Solid-state ion doping and crystal structure engineering for enhanced ionic conductivity in LiTi2(PO4)3 electrolytes

Luo, Yinyi; Liu, Xinyu; Wen, Ching–ju; Ning, Tianxiang; Jiang, Xingxing; Lu, Anxian

doi:10.1007/s00339-023-06796-7

Cited by 3 publications

(2 citation statements)

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“…[26,27] Compared to sulfide-based solid electrolytes, NASICON-type solid electrolytes require high-temperature sintering above 1000 °C to achieve the maximum ionic conductivity. [26,[28][29][30] Unfortunately, a high sintering temperature leads to the loss of volatile materials, such as Li, and facilitates the formation of impurities at grain boundaries. [31][32][33][34] Therefore, numerous studies have been performed to minimize the sintering temperature of oxide-based solid electrolytes.…”

Section: Introductionmentioning

confidence: 99%

“…NASICON-type solid electrolytes have been synthesized using solid-or liquid-phase methods, such as melt quenching or sol-gel method, which possess certain disadvantages. [26,[28][29][30]51] The sol-gel method typically requires expensive and toxic solvents, whereas the prepared powders in the solid-state reaction method have irregular shapes, which can produce pores during the sintering process. These synthesis methods usually involve a multistep process, including a milling procedure which can introduce unwanted impurities from the balls or containers.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and Sintering of Li_1.3Al_0.3Ti_1.7(PO₄)₃@Li₂O–2B₂O₃ Core–Shell Solid Electrolyte Powders Prepared via One‐Pot Spray Pyrolysis

Shin,

Kim,

Jung

et al. 2024

Adv Eng Mater

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Developing a rational design for oxide‐based solid electrolytes to promote ionic conductivity, decrease the sintering temperature, and improve stability with metallic Li is challenging. Herein, core–shell‐structured Li1.3Al0.3Ti1.7(PO4)3@Li2O–2B2O3 (LATP–LBO) microspheres are prepared using one‐pot spray pyrolysis. Phase separation between crystalline LATP and amorphous LBO leads to the formation of a core–shell‐structured LATP–LBO composite. On the surface of LATP–LBO composite, the LBO shell forms a liquid phase during low‐temperature sintering, thereby enhancing the densification. The LBO shell also decreases the grain boundary resistance by forming a thin layer between the LATP grains, thus increasing the total ionic conductivity. Because Li‐ion conductive LBO occupies the grain boundary, a total ionic conductivity of 1.519 × 10−4 S cm−1 is achieved at a low sintering temperature of 700 °C. Additionally, the LBO shell provides good electrochemical stability for LATP with metallic Li. The improved ionic conductivity and chemical stability can be attributed to the synergistic advantages of the spherical morphology, core–shell structure, and uniformity of LBO.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis and Sintering of Li_1.3Al_0.3Ti_1.7(PO₄)₃@Li₂O–2B₂O₃ Core–Shell Solid Electrolyte Powders Prepared via One‐Pot Spray Pyrolysis

Shin,

Kim,

Jung

et al. 2024

Adv Eng Mater

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Synthesis, phase transitions, and thermal expansion in arsenate-phosphate solid solution with garnet structure

Pet’kov,

Piaterikov,

Fukina

2023

J Therm Anal Calorim

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Migration properties of Li+ in Li1+x AlxTi2–x(PO4)3

Li,

Zhong,

et al. 2024

Acta Phys. Sin.

