Preparation and characterization of sol–gel derived high lithium ion conductive NZP-type ceramics Li1+x AlxTi2−x(PO4)3

Bucharsky, Ethel C.; Schell, Karl G.; Hintennach, Andreas; Hoffmann, Michael J.

doi:10.1016/j.ssi.2015.03.009

Cited by 108 publications

(67 citation statements)

References 33 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…We attribute this effect to the inuence of moisture on ion dynamics; further studies are in progress to elucidate the change in conductivity. Considering the work by Bucharsky et al, 38 the authors found the same inuence of sintering on ionic conductivity. 35 Moreover, LATP turned out to be relatively resistant to static corrosion in a hot, aqueous LiOH solution.…”

Section: Resultsmentioning

confidence: 66%

“…35 Moreover, LATP turned out to be relatively resistant to static corrosion in a hot, aqueous LiOH solution. Hence, the activation energies announced by Bucharsky et al 38 are by a factor of 0.43 too small. 34,37 Values slightly below 0.3 eV seem to accurately describe bulk long-range ion transport.…”

Section: Resultsmentioning

confidence: 87%

“…Irrespective of the conductivity drop observed here, recent studies have been published that demonstrate the usability of water-stable LATP as electrolyte in aqueous battery systems such as Li-air batteries. Worth noting, we have re-calculated the activation energies using the data of Bucharsky et al 38 because there is an error in their publication, which leads to much smaller values for E a : the authors calculated activation energies from a log 10 plot but forgot to take into account the conversion factor of log(e) z 2.3 originating from the log 10 to ln ¼ log e (logarithmus naturalis) transformation. 36 Comparing our activation energies with those recently presented in literature, there is good agreement with recent studies.…”

Section: Resultsmentioning

confidence: 99%

See 2 more Smart Citations

Separating bulk from grain boundary Li ion conductivity in the sol–gel prepared solid electrolyte Li_1.5Al_0.5Ti_1.5(PO₄)₃

et al. 2015

View full text Add to dashboard Cite

Lithium aluminium titanium phosphate (LATP) belongs to one of the most promising solid electrolytes.Besides sufficiently high electrochemical stability, its use in lithium-based all-solid-state batteries crucially depends on the ionic transport properties. While many impedance studies can be found in literature that report on overall ion conductivities, a discrimination of bulk and grain boundary electrical responses via conductivity spectroscopy has rarely been reported so far. Here, we took advantage of impedance measurements that were carried out at low temperatures to separate bulk contributions from the grain boundary responses. It turned out that bulk ion conductivity is by at least three orders of magnitude higher than ion transport across the grain boundary regions. At temperatures well below ambient long-range Li ion dynamics is governed by activation energies ranging from 0.26 to 0.29 eV depending on the sintering conditions. As an example, at temperatures as low as 173 K, the bulk ion conductivity, measured in N 2 inert gas atmosphere, is in the order of 8.1 Â 10 À6 S cm À1 . Extrapolating this value to room temperature yields ca. 3.4 Â 10 À3 S cm À1 at 293 K. Interestingly, exposing the dense pellets to air atmosphere over a long period of time causes a significant decrease of bulk ion transport.This process can be reversed if the phosphate is calcined at elevated temperatures again.

show abstract

Section: Resultsmentioning

confidence: 66%

Section: Resultsmentioning

confidence: 87%

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Separating bulk from grain boundary Li ion conductivity in the sol–gel prepared solid electrolyte Li_1.5Al_0.5Ti_1.5(PO₄)₃

et al. 2015

View full text Add to dashboard Cite

show abstract

“…Only a few materials have been identified whose ionic conductivities are on par with those of liquid electrolytes. 25,[30][31][32] To some extent, the present electrolytes suffer from the disadvantages of high-temperature synthesis routes, reproducibility issues concerning stoichiometry and defect chemistry, blocking grain boundaries, metastability, or even electrochemical instability. 25,[30][31][32] To some extent, the present electrolytes suffer from the disadvantages of high-temperature synthesis routes, reproducibility issues concerning stoichiometry and defect chemistry, blocking grain boundaries, metastability, or even electrochemical instability.…”

Section: Introductionmentioning

confidence: 99%

Very fast bulk Li ion diffusivity in crystalline Li_1.5Al_0.5Ti_1.5(PO₄)₃as seen using NMR relaxometry

