The ionomer concept was introduced to the field of flame-retardant polyesters for the first time. The ionic monomer, sodium salt of 2-hydroxyethyl 3-(phenylphosphinyl)propionate (SHPPP), was synthesized by selective esterification of 3-(hydroxyphenylphosphinyl)propionic acid with ethylene glycol, followed by neutralization with sodium carbonate anhydrous. SHPPP was characterized with 1 H, 13 C, and 31 P NMR spectroscopy, Fourier transform infrared spectroscopy, and X-Ray photoelectron spectroscopy. Poly(ethylene terephthalate)-based ionomers containing terminal units derived from this ionic monomer, were synthesized by melt polycondensation. The chemical structure of the ionomers was characterized with 1 H, 13 C, and 31 P NMR spectroscopy. The effects of SHPPP on the thermal properties and melting behaviors of the ionomers were investigated by thermogravimetric analysis and differential scanning calorimetry. The flammability of the ionomers was characterized by the limiting oxygen index test. The test results show that the ionomers themselves possess both excellent flame retardancy and antidripping properties.
All-solid-state lithium batteries (ASSLBs), which use solid electrolytes instead of liquid ones, have become a hot research topic due to their high energy and power density, ability to solve battery safety issues, and capabilities to fulfill the increasing demand for energy storage in electric vehicles and smart grid applications. Garnet-type solid electrolytes have attracted considerable interest as they meet all the properties of an ideal solid electrolyte for ASSLBs. The garnet-type Li7La3Zr2O12 (LLZO) has excellent environmental stability; experiments and computational analyses showed that this solid electrolyte has a high lithium (Li) ionic conductivity (10−4–10−3 S·cm−1), an electrochemical window as wide as 6 V, stability against Li metal anode, and compatibility with most of the cathode materials. In this review, we present the fundamentals of garnet-type solid electrolytes, preparation methods, air stability, some strategies for improving the conductivity based on experimental and computational results, interfacial issues, and finally applications and challenges for future developments of LLZO solid electrolytes for ASSLBs.
Recently, all-solid-state batteries (ASSBs) have attracted increasing interest owing to their higher energy density and safety. As the core material of ASSBs, the characteristics of the solid electrolyte largely determine the performance of the battery. Thus far, a variety of inorganic solid electrolytes have been studied, including the NASICON-type, LISICON-type, perovskite-type, garnet-type, glassy solid electrolyte, and so on. The garnet Li 7 La 3 Zr 2 O 1 2 (LLZO) solid electrolyte is one of the most promising candidates because of its excellent comprehensively electrochemical performance. Both, experiments and theoretical calculations, show that cubic LLZO has high room-temperature ionic conductivity and good chemical stability while contacting with the lithium anode and most of the cathode materials. In this paper, the crystal structure, Li-ion transport mechanism, preparation method, and element doping of LLZO are introduced in detail based on the research progress in recent years. Then, the development prospects and challenges of LLZO as applied to ASSBs are discussed.
Bottleneck size is the minimum Li+ migration channel of Li7La3Zr2O12 (LLZO) and it greatly influences the Li+ conductivity. Doping different elements on the Zr site of LLZO can adjust the bottleneck size and improve the Li+ conductivity. However, the regulation mechanism is not clear. In this work, Li6.4La3Zr1.4M0.6O12 (M = Sb, Ta, Nb) has been prepared and the bottleneck size has been adjusted by doping different pentavalent ions. The results manifest that the cell parameter and bottleneck size decrease with the rise of the radius of doped pentavalent ions. This is because larger pentavalent ion leads to larger bond length of M–O, and weaker covalent component between M5+ and O2‐, corresponding, the formal charge on the M5+ become larger, and the bond length of La–O slightly decreases due to the coulomb repulsion between La3+ and M5+ increase. While, the activation energy drop firstly and then rise with the rise of bottleneck size because of the migration of Li+ not only relate to the size of the migration channel but also to the strength of M–O covalent bonding. The bottleneck size and bond length of M–O synergistically affect the migration of Li+.
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