Interactions of Li2O volatilized from ternary lithium-ion battery cathode materials with mullite saggar materials during calcination

In recent years, the rapid development of Li(Ni_xCo_yMn_1-x-y)O₂ (LNCM) materials for application in ternary lithium-ion batteries has led to an increased demand for refractory kiln saggars in industries. However, saggars used for firing ternary Li-ion battery cathode materials are often subjected to severe corrosion and spalling. To investigate the damage mechanism of the saggar materials, non-contact corrosion experiments were designed to study the effects of the precursor additions, calcination temperature, and number of calcinations during the interaction between mullite saggar and LNCM materials. The phase composition and microstructure of the mullite saggar specimens before and after corrosion were characterized using X-ray diffraction and scanning electron microscopy, respectively, to obtain a comprehensive understanding of the causes of the deterioration of mullite saggar materials during corrosion.     

New horizon in mechanochemistry—high-temperature,high-pressure mechanical synthesis in a planetary ball mill—with magnesium hydride synthesis as an example

A new route of materials synthesis, namely, high-temperature, high-pressure reactive planetary ball milling (HTPRM), is presented. HTPRM allows for the mechanosynthesis of materials at fully controlled temperatures of up to 450 °C and pressures of up to 100 bar of hydrogen. As an example of this application, a successful synthesis of magnesium hydride is presented. The synthesis was performed at controlled temperatures (room temperature (RT), 100, 150, 200, 250, 300, and 325 °C) while milling in a planetary ball mill under hydrogen pressure ($>$50 bar). Very mild milling conditions (250 rpm) were applied for a total milling time of 2 h, and a milling vial with a relatively small diameter (φ = 53 mm, V = ～0.06 dm³) was used. The effect of different temperatures on the synthesis kinetics and outcome were examined. The particle morphology, phase composition, reaction yield, and particle size were measured and analysed by scanning electron microscopy, X-ray diffraction, differential scanning calorimetry (DSC) techniques. The obtained results showed that increasing the temperature of the process significantly improved the reaction rate, which suggested the great potential of this technique for the mechanochemical synthesis of materials.     

Boron doping induced electronic reconfiguration of Fe-Nx sites in N-doped carbon matrix for efficient oxygen reduction reaction in both alkaline and acidic media

Developing non-precious metal-based catalysts as the substitution of precious catalysts (Pt/C) in oxygen reduction reaction (ORR) is crucial for energy devices. Herein, a template and organic solvent-free method was adopted to synthesize Fe, B, and N doped nanoflake-like carbon materials (Fe/B/N–C) by pyrolysis of monoclinic ZIF-8 coated with iron precursors and boric acid. Benefiting from introducing B into Fe–N–C, the regulated electron cloud density of Fe-N_x sites enhance the charge transfer and promotes the ORR process. The as-synthesized Fe/B/N–C electrocatalyst shows excellent ORR activity of a half-wave potential (0.90 V vs 0.87 V of Pt/C), together with superior long-term stability (95.5% current density retention after 27 h) in alkaline media and is even comparable to the commercial Pt/C catalyst (with a half-wave potential of 0.74 V vs 0.82 V of Pt/C) in an acidic electrolyte. A Zn-air battery assembled with Fe/B/N–C as ORR catalyst delivers a higher open-circuit potential (1.47 V), specific capacity (759.9 mA h g^?1_Zn at 10 mA cm^?2), peak power density (62 mW cm^?2), as well as excellent durability (5 mA cm^?2 for more than 160 h) compared to those with commercial Pt/C. This work provides an effective strategy to construct B doped Fe–N–C materials as nonprecious ORR catalyst. Theoretical calculations indicate that introduction of B could induce Fe-N_x species electronic configuration and is favorable for activation of OH1 intermediates to promote ORR process.     

