O2 Cathode Research Articles

Solvation Regulation Reinforces Anion-Derived Inorganic-Rich Interphase for High-Performance Quasi-Solid-State Li Metal Batteries.

Solid-state polymer lithium metal batteries are an important strategy for achieving high safety and high energy density. However, the issue of Li dendrites and inherent inferior interface greatly restricts practical application. Herein, this study introduces tris(2,2,2-trifluoroethyl)phosphate solvent with moderate solvation ability, which can not only complex with Li+ to promote the in-situ ring-opening polymerization of 1,3-dioxolane (DOL), but also build solvated structure models to explore the effect of different solvation structures in the polymer electrolyte. Thereinto, it is dominated by the contact ion pair solvated structure with pDOL chain segments forming less lithium bonds, exhibiting faster kinetic process and constructing a robust anion-derived inorganic-rich interphase, which significantly improves the utilization rate of active Li and the high-voltage resistance of pDOL. As a result, it exhibits stable cycling at ultra-high areal capacity of 20 mAh cm-2 in half cells, and an ultra-long lifetime of over 2000h in symmetric cells can be realized. Furthermore, matched with LiNi0.9Co0.05Mn0.05O2 cathode, the capacity retention after 60 cycles is as high as 96.8% at N/P value of 3.33. Remarkably, 0.7 Ah Li||LiNi0.9Co0.05Mn0.05O2 pouch cell with an energy density of 461Wh kg-1 can be stably cycled for five cycles at 100% depth of discharge.

An Efficient and Eco-Friendly Recycling Route of Valuable Metals from Spent Ternary Li-Ion Batteries: Kinetics Evaluation of Chlorination Processes and Regeneration of LiNi0.8Co0.1Mn0.1O2 Cathode Materials.

The recycling of spent Li-ion batteries is urgent, and the effective recovery of valuable metals from spent cathode material is an economic and eco-friendly approach. In this study, Ni, Cu, Co, and Mn were extracted synchronously from spent LiNixCoyMn1-x-yO2 by chlorination and the complexation reaction of ammonium chloride at low temperatures. The kinetics of the chlorination process was investigated by nonisothermal thermal analysis to determine the rate equation of metal conversion, and the apparent activation energies were calculated to be 99.96 kJ·mol-1 for lithium and 146.70 kJ·mol-1 for nickel, cobalt, and manganese, respectively. The separation of valuable metals from polymetallic leaching solution and the regeneration of cathode materials were further investigated to promote the industrialization of the process. The recoveries of Ni, Co, Mn, and Li can reach 97.75, 99.99, 99.99, and 92.23%, respectively. The prepared LiNi0.8Co0.1Mn0.1O2 precursor is a multilayer spherical particle formed by stacking primary hexagonal nanosheets along the (010) crystal axis, the formation mechanism of which was discussed. The effect of temperature, time, and mixed lithium ratio on the performance of single crystal LiNi0.8Co0.1Mn0.1O2 cathode in the synthesis process was investigated to determine the optimum conditions. Compared with commercial materials, the prepared single crystal LiNi0.8Co0.1Mn0.1O2 cathode has a more regular crystal structure and higher initial discharge capacity (215.9 mAh·g-1 at 0.1 C).

Electrochemical and mechanical characterization of thermosets as fluorine‐free cathode binders for Li‐ion batteries

AbstractThis study demonstrates fluorine‐free cross‐linked (meth)acrylate polymers as alternatives to polyvinylidene fluoride (PVDF) in LiNi0.33Mn0.33Co0.33O2 (NMC111) cathodes. We determine the effects of thermal initiator content, polymer content, and curing environment for two polymer chemistries: a flexible acrylate polymer, and a stiff methacrylate polymer. Electrodes are manufactured and tested for final electrochemical performance and mechanical properties. The results show that the flexible acrylate polymer exhibits higher rate capability compared to the stiff methacrylate polymer because calendering fractures the brittle network of stiff polymer. Electrode adhesion to the current collector and cohesion between particles are found to be a strong function of thermal initiator ratio and oxygen inhibition. Furthermore, there exists an optimal binder concentration that maximizes rate capability performance. Under the right conditions, the two polymers exhibit comparable performance to PVDF electrodes. These results provide important implications for designing cross‐linked polymers as cathode binder alternatives to PVDF.

