Sol-gel synthesis of Al- and Nb-co-doped Li7La3Zr2O12 solid electrolytes

Il’ina, E. A.; Lyalin, E. D.; Антонов, Б. Д.; Панкратов, А. А.; Вовкотруб, Э. Г.

doi:10.1007/s11581-020-03492-x

Cited by 17 publications

(9 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Moreover, a band due to stretching near 720 cm –1 , corresponds to TaO 6 /NbO 6 octahedra units (Figure c,d). A similar stretching band near 720 cm –1 was also observed by other researchers for doped LLZO garnets, for instance, Rettenwander et al observed for Mo-doped LLZO, Meesala et al found for Ta-doped LLZO, Dubey et al reported for Mn-doped LLZO, Shen detected for Te-doped LLZO, and Vovkotrub and co-worker observed for Nb-doped LLZO …”

Section: Results and Discussionsupporting

confidence: 83%

“…A similar stretching band near 720 cm −1 was also observed by other researchers for doped LLZO garnets, for instance, Rettenwander et al observed for Mo-doped LLZO, 17 Meesala et al found for Ta-doped LLZO, 18 Dubey et al reported for Mn-doped LLZO, 19 Shen detected for Te-doped LLZO, 20 and Vovkotrub and co-worker observed for Nb-doped LLZO. 21 3.3. Ionic Conduction Characteristics.…”

Section: Structural Analysismentioning

confidence: 99%

See 1 more Smart Citation

Elucidating the Importance of Quaternary Dopants in Stabilizing Cubic LLZO at Low Temperature

Umesh,

Jayaraman,

Prakash

2024

J. Phys. Chem. C

View full text Add to dashboard Cite

Future-generation solid-state Li batteries could benefit from the use of garnet-type Li 7 La 3 Zr 2 O 12 (LLZO) as an electrolyte. However, attaining a stable and highly ionic conducting LLZO garnet at low temperature is a big challenge. In this work, cubic phase stabilized LLZO with enhanced ionic conduction was achieved at low temperature by "quaternary substitution," in specific substitution of Ga−Mg and Ta−Nb at Li and Zr sites, respectively. Investigations on the structural, morphological, and electrochemical properties were conducted to study the impact of the quaternary dopants. Structural analysis revealed that quaternary substitution in LLZO forms a direct cubic phase Li 7 La 3 Zr 2 O 12 without the need for hightemperature sintering. Morphological studies demonstrated that quaternary substitution promotes grain growth and reduces the size of the grain boundaries. Impedance measurements proved that cubic LLZO achieved by substituting quaternary dopants show an ionic conduction of ∼1.5923 × 10 −4 S/cm, which is four orders higher than tetragonal LLZO (∼2.9945 × 10 −8 S/cm). Galvanostatic stripping and plating profiles assured the appropriateness of LLZO as a solid-state electrolyte for solid-state batteries. Additionally, band valence site energy analysis was used to theoretically justify the improvement in ionic conduction achieved by quaternary dopants.

show abstract

Section: Results and Discussionsupporting

confidence: 83%

Section: Structural Analysismentioning

confidence: 99%

Elucidating the Importance of Quaternary Dopants in Stabilizing Cubic LLZO at Low Temperature

Umesh,

Jayaraman,

Prakash

2024

J. Phys. Chem. C

View full text Add to dashboard Cite

show abstract

“…Another approach to obtain solid electrolytes is sol–gel synthesis, and it is known ,, that ceramics synthesized by this method show higher conductivity values compared to those obtained by solid-phase synthesis. Additionally, sol–gel synthesis provides more homogeneous products with smaller grain sizes and reduces the sintering time and temperature of solid electrolytes.…”

Section: Introductionmentioning

confidence: 99%

“…Particularly, the conductivity of LLZO obtained by solid-phase synthesis without any dopants is equal to ∼10 −5 S cm −1 , 11,15 while uncontrolled introduction of aluminum from crucibles 22,24,25 or codoping (introduction of other elements besides Ta into the LLZO structure) 17,18,28−32 leads to higher conductivity values from 10 −3 to 10 −4 S cm −1 . For example, in another work, 32 Another approach to obtain solid electrolytes is sol−gel synthesis, and it is known 11,33,34 that ceramics synthesized by this method show higher conductivity values compared to those obtained by solid-phase synthesis. Additionally, sol−gel synthesis provides more homogeneous products with smaller grain sizes and reduces the sintering time and temperature of solid electrolytes.…”

Section: Introductionmentioning

confidence: 99%

Structural Features and the Li-Ion Diffusion Mechanism in Tantalum-Doped Li₇La₃Zr₂O₁₂ Solid Electrolytes

Il’ina

Lyalin

Vlasov

et al. 2022

ACS Appl. Energy Mater.

