Synthesis, Crystal Structure, and Stability of Cubic Li7–xLa3Zr2–xBixO12

Wagner, Reinhard; Rettenwander, Daniel; Redhammer, Günther J.; Tippelt, Gerold; Sabathi, Gebhard; Musso, Maurizio; Stanje, Bernhard; Wilkening, Martin; Suard, Emmanuelle; Amthauer, Georg

doi:10.1021/acs.inorgchem.6b01825

Cited by 51 publications

(36 citation statements)

References 65 publications

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“…To compensate for Li loss during calcination, an excess of 10% of LiNO3 (99.0%, Sigma Aldrich) was utilized. Bi doping was chosen for aliovalent substitution in LLZO garnets at the Zrsite, as it stabilizes the cubic phase formation at significantly lower calcination temperatures than when other dopants are added [25][26][27][28][29]. The high-IC garnet cubic phase was obtained upon powder calcination at 700°C for 10h.…”

Section: Methodsmentioning

confidence: 99%

Ionic conductivity optimization of composite polymer electrolytes through filler particle chemical modification

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et al. 2021

Ionics

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The addition of filler particles to polymer electrolytes is known to increment their ionic conductivity (IC). A detailed understanding of how the interactions between the constituent materials are responsible for the enhancement, remains to be developed. A significant contribution is ascribed to an increment of the polymer amorphous fraction, induced by the fillers, resulting in the formation of higher ionic conductivity channels in the polymer matrix. However, the dependence of IC on the particle weight load and its composition on the polymer morphology is not fully understood. This work investigates Li ion transport in composite polymer electrolytes (CPE) comprising Bi-doped LLZO particles embedded in PEO: LiTFSI matrixes. We find that the IC optimizes for very low particle weight loads (5 -10%) and that both its magnitude and the load required, strongly depend on the garnet particle composition. Based on structural characterization results and electrochemical impedance spectroscopy, a mechanism is proposed to explain these findings. It is suggested that the Li-molar content in the garnet particle controls its interactions with the polymer matrix, resulting at the optimum loads reported, in the formation of high ionic conductivity channels. We propose that filler particle chemical manipulation of the polymer morphology is a promising avenue for the further development of composite polymer electrolytes.

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Section: Methodsmentioning

confidence: 99%

Ionic conductivity optimization of composite polymer electrolytes through filler particle chemical modification

Villa

Verduzco

Libera

et al. 2021

Ionics

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“…[1][2][3][4] Numerous doping elements were tested, including Al, Ga, Ta, Nb, Mo and Fe and conductivities in the range of 10 À4 to 10 À3 S cm À1 have been achieved so far. [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] A lot of recent research has focused on LLZO and knowledge became available on the ideal synthesis route, effects of water, degradation phenomena, maximizing ionic conductivity, conduction paths, etc. However, many aspects are still not understood and several challenges remain.…”

Section: Introductionmentioning

confidence: 99%

Local Li-ion conductivity changes within Al stabilized Li₇La₃Zr₂O₁₂ and their relationship to three-dimensional variations of the bulk composition

et al. 2019

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“…However, the relative intensity of the Li-O stretching band between 300 and 550 cm À1 is obviously reduced showing broadening of the bands in this region, which can be attributed to the disorder caused by the migration of highly mobile Li þ ions along the Li þ diffusion pathways. [30,31] Electrochemical impedance spectroscopy (EIS) studies were carried out on the solid-state electrolytes using a symmetrical cell between two copper sheets at room temperature (25 C) in the frequency range from 0.1 Hz to 1 MHz. The Nyquist plots (Figure 4) consist of an incomplete semicircle and an approximately linear region in the high and low frequency ranges, respectively.…”

Section: Resultsmentioning

confidence: 99%

Ionic Liquid and Polymer Coated Garnet Solid Electrolytes for High‐Energy Solid‐State Lithium Metal Batteries