High-Performance Sheet-Type Sulfide All-Solid-State Batteries Enabled by Dual-Function Li4.4Si Alloy-Modified Nano Silicon Anodes.

The silicon-based anodes are one of the promising anodes to achieve the high energy density of all-solid-state batteries (ASSBs). Nano silicon (nSi) is considered as a suitable anode material for assembling sheet-type sulfide ASSBs using thin free-standing Li6PS5Cl (LPSC) membrane without causing short circuit. However, nSi anodes face a significant challenge in terms of rapid capacity degradation during cycling. To address this issue, dual-function Li4.4Si modified nSi anode sheets are developed, in which Li4.4Si serves a dual role by not only providing additional Li+ but also stabilizing the anode structure with its low Young's modulus upon cycling. Sheet-type ASSBs equipped with the Li4.4Si modified nSi anode, thin LPSC membrane, and LiNi0.83Co0.11Mn0.06O2 (NCM811) cathode demonstrate exceptional cycle stability, with a capacity retention of 96.16% at 0.5 C (1.18mA cm-2) after 100 cycles and maintain stability for 400 cycles. Furthermore, a remarkable cell-level energy density of 303.9Wh kg-1 is achieved at a high loading of 5.22 mAh cm-2, representing a leading level of sulfide ASSBs using electrolyte membranes at room temperature. Consequently, the chemically stable slurry process implemented in the fabrication of Li4.4Si-modified nSi anode sheet paves the way for scalable applications of high-performance sulfide ASSBs.

Mo-doped LiNi0.8Co0.1Mn0.1O2 cathode materials with improved performance for lithium ion batteries

The high nickel ternary LiNi[Formula: see text]Co[Formula: see text]Mn[Formula: see text]O2 (NCM811) cathode material has attracted much attention owing to its advantages of high capacity and low price. However, NCM811 suffers from surface side reactions and cation mixing, which results in an unstable crystal structure and lower Coulomb efficiency and capacity in lithium ion batteries. In this work, Mo-doped cathode material NCM811 is effectively synthesized by high-temperature solidification approach. The characterization results show that the doped NCM811 can form a coating layer on the surface, preventing electrolyte side reactions with the electrode. As the cathode for lithium ion batteries, the Mo-doped NCM811 electrode shows an initial discharge capacity of 185.21[Formula: see text]mAh/g and obtains 156.33[Formula: see text]mAh/g with a capacity retention of 84.5% after 100 cycles at 1C. This study provides a simple and reliable method of fabricating high-performance NCM811 cathode materials.

Enhancing Li-ion diffusivity of Li1.3Al0.3Ti1.7(PO4)3 through liquid-electrolytes-induced secondary crystallization

Solid electrolytes (SEs) offer promising avenues for improving both the energy density and safety of lithium-ion batteries (LIBs). However, the grain boundary resistance remains a significant hurdle that impact the performance of LIBs, particularly when utilizing SEs in powder form. In this study, we introduce a novel approach to reduce grain boundary resistance in Li1.3Al0.3Ti1.7(PO4)3 (LATP) via secondary crystallization induced by liquid electrolytes (LEs). By immersing nano-sized LATP powders in LiPF6/carbonates LEs, rapid aggregation and recrystallization into bulk micrometer-sized particles occur within minutes under ambient conditions. This secondary crystallization process alters the Li distribution within LATP bulk phase, substantially reducing the grain boundary resistance and enhancing Li-ion diffusivity. Consequently, the assembled LATP-modified commercial LiNi0.89Co0.07Mn0.04O2 cathode using LiPF6 electrolyte delivers a remarkable discharge capacity of 105.4 mAh g−1 at 4C, significantly superior to the bare electrode (44.7 mAh g−1). The recrystallized LATP enhances the transport properties and pathways of Li+ ions within the cathode material, especially at high current densities. Multinuclear and multi-dimensional solid-state NMR analysis reveal that active F− ions released from the hydrolysis of LiPF6 electrolytes act as mineralizing agent, facilitating rapid agglomeration and secondary growth of LATP grains. Our findings underscore the efficacy of secondary crystallization using LEs as a promising strategy for eliminating grain boundary resistance and facilitating fast Li-ion conduction of SEs, thereby advancing LIB performance.

