The mechanism of enhanced ionic conductivity in Li1.3Al0.3Ti1.7(PO4)3–(0.75Li2O·0.25B2O3) composites

Kwatek, K.; Ślubowska, Wioleta; Ruiz, Constanza; Sobrados, Isabel; Sanz, J.; Garbarczyk, Jerzy E.; Nowiński, J.L.

doi:10.1016/j.jallcom.2020.155623

Cited by 32 publications

(31 citation statements)

References 53 publications

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“…The occurrence of two LATP phases was also observed by C. Vinod Chandran in Li 1+x A lx Ti 2-x (PO 4 ) 3 samples with x > 0.5 [58]. The peak at −20.1 ppm can be attributed to aluminum environment in LiAlP 2 O 7 compound [53,57]. Furthermore, the weak signal observed at −9.6 ppm may be assigned to some other unknown phase containing Al ions (see Table 4).…”

Section: Magic-angle Spinning Nuclear Magnetic Resonance (Mas Nmr) (Bsupporting

confidence: 54%

“…The signal at 40.5 ppm is characteristic for AlPO 4 compound in AlO 4 coordination of aluminum [30,[49][50][51][52]. The resonances located at −14.3 and −15.7 ppm correspond to aluminum in AlO 6 environment in two slightly different LATP phases [53,54,58]. The occurrence of two LATP phases was also observed by C. Vinod Chandran in Li 1+x A lx Ti 2-x (PO 4 ) 3 samples with x > 0.5 [58].…”

Section: Magic-angle Spinning Nuclear Magnetic Resonance (Mas Nmr) (Bmentioning

confidence: 56%

“…In the region of AlO 6 sites, two resonances at −15.3 and −17.7 ppm are characteristic for aluminum coordination in the NASICON-type phase [30], meaning that two LATP phases with similar chemical composition may coexist. The last signal at −21.4 ppm might be ascribed to aluminum in octahedral coordination in the LiAlP 2 O 7 phase [53].…”

Section: Magic-angle Spinning Nuclear Magnetic Resonance (Mas Nmr) (Mmentioning

confidence: 99%

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B2O3-Doped LATP Glass-Ceramics Studied by X-ray Diffractometry and MAS NMR Spectroscopy Methods

Ślubowska

Montagne²,

Lafon

et al. 2021

Nanomaterials

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Two families of glasses in the Li2O-Al2O3-B2O3-TiO2-P2O5 system were prepared via two different synthesis routes: melt-quenching and ball-milling. Subsequently, they were submitted to crystallization and yielded the Li1.3Al0.3Ti1.7(PO4)3 (LATP)-based glass-ceramics. Glasses and corresponding glass-ceramics were studied by complementary X-ray diffraction (XRD) and 27Al, 31P, 7Li, 11B magic-angle spinning nuclear magnetic resonance (MAS NMR) methods in order to compare their structure and phase composition and elucidate the impact of boron additive on their glass-forming properties and crystallization process. XRD studies show that the addition of B2O3 improves the glass-forming properties of glasses prepared by either method and inhibits the precipitation of unwanted phases during heat treatment. MAS NMR studies allowed us to distinguish two LATP phases of slightly different chemical composition suggesting that LATP grains might not be homogeneous. In conclusion, the crystallization of boron-incorporated LATP glasses can is an effective way of obtaining LATP-based solid state electrolytes for the next generation of lithium-ion batteries provided the proper heat-treatment conditions are chosen.

