation surrounding oxygen. Furthermore, optimized Na+ diffusion is effectively attainable via regulating intergrown structures, successfully achieved by the Zn2+ inducer. Greatly, good redox reversibility with an initial Coulombic efficiency of 92.6%, impressive rate capability (86.5 mAh g-1 with 70.4% retention at 10C), and enhanced cycling stability (71.6% retention after 300 cycles at 5C) are exhibited in the P2/O3 biphasic cathode. It is believed that a profound comprehension of layered oxides will herald fresh perspectives to develop high-voltage cathode materials for sodium-ion batteries.

Constructing Nano-Interlayer Inhibiting Interfacial Degradation toward High-Voltage PEO-Based All-Solid-State Lithium Batteries.

The interfacial instability between PEO-based solid electrolyte (SPE) and high-voltage cathode materials inhibits the longevity of high-energy-density all-solid-state polymer lithium metal batteries (ASSPLBs). Herein, for the first time it is demonstrated, that contact loss caused by gas generation from interfacial side reactions between the high-voltage cathode and solid polymer electrolyte (SPE) can also arise in ASSPLBs. To alleviate the interfacial side reactions, a LiNb0.6Ti0.5O3 (LNTO) layer is well coated on LiNi0.83Co0.07Mn0.1O2 (NCM83), denoted as (CNCM83). The LNTO layer with low electronic conductivity reduces the decomposition drive force of SPE. Furthermore, Ti and Nb in the LNTO layer spontaneously migrate inside the NCM83 surface to form a strong Ti/Nb─O bond, stalling oxygen evolution in high-voltage cathodes. The interfacial degradation phenomena, including SPE decomposition, detrimental phase transition and intragranular cracks of NCM83, and void formation between cathode and SPE, are effectively mitigated by the LNTO layer. Therefore, the growth rate of interfacial resistance (RCEI) decreases from 37.6 Ω h-0.5 for bare NCM83 to 2.4 Ω h-0.5 for CNCM83 at 4.2V. Moreover, 4.2V PEO-based ASSPLBs achieve impressive cyclability with high capacity retention of 135 mAh g-1 (75%) even after 300 cycles at 0.5 C.

Employing Graph Neural Networks for Predicting Electrode Average Voltages and Screening High-Voltage Sodium Cathode Materials.

For many years, humans have been relentlessly focused on enhancing battery longevity and boosting energy storage capacities. The performance and durability of a battery depend significantly on the material used for its electrodes. In this context, merging machine learning with density functional theory (DFT) calculations has emerged as a pivotal approach to advancing the exploration of battery crystal structures. We present a new method that combines a graph convolutional neural network (GNN) with a Transformer convolutional layer, which we call Transformer-GNN. To underscore its efficacy, we benchmarked Transformer-GNN against three established statistical machine learning models: Support Vector Machine, Random Forest, and XGBoost. We also developed a standard GNN, which we refer to as Basic-GNN. Additionally, we compared Basic-GNN with Transformer-GNN to highlight the improvements brought about by incorporating the Transformer convolutional layer. The Transformer-GNN model outperforms the other models, achieving the highest R2 value of 0.82 and the lowest mean squared error of 0.3161. Our findings demonstrate that the Transformer-GNN can profoundly understand battery crystal structures, thus forging the path toward more sophisticated and durable battery systems. Leveraging the GNN model's voltage predictions in tandem with the capacity data sourced from the database, we screened and pinpointed Na(NiO2)2 as a high-voltage (higher than 5 V), high-capacity sodium cathode material. We conducted DFT calculations on Na(NiO2)2 and revealed the migration mechanism of the Na ions.

Enhancing Structural Rigidity of Ultrahigh-Ni Oxide Through Al and Nb Dual-Bulk-Doping for High-Voltage Lithium-Ion Batteries.

The pursuit of high energy densities propels the design of next-generation nickel-based layered oxide cathodes. The utilization of low-cobalt, ultrahigh-nickel layered oxide cathodes, and the extension of operating voltages promise enhanced energy density. However, stability and safety face challenges associated with nickel content, including structural degradation, lattice oxygen evolution, and thermal instability. In this study, a promising strategy of Al and Nb dual-bulk-doping is presented in high-Ni cathode materials of LiNi0.96Co0.04O2 (NC) to stabilize the bulk structure, suppress oxygen release, and attain superior electrochemical performance at high voltages. The introduction of Al and Nb effectively raises the migration energy of Ni2+ into Li sites and stabilizes lattice oxygen through strengthened Al─O and Nb─O bonds. Furthermore, the substitution of high-valence Nb ions reduces the charge depletion of lattice oxygen and induces an ordered microstructure. The Al and Nb dual-bulk-doping strategy mitigates strain and stress associated with the H2↔H3 phase transition, reducing the generation and propagation of microcracks. The resulting Li(Ni0.96Co0.04)0.985Al0.01Nb0.005O2 (NCAN) cathode exhibits superior cycling stability, with a capacity retention of 77.8% after 300 cycles, even when operating at a high-voltage of 4.4V, outperforming the NC (48.5%). This work provides a promising perspective for developing high-voltage and high-Ni cathode materials.