Highly‐Dispersed Single‐Crystalline Ni‐Rich Cathodes with Low Li/O Loss for High‐Power and Long‐Life Li‐Ion Batteries

AbstractHighly‐dispersed single‐crystalline Ni‐rich cathodes with low Li/O loss are the key for high‐power Li‐ion batteries, but it is still a big challenge because an additional 60–110 °C higher synthesis temperature is required in comparison with the polycrystalline counterparts. Herein, a highly‐ordered and monodisperse single‐crystalline LiNi0.83Co0.12Mn0.05O2 (NCM83) cathode with an average size of 3.24 µm is reported by a Sr/Nb synergically controlling the grain surface energy strategy based on the Vegard's slopes of various ions. The solid‐phase lithiation temperature is reduced by ≈80 °C, greatly reducing Li/Ni disorder and oxygen vacancies with rapid Li‐ion diffusion kinetics and high structure stability. The introduced Sr/Nb ions remarkably increase the electron cloud density near the Fermi level, while alleviating the H2‐H3 phase transition with reduced lattice shrinkage. The as‐prepared single‐crystalline NCM83 cathode exhibits obvious increased capacity retention of 60% at 10C (vs. 0.1C) in coin‐type half‐cells and 89% after cycling 1000 times at 0.5C in pouch‐type full‐cells. The work sheds light on the low‐temperature synthesis of monodisperse and uniform single‐crystalline Ni‐rich cathodes for high‐power and long‐life Li‐ion batteries.

Mechanism of chromium poisoning on La0.5Sr0.5Co0.25Fe0.75O3 cathode and enhancing chromium tolerance using a novel anion doping strategy

Chromium poisoning the La1-xSrxCoyFe1-yO3(LSCF) cathode for solid oxide fuel cells is a severe issue that can lead to its electrochemical performance degradation. To clarify poisoning mechanism of chromium species and develop a novel anion doping strategy with enhancing chromium tolerance, the adsorption behavior of Cr species on LSCF and F-doping LSCF surface are explored by density functional theory (DFT) calculations. Our results indicate that CrO3 molecule prefers to be adsorbed on the La(Sr)O-terminated surface rather that the Co(Fe)O2-terminated LSCF(001) surface. The adsorption energies of CrO3 molecule are much larger than that of O2 molecules, implies that the CrO3 is more favorable to absorb on the LSCF surface. Bader charge analysis shows the CrO3 molecule behaves as an electron acceptor through an adsorption process. The adsorption of Cr atom is a weak physical adsorption for Sr site and La site and the Cr atom chemisorption is found to occur on hollow site and O site. In addition, F-doping efficiently improves chromium tolerance by weakening the adsorption strength of chromium species that poisons LSCF surface and this may be a feasible strategy to develop cathode for high performance solid oxide fuel cells.

Electrochemical properties of tungsten doped LiNi0.9Co0.1O2 lithium-ion battery cathode materials

High-nickel layered cathode materials for lithium-ion batteries have received widespread attention in new energy vehicles for their excellent specific energy and cost advantages, and are considered to be the most promising cathode materials for high-energy density lithium-ion batteries. Despite its many advantages, poor thermal stability and rapid capacity degradation have greatly limited its large-scale application. Ion doping is considered to be an effective way to improve its drawbacks, and in this paper, a series of W-doped LiNi0.9Co0.1O2 cathode materials were prepared using WO3 as a tungsten source. Among them, 1 mol% W doping was the most effective, and its reversible capacity of 204.44 mA g −1 still had 93.25 % capacity retention after 100 this cycles at 1C. Combined with DFT calculations, it is found that the introduction of W does not change the original layered structure and the material transitions from semi-metallic to metallic at lower doping concentrations, resulting in more electrons occupying the Fermi energy levels to enhance its electrical conductivity and leading to an elevated spin state and a lower oxidation state of Ni.

Unveiling the Stability Mechanism of Oriented Ni-Rich Layered Oxides.

