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.     

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.     

Novel electrospun polymer electrolytes incorporated with Keggin‐type hetero polyoxometalate fillers as solvent‐free electrolytes for lithium ion batteries

In this study, solvent‐free nanofibrous electrolytes were fabricated through an electrospinning method. Polyethylene oxide (PEO), lithium perchlorate and ethylene carbonate were used as polymer matrix, salt and plasticizer respectively in the electrolyte structures. Keggin‐type hetero polyoxometalate (Cu‐POM@Ru‐rGO, Ni‐POM@Ru‐rGO and Co‐POM@Ru‐rGO (POM, polyoxometalate; rGO, reduced graphene oxide)) nanoparticles were synthesized and inserted into the PEO‐based nanofibrous electrolytes. TEM and SEM analyses were carried out for further evaluation of the synthesized filler structures and the electrospun nanofibre morphologies. The fractions of free ions and crystalline phases of the as‐spun electrolytes were estimated by obtaining Fourier transform infrared and XRD spectra, respectively. The results showed a significant improvement in the ionic conductivity of the nanofibrous electrolytes by increasing filler concentrations. The highest ionic conductivity of 0.28 mS cm^?1 was obtained by the introduction of 0.49 wt% Co‐POM@Ru‐rGO into the electrospun electrolyte at ambient temperature. Compared with solution‐cast polymeric electrolytes, the electrospun electrolytes present superior ionic conductivity. Moreover, the cycle stability of the as‐spun electrolytes was clearly improved by the addition of fillers. Furthermore, the mechanical strength was enhanced with the insertion of 0.07 wt% fillers to the electrospun electrolytes. The results implied that the prepared nanofibres are good candidates as solvent‐free electrolytes for lithium ion batteries. © 2020 Society of Chemical Industry     

Performance of LiNi1/3Co1/3Mn1/3O2 prepared from spent lithium-ion batteries by a carbonate co-precipitation method

Spherical LiNi_1/3Co_1/3Mn_1/3O₂ cathode particles were resynthesized by a carbonate co-precipitation method using spent lithium-ion batteries (LIBs) as a raw material. The physical characteristics of the Ni_1/3Co_1/3Mn_1/3CO₃ precursor, the (Ni_1/3Co_1/3Mn_1/3)₃O₄ intermediate, and the regenerated LiNi_1/3Co_1/3Mn_1/3O₂ cathode material were investigated by laser particle-size analysis, scanning electron microscopy–energy-dispersive spectroscopy (SEM-EDS), thermogravimetry–differential scanning calorimetry (TG-DSC), X-ray diffraction (XRD), inductively coupled plasma–atomic emission spectroscopy (ICP-AES), and X-ray photoelectron spectroscopy (XPS). The electrochemical performance of the regenerated LiNi_1/3Co_1/3Mn_1/3O₂ was studied by continuous charge–discharge cycling and cyclic voltammetry. The results indicate that the regenerated Ni_1/3Co_1/3Mn_1/3CO₃ precursor comprises uniform spherical particles with a narrow particle-size distribution. The regenerated LiNi_1/3Co_1/3Mn_1/3O₂ comprises spherical particles similar to those of the Ni_1/3Co_1/3Mn_1/3CO₃ precursor, but with a narrower particle-size distribution. Moreover, it has a well-ordered layered structure and a low degree of cation mixing. The regenerated LiNi_1/3Co_1/3Mn_1/3O₂ shows an initial discharge capacity of 163.5 mA h g^?1 at 0.1 C, between 2.7 and 4.3 V; the discharge capacity at 1 C is 135.1 mA h g^?1, and the capacity retention ratio is 94.1% after 50 cycles. Even at the high rate of 5 C, LiNi_1/3Co_1/3Mn_1/3O₂ delivers the high capacity of 112.6 mA h g^?1. These results demonstrate that the electrochemical performance of the regenerated LiNi_1/3Co_1/3Mn_1/3O₂ is comparable to that of a cathode synthesized from fresh materials by carbonate co-precipitation.     

Residual learning rates in lead-acid batteries: Effects on emerging technologies

The low price of lead-acid, the most popular battery, is often used in setting cost targets for emerging energy storage technologies. Future cost reductions in lead acid batteries could increase investment and time scales needed for emerging storage technologies to reach cost-parity. In this paper the first documented model of cost reductions for lead-acid batteries is developed. Regression to a standard experience curve using 1989–2012 data yield a poor fit, with R² values of 0.17 for small batteries and 0.05 for larger systems. To address this problem, battery costs are separated into material and residual costs, and experience curves developed for residual costs. Depending on the year, residual costs account for 41–86% of total battery cost. Using running-time averages to address volatility in material costs, a 4-year time average experience curve for residual costs yield much higher R², 0.78 for small and 0.74 for large lead-acid batteries. The learning rate for residual costs in lead-acid batteries is 20%, a discovery with policy implications. Neglecting to consider cost reductions in lead-acid batteries could result in failure of energy storage start-ups and public policy programs. Generalizing this result, learning in incumbent technologies must be understood to assess the potential of emerging ones.