journal article·2022-01Open access

Conductivity, microstructure and mechanical properties of tape-cast LATP with LiF and SiO2 additives

Jürgen Peter Gross, Jürgen Malzbender, Enkhtsetseg Dashjav, Frank Tietz, Ruth Schwaiger

Journal of Materials Science· Volume 57· Issue 2

Abstract

Abstract LATP sheets with LiF and SiO2 addition prepared by tape cast as electrolytes for solid-state batteries were characterized regarding conductivity, microstructure and mechanical properties aiming toward an optimized composition. The use of additives permitted a reduction of the sintering temperature. Rietveld analyses of the samples with additives revealed a phase mixture of NaSICON modifications crystallizing with rhombohedral and orthorhombic symmetry as a superstructure with space group Pbca. It seems that LiF acts as a sintering additive but also as a mineralizer for the superstructure of LATP. As general trend, higher LiF to SiO2 ratios led to lower porosities and higher values of elastic modulus and hardness determined by indentation testing, but the presence of the orthorhombic LATP leads to a decrease in the ionic conductivity. Micro-pillar testing was used to assess the crack growth behavior revealing weak grain boundaries.
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Research context

OpenAlex topics: Advanced Battery Materials and Technologies · Advancements in Battery Materials · Conducting polymers and applications

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References (48)