Design of Na3MnZr(PO4)3/Carbon Nanofiber Free-Standing Cathodes for Sodium-Ion Batteries with Enhanced Electrochemical Performances through Different Electrospinning Approaches.

The NASICON-structured Na3MnZr(PO4)3 compound is a promising high-voltage cathode material for sodium-ion batteries (SIBs). In this study, an easy and scalable electrospinning approach was used to synthesize self-standing cathodes based on Na3MnZr(PO4)3 loaded into carbon nanofibers (CNFs). Different strategies were applied to load the active material. All the employed characterization techniques (X-ray powder diffraction (XRPD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), thermal gravimetric analysis (TGA), and Raman spectroscopy) confirmed the successful loading. Compared to an appositely prepared tape-cast electrode, Na3MnZr(PO4)3/CNF self-standing cathodes demonstrated an enhanced specific capacity, especially at high C-rates, thanks to the porous conducive carbon nanofiber matrix. Among the strategies applied to load Na3MnZr(PO4)3 into the CNFs, the electrospinning (vertical setting) of the polymeric solution containing pre-synthesized Na3MnZr(PO4)3 powders resulted effective in obtaining the quantitative loading of the active material and a homogeneous distribution through the sheet thickness. Notably, Na3MnZr(PO4)3 aggregates connected to the CNFs, covered their surface, and were also embedded, as demonstrated by TEM and EDS. Compared to the self-standing cathodes prepared with the horizontal setting or dip-drop coating methods, the vertical binder-free electrode exhibited the highest capacity values of 78.2, 55.7, 38.8, 22.2, 16.2, 12.8, 10.3, 9.0, and 8.5 mAh/g at C-rates of 0.05C, 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C, and 20C, respectively, with complete capacity retention at the end of the measurements. It also exhibited a good cycling life, compared to its tape-cast counterpart: it displayed higher capacity retention at 0.2C and 1C, and, after cycling 1000 cycles at 1C, it could be further cycled at 5C, 10C, and 20C.

In-Situ Cross-linked F- and P-Containing Solid Polymer Electrolyte for Long-Cycling and High-Safety Lithium Metal Batteries with Various Cathode Materials.

The practical application of lithium metal batteries (LMBs) has been hindered by limited cycle-life and safety concerns. To solve these problems, we develop a novel fluorinated phosphate cross-linker for gel polymer electrolyte in high-voltage LMBs, achieving superior electrochemical performance and high safety simultaneously. The fluorinated phosphate cross-linked gel polymer electrolyte (FP-GPE) by in-situ polymerization method not only demonstrates high oxidation stability but also exhibits excellent compatibility with lithium metal anode. LMBs utilizing FP-GPE realize stable cycling even at a high cut-off voltage of 4.6 V (vs Li/Li+) with various high-voltage cathode materials. The LiNi0.6Co0.2Mn0.2O2|FP-GPE|Li battery exhibits an ultralong cycle-life of 1200 cycles with an impressive capacity retention of 80.1 %. Furthermore, the FP-GPE-based batteries display excellent electrochemical performance even at practical conditions, such as high cathode mass loading (20.84 mg cm-2), ultrathin Li (20 μm), and a wide temperature range of -25 to 80 °C. Moreover, the first reported solid-state 18650 cylindrical LMBs have been successfully fabricated and demonstrate exceptional safety under mechanical abuse. Additionally, the industry-level 18650 cylindrical LiMn2O4|FP-GPE|Li4Ti5O12 cells demonstrate a remarkable cycle-life of 1400 cycles. Therefore, the impressive electrochemical performance and high safety in practical batteries demonstrate a substantial potential of well-designed FP-GPE for large-scale industrial applications.

