Abnormal Ionic Conductivities in Halide NaBi3 O4 Cl2 Induced by Absorbing Water and a Derived Oxhydryl Group.

In hunting for safe and cost-effective materials for post-Li-ion energy storage, the design and synthesis of high-performance solid electrolytes (SEs) for all-solid-state batteries are bottlenecks. Many issues associated with chemical stability during processing and storage and use of the SEs in ambient conditions need to be addressed. Now, the effect of water as well as oxyhdryl group (. OH) on NaBi3 O4 Cl2 are investigated by evaluating ionic conductivity. The presence of water and . OH results in an increase in ionic conductivity of NaBi3 O4 Cl2 owing to diffusion of H2 O into NaBi3 O4 Cl2 , partially forming binding . OH through oxygen vacancy repairing. Ab initio calculations reveal that the electrons significantly accumulate around . OH and induce a more negative charge center, which can promote Na+ hopping. This finding is fundamental for understanding the essential role of H2 O in halide-based SEs and provides possible roles in designing water-insensitive SEs through control of defects.

Preparation of Nanocomposite Polymer Electrolyte via In Situ Synthesis of SiO2 Nanoparticles in PEO.

Composite polymer electrolytes provide an emerging solution for new battery development by replacing liquid electrolytes, which are commonly complexes of polyethylene oxide (PEO) with ceramic fillers. However, the agglomeration of fillers and weak interaction restrict their conductivities. By contrast with the prevailing methods of blending preformed ceramic fillers within the polymer matrix, here we proposed an in situ synthesis method of SiO2 nanoparticles in the PEO matrix. In this case, robust chemical interactions between SiO2 nanoparticles, lithium salt and PEO chains were induced by the in situ non-hydrolytic sol gel process. The in situ synthesized nanocomposite polymer electrolyte delivered an impressive ionic conductivity of ~1.1 × 10-4 S cm-1 at 30 °C, which is two orders of magnitude higher than that of the preformed synthesized composite polymer electrolyte. In addition, an extended electrochemical window of up to 5 V vs. Li/Li+ was achieved. The Li/nanocomposite polymer electrolyte/Li symmetric cell demonstrated a stable long-term cycling performance of over 700 h at 0.01-0.1 mA cm-2 without short circuiting. The all-solid-state battery consisting of the nanocomposite polymer electrolyte, Li metal and LiFePO4 provides a discharge capacity of 123.5 mAh g-1, a Coulombic efficiency above 99% and a good capacity retention of 70% after 100 cycles.

Exploring the Role of Manganese on Structural, Transport, and Electrochemical Properties of NASICON-Na3Fe2-yMny(PO4)3-Cathode Materials for Na-Ion Batteries.

Given the extensive efforts focused on protecting the environment, eco-friendly cathode materials are a prerequisite for the development of Na-ion battery technology. Such materials should contain abundant and inexpensive elements. In the paper, we present NASICON-Na3Fe2-yMny(PO4)3 (y = 0, 0.1, 0.2, 0.3, and 0.4) cathode materials, which meet these requirements. Na3Fe2-yMny(PO4)3 compounds were prepared via a solid-state reaction at 600 °C, which allowed to obtain powders with submicron particles. The presence of manganese in the iron sub-lattice inhibits phase transitions, which occurs at ∼95 and ∼145 °C in Na3Fe2(PO4)3, changing the monoclinic structure to rhombohedral and affecting the structural and transport properties. The chemical stability of Na3Fe2-yMny(PO4)3 was thus higher than that of Na3Fe2(PO4)3, and it also exhibited enhanced structural, transport, and electrochemical properties. The observed correlation between the chemical composition and electrochemical properties proved the ability to precisely tune the crystal structure of NASICONs, allowing cathode materials with more desirable properties to be designed.

Preparation of thin solid electrolyte by hot-pressing and diamond wire slicing.

The thickness of a solid electrolyte influences the performance of all-solid-state batteries due to increased impedance with a thick electrolyte. Thin solid electrolytes are favourable to improve the performance of all-solid-state batteries due to the short Li ion diffusion path and small volume of the solid electrolytes. Therefore, the preparation of thin solid electrolyte is one of the key process techniques for development of all-solid-state batteries. In this study, thin Li1.5Ge1.5Al0.5(PO4)3 solid electrolyte with a Na super ion conductor structure is prepared by diamond wire slicing. The Li1.5Ge1.5Al0.5(PO4)3 solid electrolyte is prepared by melt-quenching followed by crystallization at 800 °C for 8 h, after which the crystallized Li1.5Ge1.5Al0.5(PO4)3 rod is subjected to wire slicing. Thin Li1.5Ge1.5Al0.5(PO4)3 with a thickness of 200 µm is obtained. The crystal structure and cross-sectional morphology are not affected by the slicing. The total Li conductivity of the thin Li1.5Ge1.5Al0.5(PO4)3 and activation energy are 3.3 × 10-4 S cm-1 and 0.32 eV, respectively. The thickness and total conductivity are comparable to those of Li1.5Ge1.5Al0.5(PO4)3 prepared by the tape-casting method which needs several steps to prepare Li1.5Ge1.5Al0.5(PO4)3 tape-sheet and high temperature and a long sintering process. The ionic transference number of the thin Li1.5Ge1.5Al0.5(PO4)3 is 0.999. The diamond wire slicing is a useful method to prepare thin solid electrolytes.