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NASICON type materials are specific skeleton structures in which ions move in three dimensions. Li1+xAlxTi2-x(PO4)3 (LATP) is a promising NASICON type solid-state electrolyte for Li-ion batteries, due to its relatively high Li-ion conductivity, chemical stability to air and moisture and mechanical strength. Motivated by this, we studied the doping and electronic properties of Li1+xAlxTi2-x(PO4)3 (x = 0.00、0.16、0.33、0.50) and the transport properties of Li+ in them using first-principles calculations based on density functional theory as implemented in Vienna ab initio Simulation Package (VASP). The results indicate that Al can substitute Ti to form stable structures. When the Al doping concentration is x = 0.16, the average bond length of Li-O bonds is the longest and the bonding strength is the weakest, This may lead to the expansion of channels for Li+ migration, which facilitates the diffusion of Li+. With the increase of Al doping concentration, the strength of Ti-O bond remains almost unchanged. The electronic structure calculations exhibit that with the increase of Al doping concentration, the bandgap of LATP does not change much, and LATP all shows semiconductor characteristics. The differential charge results indicate that more electrons are localized on O-atoms surrounding the Al-dopant, causing the AlO6 groups to form polarization centers. The study on the migration properties of Li+ indicates that Li+ exhibits different migration characteristics when it adopts one of three different migration modes (vacancy migration, interstitial migration and cooperative migration) : With the increase of Al doping concentration, the migration barriers of Li+ increase in migration via vacancies involving only lattice site migration, And the migration barrier for LATP-0.16 is the lowest (0.369 eV). While in interstitial migration involving only interstitial sites, the migration barrier of Li+ decreases accordingly. When the Al doping concentration is x=0.50, the migration barrier is the lowest (0.342 eV). In terms of cooperative migration, this migration mode involves both vacancy and interstitial sites, so the migration barrier first decreases and then increases with the increase of Al doping concentration. Thus, our study suggests that by varying the concentration of Al doping, the interstitial Li+content, migration channel structure, and the migration performance of Li+ can be changed favorably. Our results provide a theoretical basis for improving the ion conductivity of Li in LATP with varying Al doping concentration in experiments.

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Solid-state ion doping and crystal structure engineering for enhanced ionic conductivity in LiTi2(PO4)3 electrolytes

Cited by 3 publications

References 65 publications

Synthesis and Sintering of Li_1.3Al_0.3Ti_1.7(PO₄)₃@Li₂O–2B₂O₃ Core–Shell Solid Electrolyte Powders Prepared via One‐Pot Spray Pyrolysis

Synthesis and Sintering of Li_1.3Al_0.3Ti_1.7(PO₄)₃@Li₂O–2B₂O₃ Core–Shell Solid Electrolyte Powders Prepared via One‐Pot Spray Pyrolysis

Synthesis, phase transitions, and thermal expansion in arsenate-phosphate solid solution with garnet structure

Migration properties of Li<sup>+ </sup>in Li<sub>1+<i>x</i> </sub>Al<sub><i>x</i></sub>Ti<sub>2–<i>x</i></sub>(PO<sub>4</sub>)<sub>3</sub>

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Solid-state ion doping and crystal structure engineering for enhanced ionic conductivity in LiTi2(PO4)3 electrolytes

Cited by 3 publications

References 65 publications

Synthesis and Sintering of Li1.3Al0.3Ti1.7(PO4)3@Li2O–2B2O3 Core–Shell Solid Electrolyte Powders Prepared via One‐Pot Spray Pyrolysis

Synthesis and Sintering of Li1.3Al0.3Ti1.7(PO4)3@Li2O–2B2O3 Core–Shell Solid Electrolyte Powders Prepared via One‐Pot Spray Pyrolysis

Synthesis, phase transitions, and thermal expansion in arsenate-phosphate solid solution with garnet structure

Migration properties of Li<sup>+ </sup>in Li<sub>1+<i>x</i> </sub>Al<sub><i>x</i></sub>Ti<sub>2–<i>x</i></sub>(PO<sub>4</sub>)<sub>3</sub>

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Synthesis and Sintering of Li_1.3Al_0.3Ti_1.7(PO₄)₃@Li₂O–2B₂O₃ Core–Shell Solid Electrolyte Powders Prepared via One‐Pot Spray Pyrolysis

Synthesis and Sintering of Li_1.3Al_0.3Ti_1.7(PO₄)₃@Li₂O–2B₂O₃ Core–Shell Solid Electrolyte Powders Prepared via One‐Pot Spray Pyrolysis