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Research Article | Open Access

Combined quantitative microscopy on the microstructure and phase evolution in Li1.3Al0.3Ti1.7(PO4)3 ceramics

Deniz Cihan GUNDUZa,b,c( ), Roland SCHIERHOLZa( ), Shicheng YUa, Hermann TEMPELa, Hans KUNGLa, Rüdiger-A. EICHELa,b,c
Forschungszentrum Jülich, Institute of Energy and Climate Research (IEK-9: Fundamental Electrochemistry), Jülich D-52425, Germany
Forschungszentrum Jülich, Institute of Energy and Climate Research (IEK-12: Helmholtz-Institute Münster: Ionics in Energy Storage), Münster D-48149, Germany
RWTH Aachen University, Institute of Physical Chemistry, Aachen D-52074, Germany
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Abstract

Lithium aluminum titanium phosphate (LATP) is one of the materials under consideration as an electrolyte in future all-solid-state lithium-ion batteries. In ceramic processing, the presence of secondary phases and porosity play an important role. In a presence of more than one secondary phase and pores, image analysis must tackle the difficulties about distinguishing between these microstructural features. In this study, we study the phase evolution of LATP ceramics sintered at temperatures between 950 and 1100 ℃ by image segmentation based on energy-dispersive X-ray spectroscopy (EDS) elemental maps combined with quantitative analysis of LATP grains. We found aluminum phosphate (AlPO4) and another phosphate phase ((Lix)PyOz). The amount of these phases changes with sintering temperature. First, since the grains act as an aluminum source for AlPO4 formation, the aluminum content in the LATP grains decreases. Second, the amount of secondary phase changes from more (Lix)PyOz at 950 ℃ to mainly AlPO4 at 1100 ℃ sintering temperature. We also used scanning electron microscopy (SEM) and confocal laser scanning microscopy (CLSM) to study the evolution of the LATP grains and AlPO4, and LATP grain size increases with sintering temperature. In addition, transmission electron microscopy (TEM) was used for the determination of grain boundary width and to identify the amorphous structure of AlPO4.

Keywords

lithium aluminum titanium phosphate (LATP)microstructurequantitative microscopygrain sizeconfocal laser scanning microscopy (CLSM)NASICON

