Field assisted sintering of fine-grained Li7−3La3Zr2Al O12 solid electrolyte and the influence of the microstructure on the electrochemical performance

Botros, Miriam; Djenadic, Ruzica; Clemens, Oliver; Möller, Matthias; Hahn, Horst

doi:10.1016/j.jpowsour.2016.01.086

Cited by 87 publications

(73 citation statements)

References 27 publications

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“…S.cm -1 for S1-SPS and S2-SPS respectively, comparable to the ones reported in literature [17,21]. Activation energies (E a ) extracted from Arrhenius plots were E a = 0.46 eV and 0.42 eV for S1-SPS and S2-SPS, respectively, slightly higher than reported values [3,12,15].…”

Section: Ionic Conductivitysupporting

confidence: 87%

Bulk Li mobility enhancement in Spark Plasma Sintered Li(7−3x)AlxLa3Zr2O12 garnet

Castillo

Charpentier

Rapaud

et al. 2018

Ceramics International

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Li (7−3x) Al x La 3 Zr 2 O 12 (LLAZO) Al-doped garnets display high ionic conductivity in the range of ~10 -4 S.cm -1 at room temperature and are thus envisioned for future solid-state batteries. In this study, LLAZO powders with two doping levels were synthetized using a solid-state route and sintered using Spark Plasma Sintering (SPS). Both pristine and SPS crushed pellet powders were investigated using X-Ray Diffraction (XRD) confirming the formation of the most conducting cubic phase. Ionic conductivity measurements were performed using electrochemical impedance spectroscopy. Li and Al distributions among available sites were identified using Magic Angle Spinning (MAS) Nuclear Magnetic Resonance (NMR) experiments, and Li mobility was explored using 7 Li static wideline NMR spectroscopy.Results show that SPS treatment, beyond producing highly densified pellets, mainly modifies Al distribution and strongly impacts the bulk Li + mobility.

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Section: Ionic Conductivitysupporting

confidence: 87%

Bulk Li mobility enhancement in Spark Plasma Sintered Li(7−3x)AlxLa3Zr2O12 garnet

Castillo

Charpentier

Rapaud

et al. 2018

Ceramics International

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“…Despite the fact that the density cannot be quantified via SEM, a comparison of the cross-section image (Fig. 2a) with SEM images of sintered LLZO pellets with reported densities above 90% [26][27][28][29] confirms the highly dense nature of the LA-CVD grown LLZO film. A film thickness of around 850 nm is estimated from this cross-section for the deposition on Si.…”

Section: Resultsmentioning

confidence: 77%

“…Especially the overall density is known to play a crucial role for obtaining high conductivities. Considerable effort has been made to achieve higher densities for bulk ceramics using nano-grained LLZO, 26 field assisted sintering technique for compaction, 27,28 or sintering aids like Ga. 29 Therefore, the fact that the performance of the tetragonal LLZO thin film grown by LA-CVD is among the best values reported for tetragonal LLZO so far, is attributed primarily to the high density of the film (see Fig. 2).…”

Section: Assignment Of the R1-cpe1 Element To The LI 7 La 3 Zr 2 O 12mentioning

confidence: 99%

Garnet-Type Li₇La₃Zr₂O₁₂Solid Electrolyte Thin Films Grown by CO₂-Laser Assisted CVD for All-Solid-State Batteries