Correlation between electronic structure, transport and electrochemical properties of a LiNi1-y-zCoyMnzO2 cathode material.

Herein, the correlation between electronic structure, transport and electrochemical properties of layered LixNi1-y-zCoyMnzO2 cathode material is revealed. Comprehensive experimental studies of physicochemical properties of LixNi1-y-zCoyMnzO2 cathode material (XRD, electrical conductivity, thermoelectric power) are supported by electronic structure calculations performed using the Korringa-Kohn-Rostoker method with the coherent potential approximation (KKR-CPA) to account for the chemical disorder. It is found that even small O defects (∼1%) could significantly modify electronic density of states DOS characteristics via the formation of extra broad peaks inside the former band gap leading to its substantial narrowing. The calculated DOS values and their changes near EF tend to support experimental findings with irregular changes in the sign of thermoelectric power as well as the behavior of electrical conductivity curves as a function of Li content. Furthermore, the variations of the electromotive force of the Li/Li+/LixNi1-y-zCoyMnzO2 cell (for 0 < x < 1) remains in a quite good agreement with the relative variation of EF on DOS calculated from the KKR-CPA method.

Anomaly in the electronic structure of the Na(x)CoO(2-y) cathode as a source of its step-like discharge curve.

In this paper we would like to show a new approach to an explanation of the nature of the discharge-charge curve of Na/Na(+)/NaxCoO2-y batteries, which can justify the existence of the step-like characteristics. This is still an open problem, which until now had no proper description in the literature. On the basis of comprehensive experimental studies of physicochemical properties of NaxCoO2-y cathode material (XRD, electrical conductivity, thermoelectric power, electronic specific heat) supported by calculations performed using the DFT method with accounting for chemical disorder, it has been shown that the observed step-like character of the discharge curve reflects the variation of the chemical potential of electrons (Fermi level) in the density of states of NaxCoO2-y, which is anomalously perturbed by the presence of the oxygen vacancy defects and sodium ordering. Our studies of structural, electronic and thermal properties of NaxCoO2-y cathode material as a function of concentration of electrochemically intercalated sodium document strong and step-like shift of the position of the Fermi level during introduction of electrons in this process. This effect is coherently supported by the shape of calculated density of states (DOS) of NaxCoO2-y having included oxygen defects and sodium ordering.

Structural, Transport and Electrochemical Properties of LiFePO4 Substituted in Lithium and Iron Sublattices (Al, Zr, W, Mn, Co and Ni).

LiFePO4 is considered to be one of the most promising cathode materials for lithium ion batteries for electric vehicle (EV) application. However, there are still a number of unsolved issues regarding the influence of Li and Fe-site substitution on the physicochemical properties of LiFePO4. This is a review-type article, presenting results of our group, related to the possibility of the chemical modification of phosphoolivine by introduction of cation dopants in Li and Fe sublattices. Along with a synthetic review of previous papers, a large number of new results are included. The possibility of substitution of Li⁺ by Al3+, Zr4+, W6+ and its influence on the physicochemical properties of LiFePO4 was investigated by means of XRD, SEM/EDS, electrical conductivity and Seebeck coefficient measurements. The range of solid solution formation in Li1-3xAlxFePO4, Li1-4xZrxFePO4 and Li1-6xWxFePO4 materials was found to be very narrow. Transport properties of the synthesized materials were found to be rather weakly dependent on the chemical composition. The battery performance of selected olivines was tested by cyclic voltammetry (CV). In the case of LiFe1-yMyPO4 (M = Mn, Co and Ni), solid solution formation was observed over a large range of y (0 < y ≤ 1). An increase of electrical conductivity for the substitution level y = 0.25 was observed. Electrons of 3d metals other than iron do not contribute to the electrical properties of LiFe1-yMyPO4, and substitution level y > 0.25 leads to considerably lower values of σ. The activated character of electrical conductivity with a rather weak temperature dependence of the Seebeck coefficient suggests a small polaron-type conduction mechanism. The electrochemical properties of LiFe1-yMyPO4 strongly depend on the Fe substitution level.