View full text Add to dashboard Cite

Solid electrolytes with high values of lithium-ion conductivity are required for the creation of high-energy lithium and lithium-ion power sources, and compounds with a garnet structure based on Li7La3Zr2O12 (LLZO) are one of the candidate materials for this purpose. In the present work, solid electrolytes of the Li7–x La3Zr2–x Ta x O12 system with x = 0.0–2.0 were synthesized using the sol–gel method. According to X-ray diffraction analysis, all of the compounds with x ≥ 0.1 have the same cubic modification with the space group Ia3̅d. However, an increase in Ta concentration affects the short-range order crystal structure of these materials, resulting in higher local distortions, which was shown by pair distribution function (PDF) analysis. Particularly, the PDF data indicate an increase in the probability of Li ions to locally occupy not only two typical positions, Li196 h and Li224 d, but also a third one, Li348 g. The maximum value of lithium-ion conductivity in the studied system was observed for the Li6.4La3Zr1.4Ta0.6O12 compound (i.e., x = 0.6) and had the value of 1.4 × 10–4 S cm–1 at 25 °C. This is consistent with the results of density functional theory (DFT) modeling, which confirmed that a moderate Ta-doping (up to x < 1.0) is most suitable for enhancing Li diffusion in LLZO materials. A combination of DFT modeling, structural characterization of the short and average structures, and conductivity measurements in this work allowed getting insight into this important class of Li-conducting oxides and ideas on improving their properties.

show abstract

“…These factors contribute to low conductivity and high purity for excellent sensitivity. Finally, the high surface area materials and their porosity composed by sol-gel methods should increase sensitivity in mechanisms dominated by surface phenomena.Sol-gel is progressively enticing the consideration of the electrochemical community as a versatile way to produce coatings for supercapacitors [13,14], electrochemical sensors [15], solid electrolytes [16], electrochromic devices [17], anti-corrosion protection [18,19], etc.…”

Section: Introductionmentioning

confidence: 99%

Sol-Gel Materials for Electrochemical Applications: Recent Advances

2022

View full text Add to dashboard Cite

This review article emphases on the modern approaches to the types of sol-gel materials that are beneficial for electrochemistry, monitored by a report of recent advances in the numerous fields of sol-gel electrochemistry. Modified electrodes for sensors and supercapacitors as well as anti-corrosion are described. Sol-gel synthesis expands the capabilities of technologists to obtain highly porous, homogeneous, and hybrid thin-film materials for supercapacitor electrode application. The widespread materials are transition metal oxides, but due to their low conductivity, they greatly impede the rate capability of electrochemical supercapacitors. The way to optimize their properties is the production of complex oxides or different composites. Among the new materials, a special place is occupied by perovskites and materials with an olivine-type structure, which can be easily obtained by the sol-gel method. The sol-gel coating process has demonstrated excellent chemical stability to advance the corrosion resistance of the various metal alloy substrates. Furthermore, the sol-gel process is a user-friendly technique for applying a hybrid sol-gel coating to provide corrosion resistance. The hybrid sol-gel coating technique is the most attractive, easy to prepare at a lower temperature, and has shown the potential to swap Cr-based coatings. The hybrid sol-gel coating has exhibited promising properties of adherent and uses chemically inert to enhance the corrosion resistance of the metal and alloys. Hence, this review article emphases on the recent advances and approaches in the sol-gel coating processes that influence the belongings of its hybrid sol-gel coating for protecting metal substrates and their alloys from corrosion. In addition, the author discusses the current problem and challenges of hybrid anti-corrosion sol-gel coatings. Metal oxides and composites based on them are actively used to create electrochemical sensors. They synthesized, including the anhydrous and citrate sol-gel methods. Such materials are widely used as glucose biosensors and harmful gas sensors.

show abstract

Sol-gel synthesis of Al- and Nb-co-doped Li7La3Zr2O12 solid electrolytes

Cited by 17 publications

References 36 publications

Elucidating the Importance of Quaternary Dopants in Stabilizing Cubic LLZO at Low Temperature

Elucidating the Importance of Quaternary Dopants in Stabilizing Cubic LLZO at Low Temperature

Structural Features and the Li-Ion Diffusion Mechanism in Tantalum-Doped Li₇La₃Zr₂O₁₂ Solid Electrolytes

Sol-Gel Materials for Electrochemical Applications: Recent Advances

Contact Info

Product

Resources

About

Sol-gel synthesis of Al- and Nb-co-doped Li7La3Zr2O12 solid electrolytes

Cited by 17 publications

References 36 publications

Elucidating the Importance of Quaternary Dopants in Stabilizing Cubic LLZO at Low Temperature

Elucidating the Importance of Quaternary Dopants in Stabilizing Cubic LLZO at Low Temperature

Structural Features and the Li-Ion Diffusion Mechanism in Tantalum-Doped Li7La3Zr2O12 Solid Electrolytes

Sol-Gel Materials for Electrochemical Applications: Recent Advances

Contact Info

Product

Resources

About

Structural Features and the Li-Ion Diffusion Mechanism in Tantalum-Doped Li₇La₃Zr₂O₁₂ Solid Electrolytes