In this study, NASICON-type Li1+XGaXTi2-X(PO4)3 (x = 0.1, 0.3 and 0.4) solid-state electrolytes for all-solid-state batteries were synthesized through the sol-gel method. In addition, the influence on the ion conductivity of solid-state electrolytes when partially substituted for Ti4+ (0.61Å) site to Ga3+ (0.62Å) of trivalent cations was investigated. The obtained precursor was heat treated at 450 °C, and a single crystalline phase of Li1+XGaXTi2-X(PO4)3 systems was obtained at a calcination temperature above 650 °C. Additionally, the calcinated powders were pelletized and sintered at temperatures from 800 °C to 1,000 °C at 100 °C intervals. The synthesized powder and sintered bodies of Li1+XGaXTi2-X(PO4)3 were characterized using TGDTA, XRD, XPS and FE-SEM. The ionic conduction properties as solid-state electrolytes were investigated by AC impedance. As a result, Li1+XGaXTi2-X(PO4)3 was successfully produced in all cases. However, a GaPO4 impurity was formed due to the high sintering temperatures and high Ga content. The crystallinity of Li1+XGaXTi2-X(PO4)3 increased with the sintering temperature as evidenced by FE-SEM observations, which demonstrated that the edges of the larger cube-shaped grains become sharper with increases in the sintering temperature. In samples with high sintering temperatures at 1,000 °C and high Ga content above 0.3, coarsening of grains occurred. This resulted in the formation of many grain boundaries, leading to low sinterability. These two factors, the impurity and grain boundary, have an enormous impact on the properties of Li1+XGaXTi2-X(PO4)3. The Li1.3Ga0.3 Ti1.7(PO4)3 pellet sintered at 900 °C was denser than those sintered at other conditions, showing the highest total ion conductivity of 7.66 × 10-5 S/cm at room temperature. The total activation energy of Li-ion transport for the Li1.3Ga0.3Ti1.7(PO4)3 solidstate electrolyte was estimated to be as low as 0.36 eV. Although the Li1+XGaXTi2-X(PO4)3 sintered at 1,000 °C had a relatively high apparent density, it had less total ionic conductivity due to an increase in the grain-boundary resistance with coarse grains.

Li1.5Al0.5Ti1.5(PO4)3 (LATP) is considered to be one of the promising solid-state electrolytes owing to its excellent chemical and thermal stability, wide potential range (~5.0 V), and high ionic conductivity (~10-4 S/cm). LATP powders are typically prepared via the sol-gel method by adding and mixing nitrate or alkoxide precursors with chelating agents. Here, the thermal properties, crystallinity, density, particle size, and distribution of LATP powders based on chelating agents (citric acid, acetylacetone, EDTA) are compared to find the optimal conditions for densely sintered LATP with high purity. In addition, the three types of LATP powders are utilized to prepare sintered solid electrolytes and observe the microstructure changes during the sintering process. The pyrolysis onset temperature and crystallization temperature of the powder samples are in the order AC-LATP > CA-LATP > ED-LATP, and the LATP powder utilizing citric acid exhibits the highest purity, as no secondary phase other than LiTi2PO4 phase is observed. LATP with citric acid and acetylacetone has a value close to the theoretical density (2.8 g/cm3) after sintering. In comparison, LATP with EDTA has a low sintered density (2.2 g/cm3) because of the generation of many pores after sintering.

Li1.3Al0.3Ti1.7(PO4)3(LATP) is considered a promising material for all-solid-state lithium batteries owing to its high moisture stability, wide potential window (~6 V), and relatively high ion conductivity (10-3–10-4 S/cm). Solid electrolytes based on LATP are manufactured via sintering, using LATP powder as the starting material. The properties of the starting materials depend on the synthesis conditions, which affect the microstructure and ionic conductivity of the solid electrolytes. In this study, we synthesize the LATP powder using sol-gel and co-precipitation methods and characterize the physical properties of powder, such as size, shape, and crystallinity. In addition, we have prepared a disc-shaped LATP solid electrolyte using LATP powder as the starting material. In addition, X-ray diffraction, scanning electron microscopy, and electrochemical impedance spectroscopic measurements are conducted to analyze the grain size, microstructures, and ion conduction properties. These results indicate that the synthesis conditions of the powder are a crucial factor in creating microstructures and affecting the conduction properties of lithium ions in solid electrolytes.