Single-crystal and polycrystalline structures are the two main structural forms of the Ni-rich layered cathode for lithium-ion batteries. The structural difference is closely related to the electrochemical performance and thermal stability, but its internal mechanism is unclear and is worthy of further exploration. In this study, both polycrystalline and single-crystal LiNi0.83Co0.12Mn0.05O2 cathodes were prepared by adjusting the calcination temperature and mechanical post-treatment, respectively. Systematic comparisons were made to assess the effects of different grain structures on the electrochemical performance and thermal stability. The study revealed the superior thermal stability of monocrystalline cathodes, attributing it to oxygen vacancies and phase transitions. From the perspective of grain boundaries, it was demonstrated that the diffusion of oxygen vacancies and the reduction of Ni in polycrystalline cathodes exhibit anisotropy. This research elucidates the origins of the superior thermal stability of monocrystalline cathodes in lithium-ion batteries, providing valuable insights into battery material design.

Influence of calcination temperature on the structural properties of hydrothermally synthesized LiMn1.5Ni0.5O4 cathode material: a comparative study for calculating crystallite size and lattice strain

Influence of calcination temperature on the structural properties of hydrothermally synthesized LiMn1.5Ni0.5O4 cathode material: a comparative study for calculating crystallite size and lattice strain

Structure and properties analysis of yttrium doped high-voltage LiNi0.5Mn1.5O4 cathode materials for Li-ion batteries

High voltage cathode spinel material of LiNi0.5Mn1.5O4 was doped by yttrium (Y) element in the form of LiNi0.5Mn1.5−x Y x O4 (x = 0, 0.05, 0.1) for Li-ion batteries. Structure and properties analysis was conducted to study the effect of Y addition on the crystal structure and the electrochemical performances of LiNi0.5Mn1.5−x Y x O4. The results show that undoped LiNi0.5-Mn1.5O4 (x = 0) fit to cubic spinel structure with space group Fd-3m with some LixNi1-xO detected as impurities. The addition of Y with x = 0.05 and 0.1 resulted in the change of LiNi0.5Mn1.5−x Y x O4 structure to space group P4 332. The Y addition was confirmed to enter 4b site co-existed with Mn and this result is closely related to the increase in lattice parameters a from 8.1384(1) Å to 8.1496(5) Å and 8.1627(1) for x = 0, 0.05 and 0.1, respectively. The cubic unit volume of LiNi0.5Mn1.5−x Y x O4 also increased with increasing Y addition. The addition of Y is liable to the formation of more stable [Mn,Y]O6 and MnO6 octahedra and whole crystal structure. The result from charge/discharge analysis shows that the addition of Y resulted in decreasing discharge capacity from 123.56 mAh g−1 to 105.175 mAh g−1 and 104.369 for x = 0.05 and 0.1, respectively. However, capacity retention after the 25th cycle increased constantly from 77% to 88% and 92% with increasing Y addition. Doped Y, in general, improves the electrochemical performance of LiNi0.5Mn1.5−x Y x O4 as cathode material for LIBs.

Prilling and Coating Strategy to Synthesize High-Performance Spherical NaNi0.4Fe0.2Mn0.4O2 Cathode Materials for Sodium Ion Batteries.

Low-cost sodium ion batteries are of great significance in large-scale energy storage applications. With its high energy density and simple synthesis process, layered transition-metal oxides have become one of the most likely sodium ion battery cathode materials to replace lithium ion batteries in the energy storage market. Here, we report a prilling and MoS2 coating strategy to prepare the spherical cathode material. The spherical micronano particles shorten the diffusion path of Na+, restrain the complexity phase transitions, and enhance the tap density of the materials. In addition, the MoS2 coating improves the electrical conductivity of the material and the structural stability of the cathode material in air. The initial specific discharge capacity is 148.4 mA h g-1 at 0.1 C, which can be maintained at 128.9 mA h g-1 after exposure to air for 10 days. This method dramatically improves the energy density and structural stability of the cathode material, which provides a new scheme for preparing high-performance sodium ion batteries.

Pore-Free Single-Crystalline Particles for Durable Na-Ion Battery Cathodes.

