O2 Cathode Research Articles

Quantitative pre-lithiation modulation of aluminum foil anode kinetics enables high rate and stable cycling of high-loading all-solid-state batteries

Aluminum (Al) foil holds great promise as a pure alloy anode for all-solid-state batteries (ASSBs) due to its suitable potential, high theoretical capacity, and excellent electronic conductivity. However, it remains challenging to achieve high reversibility and stability of the Al foil anode for ASSBs. Herein, we investigate the morphological and lithium (Li) kinetics evolutions of the Al foil anode paired with sulfide solid-state electrolyte (SSE). We identify that the significant reversible capacity loss stems from diminished Li kinetics at low Li contents (LixAl, 0 < x < 0.5), where the accumulation of pores and pure delithiated Al phase obstructs Li diffusion, increasing interfacial resistance and overpotential. Conversely, the Al foil anode with high Li contents (LixAl, 0.5 < x < 1) demonstrates reversible structures and rapid Li kinetics. Through precise pre-lithiation control, ASSBs with LiNi0.8Co0.1Mn0.1O2 (NCM811) cathodes exhibit outstanding rate capabilities and cycling stability, achieving over 4,000 cycles with 82.1 % capacity retention at 5C and demonstrating long-term cycling over 1,000 cycles with nearly 100 % capacity retention at ultra-high loadings. This work offers a viable strategy for advancing practical-level ASSBs with enhanced performance and longevity, contributing valuable insights to future battery technology.

A family of dual-anion-based sodium superionic conductors for all-solid-state sodium-ion batteries.

The sodium (Na) superionic conductor is a key component that could revolutionize the energy density and safety of conventional Na-ion batteries. However, existing Na superionic conductors are primarily based on a single-anion framework, each presenting inherent advantages and disadvantages. Here we introduce a family of amorphous Na-ion conductors (Na2O2-MCly, M = Hf, Zr and Ta) based on the dual-anion framework of oxychloride. Benefiting from a dual-anion chemistry and with the resulting distinctive structures, Na2O2-MCly electrolytes exhibit room-temperature ionic conductivities up to 2.0 mS cm-1, wide electrochemical stability windows and desirable mechanical properties. All-solid-state Na-ion batteries incorporating amorphous Na2O2-HfCl4 electrolyte and a Na0.85Mn0.5Ni0.4Fe0.1O2 cathode exhibit a superior rate capability and long-term cycle stability, with 78% capacity retention after 700 cycles under 0.2 C (1C = 120 mA g-1) at room temperature. The discoveries in this work could trigger a new wave of enthusiasm for exploring new superionic conductors beyond those based on a single-anion framework.

Zn Doping Strategy to Suppress the Jahn-Teller Effect to Stabilize Mn-Based Layered Oxide Cathode toward High-Performance Potassium Ion Batteries.

In the research report of cathode of potassium ion battery, Mn-based layered structural oxides have attracted the researcher's attention because of its good energy density and high specific rate capacity. However, the Jahn-Teller effect is the main limiting factor for their development. It leads to the expansion and deactivation of Mn-based layered metal oxides during cycling for a long time. Therefore, mitigation of the Jahn-Teller effect is considered a useful measure to enhance the electrochemical capability of Mn-based layered oxide. In this paper, an R3m-type K0.4Mn0.7Co0.25Zn0.05O2 cathode material is designed through a Zn doping strategy. X-ray diffraction techniques and electrochemical tests verified that the Jahn-Teller effect is effectively mitigated. High performance is achieved in the rate capacity test with 113 mAh g-1 at 50mA g-1. Comparison with similar materials in recent years has demonstrated its superiority, leading rate performance among Mn-based metal oxides reported in recent years. The practical feasibility is verified in the assembled full cell with soft carbon in anode materials and K0.4Mn0.7Co0.25Zn0.05O2 as cathode. In the full cell rate test, 104.8 mAh g-1 discharging capacity is achieved at 50mA g-1 current density.