Spherical Li3V2(PO4)3 (LVP) and carbon-coated LVP with a monoclinic phase for the cathode materials are synthesized by a hydrothermal method using N2H4 as the reducing agent and saccharose as the carbon source. The results show that single phase monoclinic LVP without impurity phases such as LiV(P2O7), Li(VO)(PO4) and Li3(PO4) can be obtained after calcination at 800 oC for 4 h. SEM and TEM images show that the particle sizes are 0.5~2 μm and the thickness of the amorphous carbon layer is approximately 3~4 nm. CV curves for the test cell are recorded in the potential ranges of 3.0~4.3 V and 3.0~4.8 V at a scan rate of 0.01 mV s–1 and at room temperature. At potentials between 3.0 and 4.8 V, the third Li+ ions from the carbon-coated LVP can be completely extracted, at voltages close to 4.51 V. The carbon-coated LVP exhibits an initial specific discharge capacity of 118 mAh g–1 in the voltage region of 3.0 to 4.3 V at a current rate of 0.2 C. The results indicate that the reducing agent and carbon source can affect the crystal structure and electrochemical properties of the cathode materials.

Impedancemetric NOx (NO and NO2) gas sensors were designed with a stacked-layer structure and fabricated using LaCrxCo1-xO3 (x = 0, 0.2, 0.5, 0.8 and 1) as the receptor material and Li1.3Al0.3Ti1.7(PO4)3 plates as the solid-electrolyte transducer material. The LaCrxCo1-xO3 layers were prepared with a polymeric precursor method that used ethylene glycol as the solvent, acetyl acetone as the chelating agent, and polyvinylpyrrolidone as the polymer additive. The effects of the Co concentration on the structural, morphological, and NOx sensing properties of the LaCrxCo1-xO3 powders were investigated with powder Xray diffraction, field emission scanning electron microscopy, and its response to 20~250 ppm of NOx at 400 oC (for 1 kHz and 0.5 V), respectively. When the as-prepared precursors were calcined at 700 oC, only a single phase was detected, which corresponded to a perovskite-type structure. The XRD results showed that as the Co concentration of the LaCrxCo1-xO3 powders increased, the crystal structure was transformed from an orthorhombic phase to a rhombohedral phase. Moreover, the LaCrxCo1-xO3 powders with 0 ≤ x < 0.8 had a rhombohedral symmetry. The size of the particles in the LaCrxCo1-xO3 powders increased from 0.1 to 0.5 μm as the Co concentration increased. The sensing performance of the stack-structured LaCrxCo1-xO3/Li1.3Al0.3Ti1.7(PO4)3 sensors was found to divide the impedance component between the resistance and capacitance. The response of these sensors to NO gas was more sensitive than that to NO2 gas. Compared to other impedancemetric sensors, the LaCr0.8Co0.2O3/Li1.3Al0.3Ti1.7(PO4)3 sensor exhibited good reversibility and reliable sensingresponse properties for NOx gases.

Li1+xAlxTi2-x(PO4)3(LATP) is a promising solid electrolyte for all-solid-state Li ion batteries. In this study, LATP isprepared through a sol-gel method using relatively the inexpensive reagents TiCl4. The thermal behavior, structuralcharacteristics, fractured surface morphology, ion conductivity, and activation energy of the LATP sintered bodies areinvestigated by TG-DTA, X-ray diffraction, FE-SEM, and by an impedance method. A gelation powder was calcined at 500oC.A single crystalline phase of the LiTi2(PO4)3(LTP) system was obtained at a calcination temperature above 650oC. The obtainedpowder was pelletized and sintered at 900oC and 1000oC. The LTP sintered at 900~1000oC for 6 h had a relatively low apparentdensity of 75~80%. The LATP(x=0.3) pellet sintered at 900oC for 6 h was denser than those sintered under other conditionsand showed the highest ion conductivity of 4.50×10−5S/cm at room temperature. However, the ion conductivity of LATP(x=0.3) sintered at 1000oC decreased to 1.81×10−5S/cm, leading to Li volatilization and abnormal grain growth. For LATPsintered at 900oC for 6 h, x=0.3 shows the lowest activation energy of 0.42eV in the temperature range of room temperatureto 300oC.