Electrochemical performance of Fe-doped modified high-voltage LiNiPO4 cathode material of lithium-ion batteries

Electrochemical performance of Fe-doped modified high-voltage LiNiPO4 cathode material of lithium-ion batteries

Improving electrochemical performance of spinel-type Ni/Mn-based high-voltage cathode material for lithium-ion batteries via La-F co-doping combined with in-situ integrated perovskite LaMnO3 coating layer

Spinel-type LiNi0.5Mn1.5O4 (LNMO) can provide high-voltage and high theoretical specific capacity as cathode material for lithium-ion batteries (LIBs), thereby LNMO is particularly suitable for electric/hybrid electric vehicles that require high power. Unfortunately, both serious structural deformation derived from the Jahn-Teller effect of Mn3+ and decomposition of electrolyte during repetitive charge/discharge processes at high operating potential result in fast capacity fade. In this work, lanthanum and fluorine co-doping LiNi0.5La0.01Mn1.49O3.97F0.03 (LF-LNMO) is proposed to eliminate its inherent defects. Fluorine can suppress Jahn-Teller effect of Mn3+ by reducing the generation of Mn3+; La3+ ions in LF-LNMO play a role in solidly riveting atoms together in the structure, and LaMnO3 coating layer acts as a physical protection barrier suppressing adverse side reactions that may damage battery performance. Thanks to the synergistic effect derived from structural modification of F−, the pinning effect of La3+ ions, and LaMnO3 surface coating interface reconstruction, the LF-LNMO cathode provides the best cycling performance and rate performance among all investigated electrode materials. Such as, LF-LNMO cathode can provide 64.02% capacity retention after the 1000th cycle at 500 mA g−1 and 30 °C, which is much higher than that (25.56%) of the undoped LiNi0.5Mn1.5O4 (P-LNMO). Besides, LF-LNMO electrode also behaves the excellent high-temperature cycling performance. This work provides a new strategy enhancing structural stability of spinel-type Ni/Mn-based oxide and would motivate us to further devise and prepare high power cathode materials for LIBs.

Unlocking the concentration polarization for Solid-State lithium metal batteries

Ceramic-polymer composite electrolytes for solid-state batteries are promising candidates due to the combination of safe reliability and mechanical flexibility. However, the sluggish lithium-ion transport and the inadequate electrochemical stability with high-voltage cathode materials limit the practical applications. Herein, we report a garnet-polymer solid electrolyte with high ionic conductivity and Li-ion transference number, favorable elasticity and good interface stability. A galvanostatic charge-relaxation process is designed to identify the inhibition effect of high Li-ionic transference number on concentration polarization and reveal its proportion to total polarization. By additionally adding lithium difluoro(oxalato)borate as stabilizer, the electrochemical window of the garnet-polymer composite electrolyte can extend to 5.3 V. The high cation conductivity and excellent antioxidant ability of composite electrolyte contribute to long cycling performance of LiNi0.8Mn0.1Co0.1O2 cathode at threshold voltage of 4.4 V. Furthermore, the pouch cell with high mass loading cathode and limited lithium anode was demonstrated successfully. Our findings provide an effective strategy on fabricating solid-state lithium-metal batteries towards practical applications.

A bimetal strategy for suppressing oxygen release of 4.6V high-voltage single-crystal high-nickel cathode

High-voltage cathode materials, such as single-crystal high-nickel layered oxide materials, are a necessary condition for achieving high energy density lithium-ion batteries, but they have to be accompanied by the structural instability and irreversible release of lattice oxygen during operation, posing serious safety hazards. Here, to solve the lattice oxygen release issue of single-crystal high-nickel cathode, we propose an improved strategy for overall cathode by synchronously addressing interface and lattice instability, ensuring stable operation at a high voltage up to 4.6 V. By Al-doping, in the bulk phase, we intensify the charge transfer between transition metals and oxygen, and the columnar effect caused by doped atoms effectively alleviates internal strain, thereby significantly limiting lattice shrinkage and then suppressing oxygen release. On the other hand, the protective layer of LiNbO3 as the fast ion conductor formed at the cathode interface suppresses parasitic reactions and hinders lattice oxygen loss caused by dissolution of transition metals. Therefore, after 200 cycles at a cut-off voltage of 4.6 V, our cathode material still maintains a capacity retention rate of 89.1%. Density functional theory (DFT) calculations predict the effective suppression of oxygen release for the modified cathode materials, which has been further confirmed by differential electrochemical mass spectrometry (DEMS) tests. This work provides a new perspective for solving the problem of oxygen release under high cut-off voltage conditions for single crystal high nickel cathode.