2021

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Current rechargeable Li-ion batteries (LIBs) employ liquid or polymer electrolytes, which are potentially toxic, flammable, and corrosive, and could result in significant safety issues. [1][2][3] Recent solid-state batteries are promising in overcoming these problems and solid-state batteries can provide high energy densities, which are comparable with traditional LIBs. [4,5] The development of an affordable solid electrolyte, which possesses high ion conductivity and good electrochemical stability, is of great importance. Inorganic type solid electrolytes, such as garnet, have demonstrated good ionic conductivities (%10 À4 S cm À1 at room temperature) and good mechanical strength. [6,7] However, due to their rigid and brittle nature, these ceramic solid electrolytes often have poor contact with the electrodes, which results in high resistance at the electrolyteÀelectrode interfaces. [8,9] In addition, uneven Li/solid electrolyte contact leads to Li dendrites growth during charging. To mitigate the shortcomings of ceramic electrolytes, several strategies have been employed, such as coating the solid electrolytes with a metallic layer including Au, Ge, or Al [10][11][12] and introducing ion conducting layers at the interfaces (polymer, gels, or liquids). [13][14][15] The aim is to fill the voids at the interface ensuring intimate electrode-electrolyte contact. However, on the one hand, Li anode can interact with them forming thick solid electrolyte interphase (SEI) layers. On the other hand, the properties in the bulk layers of the solid electrolytes are not changed. During charge/discharge, the lithium could go beyond these layers and still form dendrites in the bulk layer.Previous results have shown that the integration of metal oxides, such as Al 2 O 3 , SiO 2 , and garnet into a polymer matrix increases the conductivity dramatically compared with that of pure polymer electrolytes. [16][17][18] The metal oxides reduce crystallization of the polymer, which is believed to promote fast Li-ion transportation. The incorporation of ionic liquids (ILs) into polymers, such as poly(ethylene oxide) (PEO) forms an amorphous polymer electrolyte, which also leads to significant increases in conductivity of the resulting hybrid electrolyte. [19][20][21] Furthermore, ILs have high ionic conductivity, high thermal, and electrochemical stability, which makes them good candidates for hybrid electrolyte materials. [22,23] Inspired by these results, in this work, we introduce an ionic liquid to the PEO polymer electrolyte, which can reduce the crystallization of the PEO and enhance the mobility of lithium ions. The PEO-IL mixture was coated on the Ga-doped LLZO solidstate electrolyte. In such a design, the PEO-IL coating improves the electrode-solid electrolyte contact, significantly reducing the interfacial resistance at both electrodes by filling the voids not only at the electrode-electrolyte interfaces but also in the bulk of the material. Their brittle and stiff natures were modified by the PEO-IL coating. This coating can in...

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Synthesis, Crystal Structure, and Stability of Cubic Li_7–xLa₃Zr_2–xBi_xO₁₂

Cited by 51 publications

References 65 publications

Ionic conductivity optimization of composite polymer electrolytes through filler particle chemical modification

Ionic conductivity optimization of composite polymer electrolytes through filler particle chemical modification

Local Li-ion conductivity changes within Al stabilized Li₇La₃Zr₂O₁₂ and their relationship to three-dimensional variations of the bulk composition

Ionic Liquid and Polymer Coated Garnet Solid Electrolytes for High‐Energy Solid‐State Lithium Metal Batteries

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Synthesis, Crystal Structure, and Stability of Cubic Li7–xLa3Zr2–xBixO12

Cited by 51 publications

References 65 publications

Ionic conductivity optimization of composite polymer electrolytes through filler particle chemical modification

Ionic conductivity optimization of composite polymer electrolytes through filler particle chemical modification

Local Li-ion conductivity changes within Al stabilized Li7La3Zr2O12 and their relationship to three-dimensional variations of the bulk composition

Ionic Liquid and Polymer Coated Garnet Solid Electrolytes for High‐Energy Solid‐State Lithium Metal Batteries

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Synthesis, Crystal Structure, and Stability of Cubic Li_7–xLa₃Zr_2–xBi_xO₁₂

Local Li-ion conductivity changes within Al stabilized Li₇La₃Zr₂O₁₂ and their relationship to three-dimensional variations of the bulk composition