An active balancer with rapid bidirectional charge shuttling and adaptive equalization current control for lithium-ion battery strings

This article proposes an active balancer, which features bidirectional charge shuttling and adaptive equalization current control, to fast counterbalance the state of charge (SOC) of cells in a lithium-ion battery (LIB) string. The power circuit consists of certain bidirectional buck-boost converters to transfer energy among the different cells back and forth. Owing to the characterization of the open-circuit voltage (OCV) vs SOC in LIB being relatively smooth near the SOC middle range, the SOC-inspected balance strategy can achieve more precise and efficient equilibrium than the voltage-based control. Accordingly, a compensated OCV-based SOC estimation is put forward to take into account the discrepancy of SOC estimation. Besides, the varied-duty-cycle (VDC) and curve-fitting modulation (CFM) methods are devised herein to tackle the problems of slow equalization rate and low balance efficacy, which arise from the diminution in balancing current as the SOC difference between the cells decreases in the later duration of equalization especially. The proposed strategies have taken the battery nonlinear characteristic and circuit parameter nonideality into account and can adaptively modulate the duty cycle with the SOC difference to keep balancing current constant throughout the balancing cycle. Simulated and experimental results are given to demonstrate the feasibility and effectiveness of the same prototype constructed. Compared with the fixed duty cycle and the VDC methods, the proposed CFM has the best balancing efficiency of 81.4%, and the balance time is shortened by 27.1% and 18.6%, respectively.     

Temperature adaptability of the soluble lead flow battery using different solutions of fluoborate,perchlorate, methanesulfonate and trifluoromethanesulfonate

The evaluation of cell's weatherability is of practical interest. To further improve the soluble lead flow battery's weatherability, physiochemical properties of electrolytes containing fluoborate, perchlorate, methanesulfonate and trifluoromethanesulfonate are investigated from ?60 to 50 °C. Activities of CF₃SO₃H and HClO₄ are poor in trifluoromethanesulfonate and perchlorate solutions due to common anion effect. The solubility of lead salt can be improved by increasing temperature, but worsened by increasing acid's content. With the temperature increasing, the conductivity is enhanced, and the viscosity is lowered for four solutions. The same results have been found by increasing acid's content except for CF₃SO₃H. The high energy efficiency can be achieved for cells over ?40–0 °C using fluoborate and perchlorate solutions, 73.2% at ?40 °C and 78.1% at ?30 °C respectively. Over the temperature range of 20–50 °C, the cells with methanesulfonate and trifluoromethanesulfonate solutions have good performance, 77.4% and 73.7% at 50 °C respectively.     

Effect of hydrometallurgical process parameters on the Mn2O3 nano catalysts derived from spent batteries used in the plasma catalytic oxidation of BTX

Manganese oxide catalysts have been synthesized from the used batteries via hydrometallurgical method and effect of hydrometallurgical parameters such as the effect of acid type (H₂SO₄, HNO₃, HCl), acid concentration (0.5, 1, 1.5, 2 %v/v) and powder to acid ratio (1/50, 1/60, 1/70, 1/80) were in detail investigated. The physico-chemical properties of as-prepared catalysts were characterized by FT-IR, XRD, FESEM, EDX, BET, TEM, and TPR-H₂ analysis. The activity of as-prepared catalysts were investigated towards the oxidation of benzene, toluene, and xylene (BTX) in a plasma-catalytic process. The results show that benzene and toluene conversion were almost constant in the range of 97–98% in case of various acid types, acid concentrations and solid to liquid ratios. However, the xylene conversion were varied in case of different hydrometallurgical factors. The highest xylene conversion was obtained in the presence of MnS0.5–60, which was prepared using H₂SO₄ with concentration of 0.5%v/v and solid to liquid ratio of 1/60. The effect of the input voltage and BTX flow rate on the BTX conversion was also investigated using MnS0.5–60 catalyst in detail.     

