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The effect of Ga3+ and Gd3+ on the performance of the composite Li7La3Zr2O12 -PVDF electrolyte membranes for solid-state micro batteries.

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Title: The effect of Ga3+ and Gd3+ on the performance of the composite Li7La3Zr2O12 -PVDF electrolyte membranes for solid-state micro batteries.
Authors: Javaheri, Masoumeh1 (AUTHOR) m.javaheri@merc.ac.ir, Nangir, Mahya1,2 (AUTHOR) m.nangir@merc.ac.ir, Massoudi, Abouzar2 (AUTHOR), Ghadamian, Hossein3 (AUTHOR), Rafiee, Marjan A.4 (AUTHOR)
Source: Materials Chemistry & Physics. Apr2025, Vol. 334, pN.PAG-N.PAG. 1p.
Subjects: Solid electrolytes, Solid state batteries, Energy density, Ionic conductivity, Difluoroethylene, Garnet, Polyelectrolytes, Superionic conductors
Abstract: The effect of Ga3+ and Gd3+ on the ion conductivity of the Li 7 La 3 Zr 2 O 12 (LLZO) garnet-type solid electrolytes for solid-state micro batteries have been investigated. Garnet powder has been synthesized via the solid-state method at 900 °C. The composite solid-state electrolyte membrane is prepared by poly (vinylidene fluoride) as a polymer and garnet particle as a filler. Phase characterization shows a single Ia-3d cubic phase for LLZO without any impurities and a mixture of cubic and tetragonal phases for the doped-LLZO. Microscopic images illustrate quasi-cube particles with smooth surfaces. The impedance spectra show the bulk ion conductivity of 0.18 × 10−4 S cm−1 for undoped-LLZO at RT with an activation energy of 0.44 eV Gd3+ dopant enhances ionic conductivity as high as 0.5 × 10−4 S cm−1 at 90 °C. Replacement of Gd by La with an ionic radius smaller (r Gd = 1.053 Å and r La = 1.16 Å) confirms tightness of LaO 8 dodecahedral and enlargement of ZrO 6 octahedral, providing tilt. Moreover, the first areal discharge capacity of the Li/Ga-LLZO@PVDF/C and Li/Gd-LLZO@PVDF/C cells reaches 381 and 169 μAh cm−2, respectively, at a current rate of 100 μA cm−2. Higher CE and retention for Ga-LLZO@PVDF thin film explains the desired role of Ga dopant in the structure of LLZO for electrochemically stable composite electrolyte for solid-state micro batteries. • Ga and Gd doped garnet-type solid electrolytes are characterized for solid-state micro batteries. • Ga-doping enlarges the interatomic distances of La (1)–O (2) in tetragonal LLZO and Gd-doping causes tight polyhedral LaO 8 , Li (1)O 4 , and Li (2)O 6. • Gd substitution with La provides a more stable cubic phase (84 %) with high ion conductivity of 0.122 × 10−4 S cm−1 at 25 °C and 0.5 × 10−4 S cm−1 at 90 °C. • The Ga3+ as a dopant in the LLZO structure provides the highest areal discharge capacity. • Normalized energy density and power density of the Li/Ga-LLZO@PVDF/C cell is 51.34 μWh cm−2 μm−1 and 13.47 μW cm−2 μm−1. [ABSTRACT FROM AUTHOR]
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Abstract:The effect of Ga3+ and Gd3+ on the ion conductivity of the Li 7 La 3 Zr 2 O 12 (LLZO) garnet-type solid electrolytes for solid-state micro batteries have been investigated. Garnet powder has been synthesized via the solid-state method at 900 °C. The composite solid-state electrolyte membrane is prepared by poly (vinylidene fluoride) as a polymer and garnet particle as a filler. Phase characterization shows a single Ia-3d cubic phase for LLZO without any impurities and a mixture of cubic and tetragonal phases for the doped-LLZO. Microscopic images illustrate quasi-cube particles with smooth surfaces. The impedance spectra show the bulk ion conductivity of 0.18 × 10−4 S cm−1 for undoped-LLZO at RT with an activation energy of 0.44 eV Gd3+ dopant enhances ionic conductivity as high as 0.5 × 10−4 S cm−1 at 90 °C. Replacement of Gd by La with an ionic radius smaller (r Gd = 1.053 Å and r La = 1.16 Å) confirms tightness of LaO 8 dodecahedral and enlargement of ZrO 6 octahedral, providing tilt. Moreover, the first areal discharge capacity of the Li/Ga-LLZO@PVDF/C and Li/Gd-LLZO@PVDF/C cells reaches 381 and 169 μAh cm−2, respectively, at a current rate of 100 μA cm−2. Higher CE and retention for Ga-LLZO@PVDF thin film explains the desired role of Ga dopant in the structure of LLZO for electrochemically stable composite electrolyte for solid-state micro batteries. • Ga and Gd doped garnet-type solid electrolytes are characterized for solid-state micro batteries. • Ga-doping enlarges the interatomic distances of La (1)–O (2) in tetragonal LLZO and Gd-doping causes tight polyhedral LaO 8 , Li (1)O 4 , and Li (2)O 6. • Gd substitution with La provides a more stable cubic phase (84 %) with high ion conductivity of 0.122 × 10−4 S cm−1 at 25 °C and 0.5 × 10−4 S cm−1 at 90 °C. • The Ga3+ as a dopant in the LLZO structure provides the highest areal discharge capacity. • Normalized energy density and power density of the Li/Ga-LLZO@PVDF/C cell is 51.34 μWh cm−2 μm−1 and 13.47 μW cm−2 μm−1. [ABSTRACT FROM AUTHOR]
ISSN:02540584
DOI:10.1016/j.matchemphys.2025.130418