Processing and Properties of Garnet-Type Li7 La3 Zr2 O12 Ceramic Electrolytes.

Garnet-type solid electrolyte Li7 La3 Zr2 O12 (LLZO) is widely considered as one of the most promising candidates for solid state batteries (SSBs) owing to its high ionic conductivity and good electrochemical stability. Since its discovery in 2007, great progress has been made in terms of crystal chemistry, chemical and electrochemical properties, and battery application. Nonetheless, reliable and controllable preparation of LLZO ceramics with desirable properties still remains as big challenges. Herein, this review summarizes various synthetic routes of LLZO ceramics and examines the influence of various key processing parameters on the chemical and electrochemical properties. Focusing on correlation of processing parameters and properties, this review aims to provide new insights on a reliable and controllable production of high-quality LLZO ceramic electrolytes for SSB application.

Ceramic-Polymer Composite Membranes for Water and Wastewater Treatment: Bridging the Big Gap between Ceramics and Polymers.

Clean water supply is an essential element for the entire sustainable human society, and the economic and technology development. Membrane filtration for water and wastewater treatments is the premier choice due to its high energy efficiency and effectiveness, where the separation is performed by passing water molecules through purposely tuned pores of membranes selectively without phase change and additional chemicals. Ceramics and polymers are two main candidate materials for membranes, where the majority has been made of polymeric materials, due to the low cost, easy processing, and tunability in pore configurations. In contrast, ceramic membranes have much better performance, extra-long service life, mechanical robustness, and high thermal and chemical stabilities, and they have also been applied in gas, petrochemical, food-beverage, and pharmaceutical industries, where most of polymeric membranes cannot perform properly. However, one of the main drawbacks of ceramic membranes is the high manufacturing cost, which is about three to five times higher than that of common polymeric types. To fill the large gap between the competing ceramic and polymeric membranes, one apparent solution is to develop a ceramic-polymer composite type. Indeed, the properly engineered ceramic-polymer composite membranes are able to integrate the advantages of both ceramic and polymeric materials together, providing improvement in membrane performance for efficient separation, raised life span and additional functionalities. In this overview, we first thoroughly examine three types of ceramic-polymer composite membranes, (i) ceramics in polymer membranes (nanocomposite membranes), (ii) thin film nanocomposite (TFN) membranes, and (iii) ceramic-supported polymer membranes. In the past decade, great progress has been made in improving the compatibility between ceramics and polymers, while the synergy between them has been among the main pursuits, especially in the development of the high performing nanocomposite membranes for water and wastewater treatment at lowered manufacturing cost. By looking into strategies to improve the compatibility among ceramic and polymeric components, we will conclude with briefing on the perspectives and challenges for the future development of the composite membranes.

First-principles density functional calculation of electrochemical stability of fast Li ion conducting garnet-type oxides.

The research and development of rechargeable all-ceramic lithium batteries are vital to realize their considerable advantages over existing commercial lithium ion batteries in terms of size, energy density, and safety. A key part of such effort is the development of solid-state electrolyte materials with high Li(+) conductivity and good electrochemical stability; lithium-containing oxides with a garnet-type structure are known to satisfy the requirements to achieve both features. Using first-principles density functional theory (DFT), we investigated the electrochemical stability of garnet-type Li(x)La(3)M(2)O(12) (M = Ti, Zr, Nb, Ta, Sb, Bi; x = 5 or 7) materials against Li metal. We found that the electrochemical stability of such materials depends on their composition and structure. The electrochemical stability against Li metal was improved when a cation M was chosen with a low effective nuclear charge, that is, with a high screening constant for an unoccupied orbital. In fact, both our computational and experimental results show that Li(7)La(3)Zr(2)O(12) and Li(5)La(3)Ta(2)O(12) are inert to Li metal. In addition, the linkage of MO(6) octahedra in the crystal structure affects the electrochemical stability. For example, perovskite-type La(1/3)TaO(3) was found, both experimentally and computationally, to react with Li metal owing to the corner-sharing MO(6) octahedral network of La(1/3)TaO(3), even though it has the same constituent elements as garnet-type Li(5)La(3)Ta(2)O(12) (which is inert to Li metal and features isolated TaO(6) octahedra).

Na superionic conductor-type LiZr2(PO4)3 as a promising solid electrolyte for use in all-solid-state Li metal batteries.