Cobalt-free spinel–layered structurally integrated Li0.8Mn0.64Ni0.183Fe0.091O2 cathodes for lithium-ion batteries

Cobalt-free, Li-rich layered-spinel structurally integrated positive electrode (cathode) materials for lithium-ion batteries (LIBs), with nominal composition 0.6(Li1.2Mn0.56Fe0.08Ni0.16O2) 0.4(LiFe0.2Mn1.4Ni0.4O4) which can otherwise be written as Li0.8Mn0.64Ni0.183Fe0.091O2 (FeSL) are synthesized via simple citric acid-assisted sol-gel route. Four different final annealing temperatures (550 °C, 650 °C, 750 °C, and 850 °C) were chosen to investigate their influence on electrochemical performance. The obtained composite materials contain spinel (space group Fd3¯m) as well as Li-rich layered phases (space group C2/m) as revealed by X-ray diffraction (XRD), HRTEM and cyclic voltammetry investigations. The excellent electrochemical performance of the composite material could be attributed to the structural stability achieved by the integration of spinel and layered components. Selected synthesized composite materials exhibit high discharge capacities close to 200 mAh g−1. The FeSL750 shows better capacity retention (92(3)% at the 50th cycle and 82(5)% at the 70th cycle) and rate capability than the FeSL550 and FeSL650 samples. However, the FeSL850 sample shows different charge-discharge behaviour. The charge capacity corresponding to FeSL850 is found to increase up to the 20th cycle, then stabilizes and displays a capacity retention of almost 100 % at the 50th cycle and 91(1)% at the 70th cycle. The electrochemical mechanism of FeSL750 was elucidated via in operando XAS investigations, which reveal electrochemical activity from all transition metals.

Sb-anchoring single-crystal engineering enables ultra-high-Ni layered oxides with high-voltage tolerance and long-cycle stability

Ni-rich layered oxides are promising cathodes for Li-ion batteries, but the inherent structural defects result in severe surface/bulk degradation during long cycling, especially at high cutoff voltage. Herein we propose a Sb-anchoring single-crystalline engineering to enhance the microstructural and electrochemical stability of ultra-high-Ni layered oxides, where the surface-enriched Sb doping inhibits Li-Ni mixing, suppressing the undesired layered to mixed/rock-salt phase transformation; the bulk-doped Sb rivets into Ni sites, reinforcing the bulk phase stability; the single-crystal endows enhanced crack resistance and reduced surface area, preventing surface parasitic reactions and the subsequent proliferation of cathode electrolyte interfaces. In-situ XRD reveals an essential correlation between cycle stability and phase reversibility, whereas Sb doping into both surface and bulk structures showcases a continuous anchoring effect, largely enhancing the phase transformation reversibility. DFT calculations prove a high oxidation tolerance, as Ni2+ diffusion barrier is higher than the pure cathode. A representative Li(Ni0.9Co0.05Mn0.05)0.99Sb0.01O2 cathode exhibits a high-voltage up to 4.6V, and a Li(Ni0.9Co0.05Mn0.05)0.99Sb0.01O2//graphite full-cell demonstrates an ultra-high capacity retention of 93.4% after 1000 cycles at 1C in 3.0−4.2V. This simple and efficient cathode engineering will promote the promising application of Ni-rich layered oxides in high-energy Li-ion batteries.

Unravelling the O-doping effect on chemical/electrochemical stability of Li5.5PS4.5Cl1.5 for all-solid-state lithium batteries

