Electrochemical performance of spherical Li-rich LMNCO cathode materials prepared using a two-step spray-drying method

In this study we synthesized Li-rich Li_1.2Ni_0.13Mn_0.54Co_0.13O₂ (LMNCO) as a composite cathode material through a two-step spray-drying method, using transition metal (TM) acetates and citric acid (CA, as a chelating agent) at various molar ratios and then calcining at various temperatures for various periods of time. This two-step spray-drying method created hierarchical nano/micro-sphere structures of the LMNCO cathode material. The LMNCO cathode exhibited the best electrochemical performance when synthesized with a TM:CA ratio of 3:2, a calcination temperature of 900 °C, and a calcination time of 5 h. This as-prepared LMNCO composite was then modified with polyimide (PI) at various weight ratios (PI/LMNCO = 0.5, 1.0, and 1.5 wt%) to improve its electrochemical properties. Among the various structures, the LMNCO cathode material coated with 1.0 wt% of PI at a layer thickness of approximately 1.88 nm achieved the best initial discharge capacities. This modified electrode also displayed enhanced cycle stability, with over 93.3 and 87.9% of the capacity retained after 30 cycles at 0.1C and 100 cycles at 1C, respectively. In comparison, the capacity retention of the unmodified LMNCO electrode measured under the same conditions was no more than 91.3% at 0.1C and 70.1% at 1C. Thus, surface modification with PI was an effective method for improving the coulombic efficiency, discharge capacity, and long-term cycling performance of the LMNCO cathode. Such PI-coated LMNCO composite cathode materials appear to be potential candidates for use in next-generation high-performance lithium-ion batteries.     

Inducing lattice defects in calcium ferrite anode materials for improved electrochemical performance in lithium-ion batteries

Enhancing the electrical conductivity of electrode materials via a cationic substitution strategy was recognized as an effective way of improving the electrochemical performance of Li-ion batteries. Thus, Li_xCa_1-xFe₂O₄ nanoparticles were synthesized via a facile inexpensive process at low temperature. XRD peaks refer to the formation of an orthorhombic structure with the Pnma space group. HR-TEM investigations reveal orthorhombic-like shape for pure CaFe₂O₄, nanoplatelet-like morphology for Li_0.05Ca_0.95Fe₂O₄ and irregular distorted crystals for Li_0.1Ca_0.9Fe₂O₄. Voids and pores in Li-doped CaFe₂O₄ were confirmed by FESEM and BET measurements. XPS spectra of O1s prove that Li-doped CaFe₂O₄ have higher conductivity due to the created lattice defects and oxygen species. Li-doped CaFe₂O₄ anodes exhibit great improvement in their initial discharge capacities ～1219 and 1606 mAhg^?1 upon substitution of Ca with 5% and 10% Li, respectively. Furthermore, 10% Li-doped CaFe₂O₄ anode displays the highest Li-ions diffusion coefficient and exchange current density due to the enhanced Li⁺ ions mobility. Moreover, the DC activation energies for the Li_xCa_1-xFe₂O₄ nanoparticles decreased with increasing Li content.     

Porous nitrogen-enriched hollow carbon nanofibers as freestanding electrode for enhanced lithium storage

One-dimensional porous carbons bearing high surface areas and sufficient heteroatom doped functional-ities are essential for advanced electrochemical energy storage devices, especially for developing free-standing film electrodes. Here we develop a porous, nitrogen-enriched, freestanding hollow carbon nanofiber (PN-FHCF) electrode material via filtration of polypyrrole (PPy) hollow nanofibers formed by in situ self-degraded template-assisted strategy, followed by NH3-assisted carbonization. The PN-FHCF retains the freestanding film morphology that is composed of three-dimensional networks from the entanglement of 1D nanofiber and delivers 3.7-fold increase in specific surface area (592 m2·g-1) com-pared to the carbon without NH3 treatment (FHCF). In spite of the enhanced specific surface area, PN-FHCF still exhibits comparable high content of surface N functionalities (8.8％, atom fraction) to FHCF. Such developed hierarchical porous structure without sacrificing N doping functionalities together enables the achievement of high capacity, high-rate property and good cycling stability when applied as self-supporting anode in lithium-ion batteries, superior to those of FHCF without NH3 treatment.     

Li0.95Na0.05MnPO4/C nanoparticles compounded with reduced graphene oxide sheets for superior lithium ion battery cathode performance

Sodium-substituted LiMnPO₄/C/reduced graphene oxide (LNMP@rGO) was synthesized in this study via freeze drying and carbon thermal reduction method with graphene oxide as carbon source. Sodium ion doping is optimized and rGO effects are evaluated by XRD, SEM, TEM, BET, Raman, and electrochemical performance measurements. Well-distributed nanoparticles with average size of ~50?nm are evenly distributed on the surface or intercalation between rGO layers, resulting in a porous ion/electronic conductive network. Compared to 122.3?mA?h?g^?1 in unmodified LNMP, the best LNMP@rGO (20?mg rGO) exhibits an excellent initial discharge capacity of 150.4?mA?h?g^?1 at 0.05?C at 122.9% of the initial capacity. The capacity retention rate is 95.8% of the initial capacity after 100 cycles at 1?C. Capacity of 101.2?mA?h?g^?1 is preserved even at rates as high as 10?C.     