The O3-type Na[Ni1-x-yCoxMny]O2 cathodes have received significant attention in sodium-ion batteries (SIBs) due to their high energy density. However, challenges such as structural instability and interfacial instability against an electrolyte solution limit their practical use in SIBs. In this study, the single-crystalline O3-type Na[Ni0.6Co0.2Mn0.2]O2 (SC-NCM) cathode has been designed and synthesized to effectively relieve the degradation pathways of the polycrystalline O3-type Na[Ni0.6Co0.2Mn0.2]O2 (PC-NCM) cathode for SIBs. The mechanically robust SC-NCM due to the absence of pores in the particles enhances tolerance to particle cracking, resulting in stable cycling performance with a cycle retention of 73% over 350 cycles. Moreover, the proposed SC-NCM is synthesized using a simple and cost-effective molten-salt synthetic route without the complex quenching process typically associated with PC-NCM synthesis methods, showing good practical applicability. This study will provide an innovative direction for the development of advanced cathode materials for practical SIBs.

Study on the influence of different manganese sources on the formation of P2/β Bi-phase cathode materials for sodium ion batteries

This work focuses on the effect of the of Mn3+/Mn4+ ratio in the reactants on the structure and electrochemical properties of NaMn0.9Cu0.1O2 cathode materials for sodium-ion batteries. By systematically varying the manganese valence states in the reactants, we observed a phase transition from the β-phase to the P2-phase with increasing Mn3+ concentrations in the reactants, contrary to the expected favorability of the β-phase at higher Mn3+ levels. This finding suggests a complex interplay between the valence states of the reactants and phase formation mechanisms, which needs further investigation. Additionally, electrochemical testing indicated that the phase composition significantly impacts the electrochemical performance of the material. Specifically, the M0 sample, possessing the optimal P2/β ratio, exhibited excellent electrochemical performances, achieving a high initial discharge capacity of 155.1 mA h g−1 and remains 88.1 % after 40 cycles. These results emphasize the importance of precursor selection and valence management in the development of high-performance cathode materials for sodium-ion batteries.

WO3 coating improves the cyclic stability of LiNi0.9Co0.05Mn0.05 as cathode materials for lithium-ion batteries

In this paper, WO3 uniformly coated LiNi0.9Co0.05Mn0.05O2 cathode materials are prepared by wet coating method using ammonium metatungstate as tungsten source. The XRD, SEM, and XPS tests show that the cladding process introduced W ions into the NCM lattice, increasing the layer spacing and improving the lithium diffusion rate. The charge/discharge test results indicate that a moderate amount of WO3 coating can enhance the rate-discharge performance and increase the long cycle life. After 100 cycles at 1C (180 mAh g−1), the reversible capacity of the material containing 0.5wt% WO3 coating is 157.9 mAh g−1, while that of the original material is only 130.9 mAh g−1, which indicates that the WO3 coating protects the cathode material from HF corrosion, thus improving the stability of the structure. DFT calculations show that the dangling bonds of O on the NCM surface are highly susceptible to binding with W, which reduces the possibility of WO3 coating exfoliation.WO3 and NCM are p-type semiconductors and semi-metallic materials, respectively, which form ohmic contacts at heterogeneous interfaces thereby increasing the electronic conductivity of the materials, and due to the synergistic effect, the diffusion barrier of Li near the heterogeneous interfaces is lower than that of the pristine materials.

In-Situ Polymerized High-Voltage Solid-State Lithium Metal Batteries with Dual-Reinforced Stable Interfaces.

Solid polymer electrolytes (SPEs) represent a pivotal advance toward high-energy solid-state lithium metal batteries. However, inadequate interfacial contact remains a significant bottleneck, impeding scalability and application. Inadequate interfacial contact remains a significant bottleneck, impeding scalability and application. Recent efforts have focused on transforming liquid/solid interfaces into solid/solid ones through in situ polymerization, which shows potential especially in reducing interface impedance. Here, we designed high-voltage SSLMBs with dual-reinforced stable interfaces by combining interface modification with an in situ polymerization technology inspired by targeted effects in medicine. Theoretical calculations and time-of-flight secondary ion mass spectrometry (TOF-SIMS) analysis demonstrate that tetramethylene sulfone (TMS) and bis(2,2,2-trifluoromethyl) carbonate (TFEC) exhibit selective adsorption at the interface of the LiNi0.8Co0.1Mn0.1O2 (NCM) cathode and Li anode, respectively. These compounds further decompose to form a stable cathode-electrolyte interface (CEI) film and a solid electrolyte interface (SEI) film, thereby simultaneously achieving a superior interface between the SPE and both the Li anode and NCM cathode. The developed Li||SPE||Li cell sustained cycling for more than 1000 h at 0.3 mA cm-2, and the NCM||SPE||Li cell also demonstrated an excellent capacity retention of 86.8% after 1000 cycles at 1 °C. This work will provide valuable insights for the rational design of high-voltage SSLMBs with stable interfaces, leveraging in situ polymerization as a cornerstone technology.