Epp

Hammer

et al. 2015

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

The realization of large powerful all-solid-state batteries is still hampered by the availability of environmentally friendly and low-cost Li ion conductors that can easily be produced on a large scale and with high reproducibility. Advanced solid electrolytes benefit from fast ion-selective transport and non-flammability, but they may have low electrochemical stability with respect to Li metal. Sol-gel-synthesized lithium titanium aluminum phosphate Li(1.5)Al(0.5)Ti(1.5)(PO4)3 (LATP), which was prepared via a new synthesis route taking advantage of an annealing step at relatively low temperatures, has the potential to become one of the major players in this field although it may suffer from reduction upon direct contact with metallic lithium. Its ion dynamics is, however, as yet poorly understood. In the present study, (7)Li nuclear magnetic resonance (NMR) spectroscopy was used to monitor the key Li jump processes on the atomic scale. NMR relaxation clearly reveals heterogeneous dynamics comprising distinct ultra-fast and slower diffusion processes. The high Li ion self-diffusion coefficients deduced originate from a rapid Li exchange with activation energies as low as 0.16 eV which means that sol-gel synthesized LATP is superior to other solid electrolytes. Our NMR results fully support recent theoretical investigations on the underlying diffusion mechanism, indicating that to rapidly jump from site to site, the ions use interstitial sites connected by low-energy barriers in LATP.

show abstract

“…Lithium aluminum titanium phosphates (LATP) are one of the best candidates due to their conductivity as high as 3 × 10 −4 S/cm for the optimized composition Li 1+ x Al x Ti 2‐ x (PO 4 ) 3 x = 0.3. A large number of preparation methods are reported for LATP powders in the literature, from solid‐state reactions that could be followed by a mechanical activation, to sol–gel possibly associated with a 3D shaping, co‐precipitation, or hydrothermal reaction . In all cases, extra treatments are then applied for shaping and sintering.…”

Section: Introductionmentioning

confidence: 99%

Dense on Porous Solid LATP Electrolyte System: Preparation and Conductivity Measurement

et al. 2016

View full text Add to dashboard Cite

A dense membrane of lithium aluminum titanium phosphate Li1+xAlxTi2−x(PO4)3, x = 0.3 (LATP) is deposited on a porous LATP substrate via wet chemistry. In the polymerized complex process, phosphate precursors with different active groups and steric hindrance are selected to tune precursor's reactivity. Rheological studies and microstructural observations lead to the selection of an LATP powder slurry charged with lithium, aluminum, titanium, and phosphate ion precursors. The optimized formulation is impregnated into a porous LATP substrate. After thermal treatment, dense LATP membranes on top of a porous LATP substrate are obtained with conductivities as high as 3 × 10−4 S/cm for the dense part, the porous part acting as a mechanical support. An original Van der Pauw impedance setup is validated for the measurement of the ionic conductivity of such dense/porous systems.

show abstract

Preparation and characterization of sol–gel derived high lithium ion conductive NZP-type ceramics Li1+x AlxTi2−x(PO4)3

Cited by 108 publications

References 33 publications

Separating bulk from grain boundary Li ion conductivity in the sol–gel prepared solid electrolyte Li_1.5Al_0.5Ti_1.5(PO₄)₃

Separating bulk from grain boundary Li ion conductivity in the sol–gel prepared solid electrolyte Li_1.5Al_0.5Ti_1.5(PO₄)₃

Very fast bulk Li ion diffusivity in crystalline Li_1.5Al_0.5Ti_1.5(PO₄)₃as seen using NMR relaxometry

Dense on Porous Solid LATP Electrolyte System: Preparation and Conductivity Measurement

Contact Info

Product

Resources

About

Preparation and characterization of sol–gel derived high lithium ion conductive NZP-type ceramics Li1+x AlxTi2−x(PO4)3

Cited by 108 publications

References 33 publications

Separating bulk from grain boundary Li ion conductivity in the sol–gel prepared solid electrolyte Li1.5Al0.5Ti1.5(PO4)3

Separating bulk from grain boundary Li ion conductivity in the sol–gel prepared solid electrolyte Li1.5Al0.5Ti1.5(PO4)3

Very fast bulk Li ion diffusivity in crystalline Li1.5Al0.5Ti1.5(PO4)3as seen using NMR relaxometry

Dense on Porous Solid LATP Electrolyte System: Preparation and Conductivity Measurement

Contact Info

Product

Resources

About

Separating bulk from grain boundary Li ion conductivity in the sol–gel prepared solid electrolyte Li_1.5Al_0.5Ti_1.5(PO₄)₃

Separating bulk from grain boundary Li ion conductivity in the sol–gel prepared solid electrolyte Li_1.5Al_0.5Ti_1.5(PO₄)₃

Very fast bulk Li ion diffusivity in crystalline Li_1.5Al_0.5Ti_1.5(PO₄)₃as seen using NMR relaxometry