Chlorine-rich Li-argyrodite sulfide solid electrolytes Li5.5PS4.5Cl1.5 are applied in all-solid-state batteries (ASSBs) due to the promising ionic transport and structural stability. However, the poor air/moisture stability and incompatibility to Li metal impede their practical applications. Herein, we synthesized a Li5.5PS4.5Cl1.5-based argyrodite exhibiting improved moisture stability and electrochemical performance to metallic Li, as well as high-voltage cathodes through O doping. The prepared oxygen-doped Li5.5PS4.5Cl1.5 samples (Li5.5PS4.425O0.075Cl1.5) possess significantly enhanced air stability and lower migration barrier in comparison with pristine Li5.5PS4.5Cl1.5. Moreover, Li5.5PS4.425O0.075Cl1.5 exhibits lower polarization voltage and better compatibility with lithium metal in the constant current charge-discharge tests of Li-Li symmetrical cell. This is attributed to the Cl-O coexistence coating interface that observed in the interface of Li/Li5.5PS4.425O0.075Cl1.5. To fully leverage the ultrafast ionic conductivity of Li5.5PS4.5Cl1.5, we construct ASSBs using optimized Li5.5PS4.425O0.075Cl1.5 as buffer layer between pristine LiNi0.6Mn0.2Co0.2O2 cathode materials and Li5.5PS4.5Cl1.5, leading to higher discharge capacities and elevated capacity retention. Based on above results, we further introduce LiNbO3-coated LiCoO2 as cathode, combined with Li5.5PS4.425O0.075Cl1.5 as an isolating layer between Li anode and Li5.5PS4.5Cl1.5 to suppress the growth of Li dendrite and achieve superior cyclability at wide voltage windows. Consequently, the all-solid-state lithium batteries exhibit promising application in a wide temperature range. This work provides a compelling strategy for achieving improved Chlorine-rich Li-argyrodite solid electrolytes with excellent air stability, high ionic conductivity and Li dendrite suppression capability, hence enabling all-solid-state batteries with high energy density and superior cyclability.

A modified separator based on ternary mixed-oxide for stable lithium metal batteries

Li metal batteries (LMBs) are among the most promising options for next-generation secondary batteries under the rapidly growing demand for high-energy–density electrochemical energy storage. However, the implementation of LMBs are hindered by major obstacles such as dentritic Li deposition and low cycling Coulombic efficiency. A practical functional separator is developed in this study, which consists of a Lewis acidic mixed oxide of ZrO2-SiO2-Al2O3 as a functional coating with anion anchoring ability to modulate ion transport in the vicinity of the Li metal anode, delivering a high Li+ transference number of 0.88 in carbonate electrolytes that suppresses dendrite formation. The strong Lewis acid sites in ZrO2-SiO2-Al2O3 originate from coordinatively unsaturated Zr4+ ions, which immobilize anions and reduce their decomposition rate. This significantly improves the chemical stability of the electrolyte and induces a more stable solid electrolyte interphase layer. The modified separator enables an anode-free cell containing a high-loading LiNi0.8Co0.1Mn0.1O2 cathode to present stable charge and discharge cycling for 150 cycles at 0.5C. By effectively suppressing Li dendrite growth and supporting the long-term operation of anode-free LMBs, this study offers a novel approach to rationally design mixed oxides with high Lewis acidity for functional separators.

Isocyanurate‐Derivative Enables Highly Compatible Poly‐Dioxane Electrolyte for Dendrite‐Free Li Metal Batteries

AbstractThe Li+ transport kinetics and electrochemical stability of advanced solid‐state Li metal batteries (SLMBs) are seriously limited by the actual electrolyte compositions. Here, a novel polyether‐based electrolyte (PTGDOX) is presented through in situ co‐polymerization by integrating 1,3‐dioxane with a multifunctional 1,3,5‐triglycidyl isocyanurate additive. The isocyanurate group in PTGDOX not only provides abundant coordinating sites for Li+ transfer and restricts the movement of anions, but also prompts a beneficial inorganic‐rich solid electrolyte interface on the Li electrode. As a result, PTGDOX exhibits a remarkably increased ionic conductivity of 0.48 mS cm−1 at 30 °C and a reasonable Li‐ion transference number of 0.68, enabling the Li||Li symmetric cells to stably cycle for over 2000 h at 1 mAh cm−2. Meanwhile, the assembled Li||LiFePO4 exhibit a 97.4% capacity retention after 700 cycles at 3 C with excellent thermal stability. Moreover, PTGDOX also demonstrates excellent interfacial compatibility with high‐voltage LiNi0.8Co0.1Mn0.1O2 cathode. As such, this work provides a facile and accessible strategy for designing interface‐stable polymer electrolytes and achieving practical dendrite‐free SLMBs.

Inorganic-Enriched Solid Electrolyte Interphases: A Key to Enhance Sodium-Ion Battery Cycle Stability?