Strain‐rate‐dependent mechanical properties of polypropylene separator for lithium‐ion batteries

The mechanical integrity of battery separators is critical for battery safety and durability. A comprehensive study of strain‐rate‐dependent tensile and puncture properties of a polypropylene lithium‐ion battery separator is presented here with a new model. Due to anisotropy of the polymeric membrane, tensile testing was conducted for different directions. Results showed that tensile strength and elastic modulus were increased 1000% and 500%, respectively, for different directions. It was also demonstrated that tensile strength changed 10 to 25% with strain rate (1.67 × 10^?4 to 1.67 × 10^?1 s^?1) for different directions. An equation was obtained for the first time for flow stress versus strain rate at varied tensile directions with respect to machine direction. Moreover, puncture testing was performed and it was shown that puncture strength was increased 140% with increasing strain rate from 0.25 to 250 mm min^?1. Two failure modes were also observed in puncture samples. Finally, Eyring's model was used to calculate activation enthalpy of the porous polypropylene separator. © 2020 Society of Chemical Industry     

Enhance cycling performance of LiMn2O4 cathode by Sr2+ and Cr3+ doping

Spinel LiSr_0·1Cr_0·1Mn_1·8O₄ was synthesised by high temperature solid state method in order to enhance the electrochemical performance. The LiSr_0·1Cr_0·1Mn_1·8O₄ (LSCMO) materials were characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical tests. The XRD and SEM studies confirm that LSCMO had spinel crystal structure with a space group of Fd3m, and the particle of LSCMO shows irregular shape. The cyclic voltammetry data illustrated that the heavy current charge–discharge performance of LMO was improved by Sr²⁺ and Cr³⁺ doping. The galvanostatic charge–discharge of LSCMO cathode materials was measured at 1, 5, 10 and 20 C. The results indicated that LSCMO improved the capacity retention.     

Polyetherimide-LaNi5 composite films for hydrogen storage applications

This study investigates the preparation of polyetherimide (PEI) – LaNi₅ composites films for hydrogen storage. Prior to the polymer addition, LaNi₅ was ball-milled at different conditions (250, 350, and 450 RPM) and annealed at 500 °C for 1 h under vacuum. The composites were produced with BM-LaNi₅-350 (PEI/LaNi₅-350) and annealed BM-LaNi₅-350 (PEI/LaNi₅-350-TT). Membranes were successfully produced through solvent casting assisted by an ultrasonic bath. The particles dispersion and the film morphology did not change after hydrogenation cycles. In the H₂ sorption experiments at 43 °C and 20 bar, the films stored H₂ without incubation time; both samples reached a capacity of ~0.6 wt%. The H₂ sorption kinetics of PEI/LaNi₅-350 was comparable to that of BM-LaNi₅-350, whereas PEI/LaNi₅-350-TT presented significantly slower kinetics. LaNi₅ oxidation was hindered by PEI, showing that it can be explored to improve metal hydrides air resistance. The results demonstrated that PEI films filled with LaNi₅ are promising materials for hydrogen storage.     

Effect of Ni/tubular g-C3N4 on hydrogen storage properties of MgH2

Additive doping is one of the effective methods to overcome the shortcomings of MgH₂ on the aspect of relatively high operating temperatures and slow desorption kinetics. In this paper, hollow g-C₃N₄ (TCN) tubes with a diameter of 2 μm are synthesized through the hydrothermal and high-temperature pyrolysis methods, and then nickel is chemically reduced onto TCN to form Ni/TCN composite at 278 K. Ni/TCN is then introduced into the MgH₂/Mg system by means of hydriding combustion and ball milling. The MgH₂–Ni/TCN composite starts to release hydrogen at 535 K, which is 116 K lower than the as-milled MgH₂ (651 K). The MgH₂–Ni/TCN composite absorbs 5.24 wt% H₂ within 3500 s at 423 K, and takes up 3.56 wt% H₂ within 3500 s, even at a temperature as low as 373 K. The apparent activation energy (E_a) of the MgH₂ decreases from 161.1 to 82.6 kJ/mol by the addition of Ni/TCN. Moreover, the MgH₂–Ni/TCN sample shows excellent cycle stability, with a dehydrogenation capacity retention rate of 98.0% after 10 cycles. The carbon material enhances sorption kinetics by dispersing and stabilizating MgH₂. Otherwise, the phase transformation between Mg₂NiH₄ and Mg₂NiH_0.3 accelerates the re/dehydrogenation reaction of the composite.