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Section: Magic-angle Spinning Nuclear Magnetic Resonance (Mas Nmr) (Bsupporting

confidence: 54%

Section: Magic-angle Spinning Nuclear Magnetic Resonance (Mas Nmr) (Bmentioning

confidence: 56%

Section: Magic-angle Spinning Nuclear Magnetic Resonance (Mas Nmr) (Mmentioning

confidence: 99%

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B2O3-Doped LATP Glass-Ceramics Studied by X-ray Diffractometry and MAS NMR Spectroscopy Methods

Ślubowska

Montagne²,

Lafon

et al. 2021

Nanomaterials

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“…Grain boundary conductivity of LATP was found to be highly dependent on the sintering process, resulting in different particle size distributions (i.e., microstructure) and different impurity phases [8,10,11,14,[23][24][25][26]. The effectiveness of the LATP sintering process can be considerably improved by the use of appropriate sintering agents, such as LiF [14,27,28], Li 3 PO 4 [29], Li 3 BO 3 [24,29], LiBO 2 [30], LiBF 4 [31], LiNO 3 [32], Li 2 O [33], and Li 4 SiO 4 [this work]. These inorganic salts are known to affect the microstructure (lower porosity) and secondary phase formation, leading to higher total ionic conductivity.…”

Section: Introductionmentioning

confidence: 99%

“…However, the increase of grain size alone is not sufficient. This is why the other approach is to modify the grain-boundary composition towards a higher conducting one [23,24,29,30,33].…”

Section: Introductionmentioning

confidence: 99%

Electrical and Structural Properties of Li1.3Al0.3Ti1.7(PO4)3—Based Ceramics Prepared with the Addition of Li4SiO4

et al. 2021

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The currently studied materials considered as potential candidates to be solid electrolytes for Li-ion batteries usually suffer from low total ionic conductivity. One of them, the NASICON-type ceramic of the chemical formula Li1.3Al0.3Ti1.7(PO4)3, seems to be an appropriate material for the modification of its electrical properties due to its high bulk ionic conductivity of the order of 10−3 S∙cm−1. For this purpose, we propose an approach concerning modifying the grain boundary composition towards the higher conducting one. To achieve this goal, Li4SiO4 was selected and added to the LATP base matrix to support Li+ diffusion between the grains. The properties of the Li1.3Al0.3Ti1.7(PO4)3−xLi4SiO4 (0.02 ≤ x ≤ 0.1) system were studied by means of high-temperature X-ray diffractometry (HTXRD); 6Li, 27Al, 29Si, and 31P magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR); thermogravimetry (TG); scanning electron microscopy (SEM); and impedance spectroscopy (IS) techniques. Referring to the experimental results, the Li4SiO4 additive material leads to the improvement of the electrical properties and the value of the total ionic conductivity exceeds 10−4 S∙cm−1 in most studied cases. The factors affecting the enhancement of the total ionic conductivity are discussed. The highest value of σtot = 1.4 × 10−4 S∙cm−1 has been obtained for LATP–0.1LSO material sintered at 1000 °C for 6 h.

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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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The mechanism of enhanced ionic conductivity in Li1.3Al0.3Ti1.7(PO4)3–(0.75Li2O·0.25B2O3) composites

Cited by 32 publications

References 53 publications

B2O3-Doped LATP Glass-Ceramics Studied by X-ray Diffractometry and MAS NMR Spectroscopy Methods

B2O3-Doped LATP Glass-Ceramics Studied by X-ray Diffractometry and MAS NMR Spectroscopy Methods

Electrical and Structural Properties of Li1.3Al0.3Ti1.7(PO4)3—Based Ceramics Prepared with the Addition of Li4SiO4

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

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The mechanism of enhanced ionic conductivity in Li1.3Al0.3Ti1.7(PO4)3–(0.75Li2O·0.25B2O3) composites

Cited by 32 publications

References 53 publications

B2O3-Doped LATP Glass-Ceramics Studied by X-ray Diffractometry and MAS NMR Spectroscopy Methods

B2O3-Doped LATP Glass-Ceramics Studied by X-ray Diffractometry and MAS NMR Spectroscopy Methods

Electrical and Structural Properties of Li1.3Al0.3Ti1.7(PO4)3—Based Ceramics Prepared with the Addition of Li4SiO4

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

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Product

Resources

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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