The characteristics of solid electrolyte interphase (SEI) at both the cathode and anode interfaces are crucial for the performance of sodium-ion batteries (SIBs). The research demonstrates the merits of a balanced organic component, specifically the organic sodium alkyl sulfonate (ROSO2Na) featured in this work, in conjunction with the inorganic sodium fluoride (NaF), to enhance the interfacial stability. Using a customized electrolyte, it has optimized the interphase, curbing excess NaF production, and created a thin and uniform NaF/ROSO2Na-rich SEI layer. It offers exceptional protection against interface deterioration, transition metal dissolution, and concurrently ensures a consistent reduction in interfacial impedance. This creative approach results in a substantial improvement in the performance of both the Na0.9Ni0.4Fe0.2Mn0.4O2 cathode and the hard carbon anode. The cathode demonstrates remarkable average Coulombic efficiency exceeding 99.9% and a capacity retention of 81% after 500 cycles. Furthermore, the Ah-level pouch cell has shown outstanding performance with an 87% capacity retention after 400 cycles. Moving beyond the prevailing focus on inorganic-rich SEI, these results highlight the effectiveness of the customized organic-inorganic hybrid SEI formulation in improving SIB technology, offering an adaptable solution that ensures superior interfacial stability.

Engineering the solvent-anion interactions of LiTFSI-based dual-salt electrolytes to sustain high-performance NCM622 cathodes

Electrolytes play a vital role in determining the performances of lithium-ion batteries (LIBs), especially the high-voltage LiNi0.6Co0.2Mn0.2O2 (NCM622) cathode in LiTFSI-based electrolytes. Herein, we report a high-capacity and stable NCM622 cathode that can be realized in LiTFSI-based (named T) carbonate electrolytes by tuning the intermolecular interactions using the added LiDFOB (named D). In the 1 M dual-salt electrolyte, the cathode failure and Al corrosion are suppressed in the 4.5 V-NCM622||Li batteries, because a uniform interfacial layer and weaker Li+-solvent interactions are built to inhibit the parasitic reactions. As a result, the capacity retention reaches 94.68% after 200 cycles and the 10 C-rate capacity is about 160 mA h g-1 in the 1 M T + D dual-salt electrolyte. Unlike the commonly used electrolyte, the FEC additive increases the de-solvation barrier and disturbs the cycle stability in (T + D) dual-salt systems. Density functional theory (DFT) calculation and nuclear magnetic resonance (NMR) spectra reveal that the additive FEC changes the solvent-solvent and solvent-anion interactions in the presence of T + D, which weakens the electrolyte-cathode compatibility. This work indicates that regulating the solvation structure and interfacial chemistry from solvent-solvent/anion interactions is promising for designing high-performance LIBs by using dual‐salt electrolytes.

A New Class of Oxyhalide Solid Electrolytes NaNbCl6-2xOx for Solid-state Sodium Batteries.

Sodium-based batteries are gaining momentum due to the abundance and lower cost of sodium compared to lithium. Solid-state sodium batteries can also provide further safety advantages. However, sodium-based solid-state electrolytes (SSEs) that meet all the rigorous requirements, such as high ionic conductivity, oxidative stability with the cathode, and ease of processability, are lacking. We present here a new class of sodium-based oxyhalide electrolytes NaNbCl6-2xOx with a facile mechanochemical synthesis. The oxyhalide NaNbCl4O exhibits close to two orders of magnitude higher ambient-temperature sodium-ion conductivity (1.03 x 10-4 S cm-1) compared to the halide counterpart NaNbCl6 (3 x 10-6 S cm-1). Structural motifs unique to the oxygen content in NaNbCl6-2xOx are identified with 23Na and 93Nb magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy and x-ray diffraction (XRD). Solid-state sodium batteries assembled with NaNbCl4O electrolyte and the cobalt- and nickel-free layered Na0.70Fe0.3Mn0.65Al0.05O2 cathode exhibit a maximum discharge capacity of 155 mA h g-1 with good cycle life at ambient temperature.