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References

[1]
JB Goodenough, KS Park. The Li-ion rechargeable battery: A perspective. J Am Chem Soc 2013, 135: 1167-1176.
Crossref Google Scholar
[2]
J Janek, WG Zeier. A solid future for battery development. Nat Energy 2016, 1: 16141.
Crossref Google Scholar
[3]
P Jakes, J Granwehr, H Kungl, et al. Mixed ionic–electronic conducting Li4Ti5O12 as anode material for lithium ion batteries with enhanced rate capability–impact of oxygen non-stoichiometry and aliovalent Mg2+-doping studied by electron paramagnetic resonance. Z Phys Chem 2015, 229: 1439-1450.
Crossref Google Scholar
[4]
Y Wang, WD Richards, SP Ong, et al. Design principles for solid-state lithium superionic conductors. Nat Mater 2015, 14: 1026-1031.
Crossref Google Scholar
[5]
JB Bates, NJ Dudney, B Neudecker, et al. Thin-film lithium and lithium-ion batteries. Solid State Ionics 2000, 135: 33-45.
Crossref Google Scholar
[6]
H Aono, E Sugimoto, Y Sadaoka, et al. Ionic conductivity of solid electrolytes based on lithium titanium phosphate. J Electrochem Soc 1990, 137: 1023-1027.
Crossref Google Scholar
[7]
SC Yu, A Mertens, X Gao, et al. Influence of microstructure and AlPO4 secondary-phase on the ionic conductivity of Li1.3Al0.3Ti1.7(PO4)3 solid-state electrolyte. Funct Mater Lett 2016, 9: 1650066.
Google Scholar
[8]
AC Luntz, J Voss, K Reuter. Interfacial challenges in solid-state Li ion batteries. J Phys Chem Lett 2015, 6: 4599-4604.
Crossref Google Scholar
[9]
JC Bachman, S Muy, A Grimaud, et al. Inorganic solid-state electrolytes for lithium batteries: Mechanisms and properties governing ion conduction. Chem Rev 2016, 116: 140-162.
Crossref Google Scholar
[10]
UV Alpen, A Rabenau, GH Talat. Ionic conductivity in Li3N single crystals. Appl Phys Lett 1977, 30: 621-623.
Crossref Google Scholar
[11]
Y Inaguma, LQ Chen, M Itoh, et al. High ionic conductivity in lithium lanthanum titanate. Solid State Commun 1993, 86: 689-693.
Crossref Google Scholar
[12]
A Paulus, S Kammler, S Heuer, et al. Sol gel vs solid state synthesis of the fast lithium-ion conducting solid state electrolyte Li7La3Zr2O12 substituted with iron. J Electrochem Soc 2019, 166: A5403-A5409.
Crossref Google Scholar
[13]
R Murugan, V Thangadurai, W Weppner. Fast lithium ion conduction in garnet-type Li7La3Zr2O12. Angew Chem Int Ed 2007, 46: 7778-7781.
Crossref Google Scholar
[14]
N Kamaya, K Homma, Y Yamakawa, et al. A lithium superionic conductor. Nat Mater 2011, 10: 682-686.
Crossref Google Scholar
[15]
H Wada, M Menetrier, A Levasseur, et al. Preparation and ionic conductivity of new B2S3-Li2S-LiI glasses. Mater Res Bull 1983, 18: 189-193.
Crossref Google Scholar
[16]
H Aono, E Sugimoto, Y Sadaoka, et al. Ionic conductivity and sinterability of lithium titanium phosphate system. Solid State Ionics 1990, 40–41: 38-42.
Crossref Google Scholar
[17]
XF Shang, H Nemori, S Mitsuoka, et al. High lithium-ion- conducting NASICON-type Li1+xAlxGeyTi2–x–y(PO4)3 solid electrolyte. Front Energy Res 2016, 4: 12.
Crossref Google Scholar
[18]
Z Y, XF He, YF Mo. Origin of outstanding stability in the lithium solid electrolyte materials: Insights from thermodynamic analyses based on first-principles calculations. ACS Appl Mater Interfaces 2015, 7: 23685-23693.
Crossref Google Scholar
[19]
M Monchak, T Hupfer, A Senyshyn, et al. Lithium diffusion pathway in Li1.3Al0.3Ti1.7(PO4)3 (LATP) superionic conductor. Inorg Chem 2016, 55: 2941-2945.
Crossref Google Scholar
[20]
T Hupfer, EC Bucharsky, KG Schell, et al. Evolution of microstructure and its relation to ionic conductivity in Li1+xAlxTi2-x(PO4)3. Solid State Ionics 2016, 288: 235-239.
Crossref Google Scholar
[21]
T Hupfer, EC Bucharsky, KG Schell, et al. Influence of the secondary phase LiTiOPO4 on the properties of Li1+xAlxTi2−x(PO4)3 (x=0; 0.3). Solid State Ionics 2017, 302: 49-53.
Crossref Google Scholar
[22]
Rettenwander D, Welzl A, Pristat S, et al. A microcontact impedance study on NASICON-type Li1+xAlxTi2−x(PO4)3 (0 ≤ x ≤ 0.5) single crystals. J Mater Chem A 2016, 4: 1506-1513.10.1039/C5TA08545D
Crossref Google Scholar
[23]