Synergistic effect of bulk phase doping and layered-spinel structure formation on improving electrochemical performance of Li-Rich cathode material

In this study, La was doped into the lithium layer of Li-rich cathode material and formed a layered-spinel hetero-structure. The morphology, crystal structure, element valence and kinetics of lithium ion migration were studied by field emission scanning electron microscope (FESEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). The La doped lithium-rich cathode material exhibited similar initial discharge capacity of 262.8 mAh g^?1 at 0.1 C compared with the undoped material, but the discharge capacity retention rate can be obviously improved to 90% after 50 cycles at 1.0 C. Besides that, much better rate capability and Li⁺ diffusion coefficient were observed. The results revealed that La doping not only stabilized the material structure and reduced the Li/Ni mixing degree, but also induced the generation of spinel phase to provide three-dimensional diffusion channels for lithium ion migration. Moreover, the porous structure of the doped samples also contributed to the remarkable excellent electrochemical performance. All of these factors combined to significantly improve the electrochemical performance of the material.     

High-rate capability of carbon-coated micron-sized hexagonal TT-Nb2O5 composites for lithium-ion battery

With excellent specific capacity, superior cycle stability, safety and strong practical, Nb₂O₅ has been considered as one of the prospective anode materials for lithium-ion batteries (LIBs). However, current study suggests that Nb₂O₅ electrode materials for LIBs still face the vital issues of low electrical conductivity and poor rate performance. Therefore, carbon-coated TT-Nb₂O₅ materials are designed and synthesized through solid state method in this work, which present high specific capacity (228 mA h g^?1 at 0.2C), satisfactory rate properties (107 mA h g^?1 at 20 C). The outstanding electrochemical property can not only give the credit to the pseudocapacitance effect of TT-Nb₂O₅, but also attribute to introduction of carbon. The homogeneous carbon-coated materials enhance the electrical conductivity, increase the electron transmission speed and alleviate particle crushing. This research not only offers a new method for preparing excellent electrode materials, but also provides a kind of excellent anode material with prospective application for LIBs.     

Review of lithium-ion battery state of charge estimation

The technology deployed for lithium-ion battery state of charge (SOC) estimation is an important part of the design of electric vehicle battery management systems. Accurate SOC estimation can forestall excessive charging and discharging of lithium-ion batteries, thereby improving discharge efficiency and extending cycle life. In this study, the key lithium-ion battery SOC estimation technologies are summarized. First, the research status of lithium-ion battery modeling is introduced. Second, the main technologies and difficulties in model parameter identification for lithium-ion batteries are discussed. Third, the development status and advantages and disadvantages of SOC estimation methods are summarized. Finally, the current research problems and prospects for development trends are summarized.     

Passive fuel cell/lithium-ion capacitor hybridization for vehicular applications

Electric recreational vehicles represent a new challenge in terms of power supply systems compared to the current light-duty electric vehicles, which achieve high performance and long-range. The recreational vehicles need to heed the limited dimension requirements while assuring the high requested power. This paper proposes an integration of Lithium-Ion Capacitor (LIC) with Fuel Cell (FC) without any power electronic device for a three-wheel electric motorcycle. Unlike other hybrid power supply systems, the proposed FC-LIC passive configuration is lighter, compact, more efficient, and simpler to implement. Due to the different impedance of the components the system is self-management, in which FC supplies the average power component and LIC operates as a low-pass filter. In this respect, a simulator is built based on experimental tests to study the system performance in terms of hydrogen consumption and FC degradation. Subsequently, the system is tested under three standard motorcycle driving cycles at three different FC system lifespan stages. The obtained results demonstrate that a passive topology can supply the requested power along different FC stages of life and reported just an increment of 12% of hydrogen consumption at the oldest condition compared to the new condition.     

New titanium (III) phosphite structure and its application as anode for lithium ion batteries

A new titanium (III) phosphite Ti₂(HPO₃)₃, has been synthesized under hydrothermal conditions. The solid-state structure of this material was solved using single-crystal X-ray diffraction. The anionic inorganic skeleton has a three-dimensional structure, which is built up by TiO₆ octahedral units linked together via bridging HPO₃ pseudo pyramids, giving rise to tunnels along the three crystallographic axes. This new compound displays a high thermal stability limit of 625 °C. IR and Raman spectroscopies show the vibrational modes of the (HPO₃)²⁻oxoanions. Electrochemical activity of this phase toward reversible insertion of Li ion was studied for the first time by galvanostatic charge-discharge measurements, an insertion host for reversible accommodation of Li⁺ was observed.     

Fabrication and performances of high lithium-ion conducting solid electrolytes based on NASICON Li1.3Al0.3Ti1.7-xZrx(PO4)3 (0≤ x≤ 0.2)

Solid electrolytes are the key component in designing all-solid-state batteries. The Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) structure and its derivatives obtained by doping various elements at Ti and Al site acts as good solid electrolytes. However, there is still scope for enhancing the ionic conductivity using simple precursors and preparation methods. In this study, the Li superionic conductors Li_1.3Al_0.3Ti_1.7-xZr_x(PO₄)₃ (LATZP) with 0 ≤ x ≤ 0.2 have been successfully prepared by the solid-state reaction route. The structural, morphological, and ionic transport properties were analyzed using several experimental techniques including powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and impedance spectroscopy (IS). The presence of two relaxation processes corresponding to grain and grain boundary was studied using various formalisms. We have observed that grain effects dominate at lower temperatures (<100 °C) while the grain boundary at higher temperatures (> 200 °C) on ionic conductivity. The relaxation mechanisms of grain and grain boundaries were investigated by the Summerfield scaling of AC conductivity. The highest total ionic conductivity of 2.48 × 10^-4 S/cm at 150 °C and 5.50 × 10^-3 S/cm at 250 °C was obtained for x = 0.1 in Li_1.3Al_0.3Ti_1.6Zr_0.1(PO₄)₃ sintered at 950 °C/6 h in the air. The ionic conductivity value was found to be higher than the ionic conductivity reported for LATP prepared via solid-state reaction mechanism using the same precursors and conditions.