Reviving Spent NCM Cathodes via Spontaneous Galvanic Corrosion in Ambient Atmospheric Condition

AbstractThe recycling of end‐of‐life Li‐ion batteries (EoL LIBs) is critical for maintaining the sustainable LIB industry. In this study, the compositional restoration method for degraded LiΔNi0.6Co0.2Mn0.2O2 cathode via spontaneous galvanic corrosion, which can be conducted at room temperature, is demonstrated. Achieving the lithiation of spent LiΔNi0.6Co0.2Mn0.2O2 to its pristine state at room temperature requires a strong reducing agent with a redox potential lower than 1.6 V (vs Li/Li+), which is very reactive and expensive. In the designed restoration system, spontaneous restoration can be achieved by using an Aluminum (Al) current collector as a reducing agent which has sufficient reducing power (Al/Al3+, 1.37 V (vs Li/Li+)). Moreover, through a galvanic reaction design that utilizes Li‐ion in the electrolyte of spent LIBs, the additional Li source required to replenish the Li‐deficient NCM is minimized. The galvanic corrosion‐based restoration mechanism is systematically analyzed, and a spent Li0.76Ni0.6Co0.2Mn0.2O2 is successfully restored to its pristine state (Li1.05Ni0.6Co0.2Mn0.2O2). Furthermore, restoration strategies accomplishable in not only the cathode state but also the battery state are presented to ensure applicability in practical recycling processes. The proposed strategy suggests a new insight into the direct cathode recycling technology, possessing economic feasibility, and environmental friendliness.

Comparative environmental and economic assessment of emerging hydrometallurgical recycling technologies for Li-ion battery cathodes

The growing demand for electric vehicles has led to a growing concern for battery recycling, particularly for critical raw materials. However, there is insufficient investigation into the environmental and economic impacts of hydrometallurgical recycling methods. In this study we explored emerging hydrometallurgical technologies in economic and environmental perspective to establish conceptual routes to recover Co, Ni and Mn oxides from waste LiNi0.33Mn0.33Co0.33O2 cathode materials from spent Li-ion batteries. After, life cycle assessment and costing techniques were utilized to compare the environmental and economical performances of each conceptual route. Recovery efficiency of metal oxides through each route was also considered as a key factor. Results suggested that deep eutectic solvent-based leaching produces the highest impact under many impact categories while electrolysis-based leaching showed the least. Under purification technologies assessed, ion-exchange based purification showed significantly lower impact under many categories except stratospheric ozone depletion. Solvent based purification has been identified as the worst technology for purification. Hydroxide based calcination has been identified as the most environmentally sustainable calcination method compared to oxalate calcination. The route consists with inorganic leaching, ion-exchange based purification and hydroxide calcination showed the lowest environmental impact (emission effect at 33.8 kg CO2 eq), with lower economic impact ($ 119) and the highest recovery efficiency (78 %) per 1 kg of cathode active materials. However, using electrolysis-based leaching can slightly increase the impacts with lower recovery efficiency (75 %) and better economic performance ($104/kg of cathode active materials). Terrestrial ecotoxicity was identified to be the most affected impact category for the recovery processes. It is recommended that technologies like deep eutectic solvent-based leaching, solvent extraction and environmentally sustainable technologies like supercritical fluid extraction need further studies prior to industrial applications.

Molecular Design of Solid Polymer Electrolytes with Enthalpy-Entropy Manipulation for Li Metal Batteries with Aggressive Cathode Chemistry.

Solid polymer electrolytes (SPEs) with high ion conductivity, high Li+ transference number, and a wide electrochemical window are promising for the next-generation high-energy Li metal batteries (LMBs). Here we describe an enthalpy-entropy manipulation strategy enabling a class of polycarbonate-based copolymeric electrolytes (PCCEs) with regulated cation/anion solvation via a molecular design of the polymer backbone. By integrating a weakly solvating linear carbonate with another strongly solvating cyclic carbonate segment in the polymer backbone, the cation-dipole coordination for Li+ ions (with two types of carbonyl groups) is weakened (low enthalpy penalty) and nondirectional (high entropy penalty), which enables a weak solvation and rapid diffusion of Li+. We further introduce a bis-acrylamide-based cross-linking segment which, other than imparting high mechanical strength, exhibits dihydrogen bonding with the difluoro(oxalate) borate anions, which is strong (high enthalpy penalty) and directional (low entropy penalty), thus restricting the migration of anions. As a result, the PCCE delivers a high ionic conductivity of 0.66 mS cm-1 with a high Li+ transference number (0.76) at 25 °C, as well as high oxidation stability. By an in situ polymerization approach, the PCCE enables LMBs using high-nikel LiNi0.8Co0.1Mn0.1O2 cathodes with a high capacity retention of 82.2% over 800 cycles with a cutoff voltage of 4.5 V and further LMBs using aggressive LiNi0.5Mn1.5O4 cathodes with a 96.4% capacity retention over 300 cycles with a cutoff voltage of 5.0 V. The described enthalpy-entropy manipulation approach offers a unique perspective for the molecular design of high-performance SPEs for high-energy Li metal batteries.