W Xiao, JY Wang, LL Fan, et al. Recent advances in Li1+xAlxTi2−x(PO4)3 solid-state electrolyte for safe lithium batteries. Energy Storage Mater 2019, 19: 379-400.
Crossref Google Scholar
[24]
A Mertens, SC Yu, N Schön, et al. Superionic bulk conductivity in Li1.3Al0.3Ti1.7(PO4)3 solid electrolyte. Solid State Ionics 2017, 309: 180-186.
Crossref Google Scholar
[25]
EC Bucharsky, KG Schell, A Hintennach, et al. Preparation and characterization of sol-gel derived high lithium ion conductive NZP-type ceramics Li1+xAlxTi2−x(PO4)3. Solid State Ionics 2015, 274: 77-82.
Crossref Google Scholar
[26]
K Waetzig, A Rost, U Langklotz, et al. An explanation of the microcrack formation in Li1.3Al0.3Ti1.7(PO4)3 ceramics. J Eur Ceram Soc 2016, 36: 1995-2001.
Crossref Google Scholar
[27]
H Aono, E Sugimoto, Y Sadaoka, et al. Electrical property and sinterability of LiTi2(PO4)3 mixed with lithium salt (Li3PO4 or Li3BO3). Solid State Ionics 1991, 47: 257-264.
Crossref Google Scholar
[28]
K Kwatek, JL Nowiński. Electrical properties of LiTi2(PO4)3 and Li1.3Al0.3Ti1.7(PO4)3 solid electrolytes containing ionic liquid. Solid State Ionics 2017, 302: 54-60.
Crossref Google Scholar
[29]
Sharma N, Dalvi A. Dispersion of Li2SO4-LiPO3 glass in LiTi2(PO4)3 matrix: Assessment of enhanced electrical transport. J Alloys Compd 2019, 782: 288-298.10.1016/j.jallcom.2018.12.153
Crossref Google Scholar
[30]
K Kwatek, JL Nowiński. Solid lithium ion conducting composites based on LiTi2(PO4)3 and Li2.9B0.9S0.1O3.1 glass. Solid State Ionics 2018, 322: 93-99.
Crossref Google Scholar
[31]
K Kwatek, JL Nowiński. The lithium-ion-conducting ceramic composite based on LiTi2(PO4)3 with addition of LiF. Ionics 2019, 25: 41-50.
Crossref Google Scholar
[32]
N Schön, DC Gunduz, SC Yu, et al. Correlative electrochemical strain and scanning electron microscopy for local characterization of the solid state electrolyte Li1.3Al0.3Ti1.7(PO4)3. Beilstein J Nanotechnol 2018, 9: 1564-1572.
Crossref Google Scholar
[33]
D Meertens, M Kruth, K Tillmann. FEI Helios NanoLab 460F1 FIB-SEM. J Large-Scale Res Facil 2016, 2: A59.
Crossref Google Scholar
[34]
M Luysberg, M Heggen, K Tillmann. FEI Tecnai G2 F20. J Large-Scale Res Facil 2016, 2: A77.
Crossref Google Scholar
[35]
A Kovács, R Schierholz, K Tillmann. FEI Titan G2 80-200 CREWLEY. J Large-Scale Res Facil 2016, 2: A43.
Crossref Google Scholar
[36]
E Dashjav, F Tietz. Neutron diffraction analysis of NASICON-type Li1+xAlxTi2-xP3O12, Z Anorg Allg Chemie 2014, 640: 3070-3073.
Crossref Google Scholar
[37]
RW Mooney, MA Aia. Alkaline earth phosphates. Chem Rev 1961, 61: 433-462.
Crossref Google Scholar
[38]
E Metwalli, RK Brow. Modifer effects on the properties and structures of aluminophosphate glasses. J Non-Cryst Solids 2001, 289: 113-122.
Crossref Google Scholar
[39]
F Moreau, A Durán, F Muñoz. Structure and properties of high Li2O-containing aluminophosphate glasses. J Eur Ceram Soc 2009, 29: 1895-1902.
Crossref Google Scholar
[40]
JA Bearden. X-ray wavelengths. Rev Mod Phys 1967, 39: 78-124.
Crossref Google Scholar
[41]
K Kanaya, S Okayama. Penetration and energy-loss theory of electrons in solid targets. J Phys D: Appl Phys 1972, 5: 43-58.
Crossref Google Scholar
[42]
L Hultman, C Mitterer. Thermal stability of advanced nanostructured wear-resistant coatings. In Nanostructured Coatings. A Cavaleiro, JTM De Hosson, Eds. New York: Springer, 2006: 480.
[43]
Rahaman MN. Ceramic Processing. Boca Raton, US: CRC Press, 2007.
[44]
M Saidi, G Coffy, F Sibieude. Les systemes binaires AlPO4–M3PO4 (M=Li, Na, K). J Therm Anal 1995, 44: 15-23.
Crossref Google Scholar
Journal of Advanced Ceramics
Volume 9 Issue 2,
April 2020
Pages 149-161
DOI: 10.1007/s40145-019-0354-0
Cite this article:
GUNDUZ DC, SCHIERHOLZ R, YU S, et al. Combined quantitative microscopy on the microstructure and phase evolution in Li1.3Al0.3Ti1.7(PO4)3 ceramics. Journal of Advanced Ceramics, 2020, 9(2): 149-161. https://doi.org/10.1007/s40145-019-0354-0

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Received: 12 May 2019
Revised: 05 October 2019
Accepted: 02 November 2019
Published: 07 April 2020
© The author(s) 2019

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