Loho

Djenadic

Bruns

et al. 2016

J. Electrochem. Soc.

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114

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The detailed characterization of garnet-type Li-ion conducting Li 7 La 3 Zr 2 O 12 (LLZO) solid electrolyte thin films grown by novel CO 2 -laser assisted chemical vapor deposition (LA-CVD) is reported. A deposition process parameter study reveals that an optimal combination of deposition temperature and oxygen partial pressure is essential to obtain high quality tetragonal LLZO thin films. The polycrystalline tetragonal LLZO films grown on platinum have a dense and homogeneous microstructure and are free of cracks. A total lithium ion conductivity of 4.2 · 10 −6 S · cm −1 at room temperature, with an activation energy of 0.50 eV, is achieved. This is the highest total lithium ion conductivity value reported for tetragonal LLZO thin films so far, being about one order of magnitude higher than previously reported values for tetragonal LLZO thin films prepared by sputtering and pulsed laser deposition. The results of this study suggest that the tetragonal LLZO thin films grown by LA-CVD are applicable for the use in all-solid-state thin film lithium ion batteries. Over the last decades a progressive miniaturization of electronic components took place. As a result there is an increasing demand for micro-sized power sources that drives the current research on thin film batteries. Possible applications range from sensors and radiofrequency identification tags to implantable medical devices. For these applications an all-solid-state thin film Li-ion battery is desirable due to considerable advantages such as excellent safety properties and easy integration in microelectronics. Furthermore, the energy density of such an all-solid-state cell can be increased compared to a cell with conventional liquid electrolyte, if the chosen solid electrolyte material is stable toward high voltage cathode materials as well as toward a lithium metal anode. The garnet-type solid electrolyte Li 7 La 3 Zr 2 O 12 (LLZO), first reported in 2007 by Murugan et al., 1 is a material that combines those properties with reasonably high lithium ion conductivity of up to 2.3 · 10 −5 S · cm −1 in its tetragonal 2 and up to 1.2 · 10 −3S · cm −1 in its cubic 3 modification. However, these high conductivity values have so far only been achieved for bulk ceramics, but not for thin films. Apparently, over the last years researchers have focused on the optimization of the lithium ion conductivity in bulk ceramics, e.g. by stabilization of the cubic LLZO phase via doping, 4,5 while only a few publications have addressed LLZO thin film deposition at all. 6-12The advantage of thin films is that their lithium ion conductivity for the use in an all-solid-state battery does not need to be as high as compared to bulk solid electrolytes, taking into account the electrolyte resistance R:where A is the contact area, l is the thickness and σ is the Li-ion conductivity of the solid electrolyte, respectively. For example, in their recent study Liu et al. 13 report on a functioning bulk all-solid-state battery using cubic LLZO as solid electrolyte with ∼ 1 mm thickn...

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“…The specific capacitance of the semicircle was ca. 10 −9 F, suggesting the semi-circle is attributed to the grain-boundary [28]. Figure 7(c) compares the temperature dependence of the conductivity of each component.…”

Section: Electrochemical Propertiesmentioning

confidence: 98%

“…Spark plasma sintering (SPS), which is also known as field assisted sintering technique (FAST) or pulsed electric current sintering (PECS), is one of techniques to sinter materials with assistance of uniaxial pressure and pulsed electric current [26][27][28]. [26].…”

Section: Introductionmentioning

confidence: 99%

Sintering Mechanisms of High-Performance Garnet-type Solid Electrolyte Densified by Spark Plasma Sintering

Yamada

Ito

Basappa

2016

Electrochimica Acta

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Garnet-type solid electrolyte Li6.5La3Zr1.5Ta0.5O12 (LLZT) was densified by using a spark plasma sintering (SPS) technique. Formation of impurities in the obtained pellets was studied in detail. It is revealed that impurities are strongly related to the SPS process: electrolysis of LLZT and electromigration of graphite. The electrolysis results in La2Zr2O7 on anode of the SPS process, which is accompanied by reduction of Li2CO3 to amorphous carbon on cathode. The electrolysis on SPS could be successfully suppressed by employing LLZT powder without Li2CO3. When these impurities were removed, pellets obtained by SPS exhibited electrochemical performance comparable with those densified by other methods: total ionic conductivity of 6.9 × 10 −4 S cm −1 at 298 K and short-circuit prevention up to 100 μA cm −2 on dc polarization. The results confirm great advantage of SPS on manufacturing the dense garnet-type solid electrolytes: a lowtemperature (900-1100°C) and short-sintering-time process (10 min).

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Field assisted sintering of fine-grained Li7−3La3Zr2Al O12 solid electrolyte and the influence of the microstructure on the electrochemical performance

Cited by 87 publications

References 27 publications

Bulk Li mobility enhancement in Spark Plasma Sintered Li(7−3x)AlxLa3Zr2O12 garnet

Bulk Li mobility enhancement in Spark Plasma Sintered Li(7−3x)AlxLa3Zr2O12 garnet

Garnet-Type Li₇La₃Zr₂O₁₂Solid Electrolyte Thin Films Grown by CO₂-Laser Assisted CVD for All-Solid-State Batteries

Sintering Mechanisms of High-Performance Garnet-type Solid Electrolyte Densified by Spark Plasma Sintering

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Field assisted sintering of fine-grained Li7−3La3Zr2Al O12 solid electrolyte and the influence of the microstructure on the electrochemical performance

Cited by 87 publications

References 27 publications

Bulk Li mobility enhancement in Spark Plasma Sintered Li(7−3x)AlxLa3Zr2O12 garnet

Bulk Li mobility enhancement in Spark Plasma Sintered Li(7−3x)AlxLa3Zr2O12 garnet

Garnet-Type Li7La3Zr2O12Solid Electrolyte Thin Films Grown by CO2-Laser Assisted CVD for All-Solid-State Batteries

Sintering Mechanisms of High-Performance Garnet-type Solid Electrolyte Densified by Spark Plasma Sintering

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Garnet-Type Li₇La₃Zr₂O₁₂Solid Electrolyte Thin Films Grown by CO₂-Laser Assisted CVD for All-Solid-State Batteries