Realizing the single-crystalline LiNi0.90Mn0.05Co0.05O2 cathode with long-life and high-safety property driven by polysiloxane covering and PO43− doping

As a promising cathode for lithium-ion batteries, the ultra-high nickel content layered oxide LiNi0.90Co0.05Mn0.05O2 demonstrates the great attention for the high discharging capacity. However, the serious capacity attenuation resulted from the instable interface, crystal structure degeneration and strong side-reactions on cathode-electrolyte interphase with charging-discharging drastically restricts its extensive application. To alleviate the intrinsic drawbacks, the combination improvement strategy for polysiloxane covering and PO43− doping is adopted to lower the surface residual alkali amounts, defend the HF/F− attacking and enhance the cation location order of LiNi0.90Co0.05Mn0.05O2. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) are used to evaluate the synthesized samples. The cathodes after the polysiloxane covering and PO43− doping deliver the improved crystal structure, larger lattice parameters and superior electrochemical properties. The polysiloxane coated and PO43− doped sample exhibits a high discharging capacity of 147.5 mAh g−1 at 10.0C rate and 155.4 mAh g−1 at −30 °C, remains a capacity of 193.2 mAh g−1 at 1.0C after 300 cycles with a retention of 91.2 %. Besides, when applied in pouch full batteries, it could pass the rigorous safety tests of Bar impact, Overcharging test and Nail penetration successfully, and still maintain the superior cycling stability in practice application.

Enhanced Structural and Electrochemical Performance of LiNi0.5Mn1.5O4 Cathode Material by PO43−/Fe3+ Co-Doping

Enhanced Structural and Electrochemical Performance of LiNi0.5Mn1.5O4 Cathode Material by PO43−/Fe3+ Co-Doping

Enhanced Cycling Performance of Spinel LiNi0.5Mn1.5O4 Cathodes through Mg-Mn Hetero-Valent Doping via Microwave Sol-Gel Method.

As a high energy density cathode material, further development of high working voltage spinel LiNi0.5Mn1.5O4 has hindered by its rapid capacity degradation. To address this, a hetero-valent substitution of magnesium for manganese was used to synthesize spinel LiNi0.5MgxMn1.5-xO4 (x = 0, 0.03, 0.05) via a microwave sol-gel method. XRD and refined results indicate that such strategy leads to the modification of the 16c interstitial sites. The electrical performance demonstrates that a modest substitution (x = 0.03) significantly improves both rate performance (113.1 mAh/g, charge and discharge at 5 C) and cycling stability (85% capacity retention after 500 cycles at 1 C). A higher substitution level (x = 0.05) markedly improves high-rate cycling performance, achieving 96% capacity retention after 500 cycles at 5 C. It offers tailored solutions for various application needs, including capacity-focused and high-current-rate applications. Furthermore, the stable LiNi0.5Mg0.05Mn1.45O4 sample could also serve as an effective coating layer for other electrode materials to enhance their cycling stability.

Ca/Li Synergetic-Doped Na0.67Ni0.33Mn0.67O2 to Realize P2-O2 Phase Transition Suppression for High-Performance Sodium-Ion Batteries.