Engineering a high-performance low-cobalt single crystalline Li1.2Ni0.167Co0.067Mn0.567O2 cathode material for lithium-ion battery

Li-rich manganese-based layered oxides (LRM) can be regarded as the next-generation cathode materials for high-energy-density Li-ion batteries. The single crystalline LRMs make it have the potential to further application due to the higher compaction density and the absence of intergranular cracks. However, it can't meet the requirements for high energy density cathode materials because of its poor discharge capacity and unsatisfactory stability. In this study, we demonstrate the F doped single-crystal LRM (F-LRM) with the size is >800 nm giving an initial discharge capacity of 309 mAh g−1 at current density of 0.1 C (25 mA g−1) and the capacity retention is reaching up to 97.4 % after 100 cycles. Additionally, its rate capability is up to 206 mAh g−1 under 250 mA g−1 with 90.6 % and 80.6 % retention after 300 and 500 cycles, respectively. X-ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS) and Raman indicated that the F-doped LRM forms strong TM-F bonds and creates a suitable oxygen vacancies (OVs) concentration. Furthermore, operando Differential Electrochemical Mass Spectrometer (DEMS) and High-resolution Transmission Electron Microscopy (HRTEM) analysis revealed that O2 for F-LRM does not appear during the (de)lithiation with the layered structure maintained after cycling. The design of high-performance, low-cobalt single crystal materials offers a novel approach for the future development of lithium-rich cathodes.

Enhanced high-rate and cyclic performance of Co-free and Ni-rich LiNi0.95Mn0.05O2 cathodes by coating electronic/Li+ conductive PANI-PEG layer

Enhanced high-rate and cyclic performance of Co-free and Ni-rich LiNi0.95Mn0.05O2 cathodes by coating electronic/Li+ conductive PANI-PEG layer

In-situ Ti4+-doped modification of layer-structured Ni-rich LiNi0.83Co0.11Mn0.06O2 cathode materials for high-energy lithium-ion batteries

The further commercialization of layer-structured Ni-rich LiNi0.83Co0.11Mn0.06O2 (NCM83) cathode for high-energy lithium-ion batteries (LIBs) has been challenged by severe capacity decay and thermal instability owing to the microcracks and harmful phase transitions. Herein, Ti4+-doped NCM83 cathode materials are rationally designed via a simple and low-cost in-situ modification method to improve the crystal structure and electrode–electrolyte interface stability by inhibiting irreversible polarizations and harmful phase transitions of the NCM83 cathode materials due to Ti4+-doped forms stronger metal-O bonds and a stable bulk structural. In addition, the optimal doping amount of the composite cathode material is also determined through the results of physical characterization and electrochemical performance testing. The optimized Ti4+-doped NCM83 cathode material presents wider Li+ ions diffusion channels (c = 14.1687 Å), lower Li+/Ni2+ mixing degree (2.68 %), and compact bulk structure. The cell assembled with the optimized Ti4+-doped NCM83 cathode material exhibits remarkable capacity retention ratio of 95.4 % after 100cycles at 2.0C and room temperature, and outstanding reversible discharge specific capacity of 148.2 mAh g−1 at 5.0C. Even under elevated temperature of 60 °C, it delivers excellent capacity retention ratio of 92.2 % after 100cycles at 2.0C, which is significantly superior to the 47.9 % of the unmodified cathode material. Thus, the in-situ Ti4+-doped strategy presents superior advantages in enhancing the structural stability of Ni-rich cathode materials for LIBs.