All-solid-state Li-ion batteries are of considerable interest as safer alternatives to Li-ion batteries containing flammable organic electrolytes. To date, however, achieving sufficient charging and discharging rates, in addition to capacity, at room temperature using these all-solid-state batteries has been challenging. To overcome these issues, material simulations and informatics investigations of a relatively new Na superionic conductor (NASICON)-type LiZr2(PO4)3 (LZP) electrolyte were conducted to elucidate its characteristics and material functions. The following thermodynamic and/or kinetic properties of NASICON-type Li-ion conductive oxides were investigated with respect to the crystal structure mainly using material simulation and informatics approaches: (1) the electrochemical stabilities of LZP materials with respect to Li metal and (2) Li-ion conductivities in the bulk and at the grain boundaries. An efficient materials informatics search method was employed to optimise the material functions of the LZP electrolyte via Bayesian optimisation. This study should promote the application of LZP in all-solid-state batteries for use in technologies such as mobile devices and electric vehicles and enable more complex composition and process control.

Ferroelectric Engineered Electrode-Composite Polymer Electrolyte Interfaces for All-Solid-State Sodium Metal Battery.

To enhance the compatibility between the polymer-based electrolytes and electrodes, and promote the interfacial ion conduction, a novel approach to engineer the interfaces between all-solid-state composite polymer electrolyte and electrodes using thin layers of ferroelectrics is introduced. The well-designed and ferroelectric-engineered composite polymer electrolyte demonstrates an attractive ionic conductivity of 7.9 × 10-5 S cm-1 at room temperature. Furthermore, the ferroelectric engineering is able to effectively suppress the growth of solid electrolyte interphase (SEI) at the interface between polymer electrolytes and Na metal electrodes, and it can also enhance the ion diffusion across the electrolyte-ferroelectric-cathode/anode interfaces. Notably, an extraordinarily high discharge capacity of 160.3 mAh g-1 , with 97.4% in retention, is achieved in the ferroelectric-engineered all-solid-state Na metal cell after 165 cycles at room temperature. Moreover, outstanding stability is demonstrated that a high discharge capacity retention of 86.0% is achieved over 180 full charge/discharge cycles, even though the cell has been aged for 2 months. This work provides new insights in enhancing the long-cyclability and stability of solid-state rechargeable batteries.

Overcoming the Trade-off between Water Permeation and Mechanical Strength of Ceramic Membrane Supports by Interfacial Engineering.

Porous ceramic membrane supports with high mechanical strength and permeation are required for highly permeable ceramic membranes. The water permeation of a ceramic membrane support is largely dependent on its level of open porosity, which can be however generally detrimental to the mechanical strength. In this work, low-cost kaolin nanoflakes were rationally composited with coarse alumina particles, and multichannel flat-sheet ceramic supports were successfully fabricated by extrusion and subsequent partial sintering. The macroscopic properties, microstructure characteristics, permeability, and mechanical strength of the ceramic membrane supports were systematically established and comprehensively studied. The incorporation of kaolin nanoflakes effectively reduced the sintering temperature to about 1200 °C. An interesting evolution of the pore structure was evidenced with the increase in sintering temperature. Interestingly, the porous ceramic supports prepared at 1400 °C with a nominal pore size of 1.47 µm showed the highest water permeability of 9911.9 ± 357.5 LMHB, and at the same time the flexural strength reached 109.6 ± 4.6 MPa. The much improved permeability was attributed to the unique multilevel pore structures, and the enhanced flexural strength mainly originated from the strongly interfacial bonding, as evidenced by the trans-granular fracture behavior. Also, the ceramic membrane supports exhibited excellent chemical resistance and good removal efficiency for oily wastewater. This work highlights the significant role of interfacial engineering in simultaneously improving the water permeation and mechanical strength, thereby overcoming their trade-off in porous ceramic membrane supports.

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.

Na-rich layered Na2Ti1-xCrxO3-x/2 (x = 0, 0.06): Na-ion battery cathode materials with high capacity and long cycle life.

Rechargeable lithium batteries have been well-known and indispensable for portable electronic devices, and have the potential to be used in electric vehicles and smart grids. However, the growing concerns about the availability of lithium resources for large-scale applications have revived interest in sodium ion batteries. Of many obstacles to commercialization of Na-ion batteries, achieving simultaneously a large reversible capacity and good cycling capability of electrode materials remains a major challenge. Here, we report a new cathode material, Na-rich layered oxide Na2Ti0.94Cr0.06O2.97, that delivers high reversible capacity of 336 mAh g-1 at current density of 18.9 mA g-1 along with promising cycling capability of 74% capacity retention over 1000 cycles at current of 378 mA g-1. The high capacity is associated to the redox reaction of oxygen, which is confirmed here by a combined experimental and theoretical study. The present work therefore shows that materials beyond mainstream layered oxides and polyanion compounds should be considered as candidate high-performance cathodes for Na-ion batteries.

Design of a micro-pattern structure for a three dimensionally macroporous Sn-Ni alloy anode with high areal capacity.

A highly patterned porous Sn-Ni anode with various patterns was investigated as an anode for a lithium battery and showed much higher areal capacity than a conventional graphite electrode. This result proves the importance of a structured electrode for development of an electrode with higher performance.