P2-type layered transition metal oxide Na0.67Ni0.33Mn0.67O2 is considered as a promising cathode for advanced sodium-ion batteries due to its high theoretical specific capacity. However, the P2-type cathode suffers severe P2-O2 phase transition during cycling process, resulting unsatisfactory cyclic stability and rate capability. Herein, a Ca/Li co-doped P2-type Na0.62Ca0.05Ni0.33Mn0.57Li0.10O2 (NCNMLO) cathode material was synthesized through a simple sol-gel method. With the synergistic effect of Ca-doping at Na sites and Li substitution at transition metal (TM) sites, the cathode achieves an excellent electrochemical performance due to the inhibited P2-O2 phase transition and improved ion diffusion with Na+/vacancy disordering arrangement. The NCNMLO cathode exhibits a good cyclic stability with 70.8% of capacity retention at 1 C after 200 cycles and excellent rate capability with 40.1 mAh g-1 at 20 C. The dual sites doping strategy provides an effective and simple approach for designing high-performance layered oxide cathode materials for sodium-ion batteries.

Effects of Li1.3Al0.3Ti1.7(PO4)3 solid-state electrolytes on the safety of hybrid solid–liquid batteries

Hybrid solid–liquid batteries (HSLBs) are emerging as promising solutions to address the safety issues of lithium-ion batteries. However, the effects of solid-state electrolytes (SSEs) on battery safety remain unclear, hindering the large-scale application of HSLBs. This paper presents a comprehensive investigation on the safety performance of HSLBs with different amounts of nano-sized Li1.3Al0.3Ti1.7(PO4)3 (LATP) SSEs in the LiNi0.9Co0.05Mn0.05O2 cathode under thermal, electrical, and mechanical abuse conditions. The HSLBs with LATP SSEs exhibit significantly enhanced tolerance to overcharge, as the battery with 5 wt% LATP does not go into thermal runaway throughout the whole overcharge process. In-depth characterizations reveal that the LATP additives experience electrochemical delithiation during overcharge and generate a protective coating layer on the cathode surface, thus effectively mitigating the cathode structural changes and cathode-electrolyte interfacial reactions. Benefiting from the coating layer, the HSLBs with LATP SSEs also exhibit reduced temperature rise rate and retarded thermal runaway during the accelerating rate calorimetry and oven tests, as well as enhanced rate performance and cycling stability. Finally, the safety, electrochemical performance, and cost of HSLBs and conventional LIBs are comprehensively compared through a radar graph, aiming to provide guidance for the rational design of high–energy density and high-safety batteries.

The effect of heating rate on microstructure and electrochemical performance of nickel-rich layered oxides cathode materials

Nickel-rich layered oxides have attracted significant attention as promising cathode materials for lithium-ion batteries due to their high specific capacity, rate capability, and relatively low cost. However, the material still faces challenges such as harsh synthesis conditions, easy cation mixing and large residual alkali on the surface, severely limiting its practical applications. To overcome these drawbacks, this study successfully synthesized a series of LiNi0.8Co0.1Mn0.1O2 (NCM) cathode materials with different heating rates. The results indicate that appropriately reducing the heating rate can improve the cycling performance of the material and reduce cation mixing and surface residual alkalinity. Specifically, among the four samples, the LiNi0.8Co0.1Mn0.1O2 sample (NCM-2 °C min-1) exhibites a lower Li⁺/Ni²⁺ mixed arrangement and fewer surface residual alkalis, demonstrating good cycling performance and rate capability. The NCM-2 °C min-1 sample provides an excellent initial discharge capacity of 210.4 mAh g⁻¹ under 0.1 C conditions, and it achieves the highest capacity retention rate (85.9%) after 100 cycles at 1 C, while the capacity retention rates for NCM-1 °C min-1, NCM-3 °C min-1, and NCM-4 °C min-1 are 75.4%, 75.2%, and 71.2%, respectively. NCM-2 °C min-1 sample also showed excellent rate performance, especially at high rates. The discharge capacity remains at 151.6 mAh g-1 at 10 C, which is much higher than that of other samples (149.3 mAh g-1 for NCM-1 °C min-1, 123.5 mAh g-1 for NCM-3 °C min-1, and 120.6 mAh g-1 for NCM-4 °C min-1). The research of synthesis technology has important guiding significance for the synthesis of high-stability high-nickel layered oxide materials.