Show source-provided references
1. T. Famprikis, P. Canepa, J. A. Dawson, M. S. Islam, and C. Masquelier (2019) Fundamentals of inorganic solid-state electrolytes for batteries. Nature materials, pp. 1–14.10.1038/s41563-019-0431-3 ↗
2. Placke T, Kloepsch R, Dühnen S, Winter M (2017) Lithium ion, lithium metal, and alternative rechargeable battery technologies: the odyssey for high energy density. J Solid State Electrochem 21(7):1939–196410.1007/s10008-017-3610-7 ↗
3. Goodenough JB, Hong H-P, Kafalas J (1976) Fast Na+-ion transport in skeleton structures. Mater Res Bull 11(2):203–22010.1016/0025-5408(76)90077-5 ↗
4. Hong H-P (1976) Crystal structures and crystal chemistry in the system Na1+ xZr2SixP3− xO12. Mater Res Bull 11(2):173–18210.1016/0025-5408(76)90073-8 ↗
5. Fu J (1997) Superionic conductivity of glass-ceramics in the system Li 2O-Al 2O 3-TiO 2-P 2O 5. Solid State Ionics 96(3–4):195–20010.1016/S0167-2738(97)00018-0 ↗
6. Jackman SD, Cutler RA (2012) Effect of microcracking on ionic conductivity in LATP. J Power Sources 218:65–7210.1016/j.jpowsour.2012.06.081 ↗
7. Soman S, Iwai Y, Kawamura J, Kulkarni A (2012) Crystalline phase content and ionic conductivity correlation in LATP glass–ceramic. J Solid State Electrochem 16(5):1761–176610.1007/s10008-011-1592-4 ↗
8. Kothari DH, Kanchan D (2016) Effect of doping of trivalent cations Ga3+, Sc3+, Y3+ in Li1. 3Al0. 3Ti1. 7 (PO4) 3 (LATP) system on Li+ ion conductivity. Physica B 501:90–9410.1016/j.physb.2016.08.020 ↗
9. Duluard S et al (2017) Dense on porous solid LATP electrolyte system: Preparation and conductivity measurement. J Am Ceram Soc 100(1):141–14910.1111/jace.14451 ↗
10. Kotobuki M, Koishi M (2013) Preparation of Li1. 5Al0. 5Ti1. 5 (PO4) 3 solid electrolyte via a sol–gel route using various Al sources. Ceram Int 39(4):4645–464910.1016/j.ceramint.2012.10.206 ↗
11. Kotobuki M, Koishi M, Kato Y (2013) Preparation of Li 1.5 Al 0.5 Ti 1.5 (PO 4) 3 solid electrolyte via a co-precipitation method. Ionics 19(12):1945–194810.1007/s11581-013-1000-4 ↗
12. Bucharsky E, Schell K, Hintennach A, Hoffmann M (2015) Preparation and characterization of sol–gel derived high lithium ion conductive NZP-type ceramics Li1+ x AlxTi2− x (PO4) 3. Solid State Ionics 274:77–8210.1016/j.ssi.2015.03.009 ↗
13. Ma F et al (2016) Preparation and evaluation of high lithium ion conductivity Li1. 3Al0. 3Ti1. 7 (PO4) 3 solid electrolyte obtained using a new solution method. Solid State Ionics 295:7–1210.1016/j.ssi.2016.07.010 ↗
14. Morimoto H et al (2013) Preparation of lithium ion conducting solid electrolyte of NASICON-type Li1+ xAlxTi2− x (PO4) 3 (x= 0.3) obtained by using the mechanochemical method and its application as surface modification materials of LiCoO2 cathode for lithium cell. J Power Sources 240:636–64310.1016/j.jpowsour.2013.05.039 ↗
15. Kim KM, Shin DO, Lee Y-G (2015) Effects of preparation conditions on the ionic conductivity of hydrothermally synthesized Li1+ xAlxTi2-x (PO4) 3 solid electrolytes. Electrochim Acta 176:1364–137310.1016/j.electacta.2015.07.170 ↗
16. Deng Z, Wang Z, Chu I-H, Luo J, Ong SP (2016) Elastic properties of alkali superionic conductor electrolytes from first principles calculations. J Electrochem Soc 163(2):A67–A7410.1149/2.0061602jes ↗
17. Nonemacher JF, Naqash S, Tietz F, Malzbender J (2019) Micromechanical assessment of Al/Y-substituted NASICON solid electrolytes. Ceram Int 45(17):21308–2131410.1016/j.ceramint.2019.07.114 ↗
18. Yan G et al (2019) Influence of sintering temperature on conductivity and mechanical behavior of the solid electrolyte LATP. Ceram Int 45(12):14697–1470310.1016/j.ceramint.2019.04.191 ↗
19. Cho Y-H, Wolfenstine J, Rangasamy E, Kim H, Choe H, Sakamoto J (2012) Mechanical properties of the solid Li-ion conducting electrolyte: Li 0.33 La 0.57 TiO 3. J Mater Sci 47:5970–5977. https://doi.org/10.1007/s10853-012-6500-510.1007/s10853-012-6500-5 ↗
20. Yan G et al (2012) Fracture behavior of solid electrolyte LATP material based on micro-pillar splitting method. J Eur Ceram Soc 41(10):5240–524710.1016/j.jeurceramsoc.2021.04.026 ↗
21. Monroe C, Newman J (2005) The impact of elastic deformation on deposition kinetics at lithium/polymer interfaces. J Electrochem Soc 152(2):A396–A40410.1149/1.1850854 ↗
22. Zhang M et al (2014) Solid state lithium ionic conducting thin film Li1. 4Al0. 4Ge1. 6 (PO4) 3 prepared by tape casting. J Alloy Compd 590:147–15210.1016/j.jallcom.2013.12.100 ↗
23. Sebastiani M, Renzelli M, Battaini P, Bemporad E (2014) Focused ion beam and nanomechanical tests for high resolution surface characterisation: new resources for platinum group metals testing. Platin Met Rev 58(1):3–1910.1595/147106714X675768 ↗
24. Sebastiani M, Johanns K, Herbert EG, Carassiti F, Pharr GM (2015) A novel pillar indentation splitting test for measuring fracture toughness of thin ceramic coatings. Phil Mag 95(16–18):1928–194410.1080/14786435.2014.913110 ↗
25. Sebastiani M, Johanns K, Herbert EG, Pharr GM (2015) Measurement of fracture toughness by nanoindentation methods: Recent advances and future challenges. Curr Opin Solid State Mater Sci 19(6):324–33310.1016/j.cossms.2015.04.003 ↗
26. Thokchom JS, Kumar B (2010) The effects of crystallization parameters on the ionic conductivity of a lithium aluminum germanium phosphate glass–ceramic. J Power Sources 195(9):2870–287610.1016/j.jpowsour.2009.11.037 ↗
27. Dashjav E et al (2020) Microstructure, ionic conductivity and mechanical properties of tape-cast Li1.5Al0.5Ti1.5P3O12 electrolyte sheets. J Eur Ceram Soc 40(5):1975–198210.1016/j.jeurceramsoc.2020.01.017 ↗
28. Marder R, Chaim R, Chevallier G, Estournès C (2011) Effect of 1 wt% LiF additive on the densification of nanocrystalline Y2O3 ceramics by spark plasma sintering. J Eur Ceram Soc 31(6):1057–106610.1016/j.jeurceramsoc.2010.12.032 ↗
29. Luo W, Xie R, Ivanov M, Pan Y, Kou H, Li J (2017) Effects of LiF on the microstructure and optical properties of hot-pressed MgAl2O4 ceramics. Ceram Int 43(9):6891–689710.1016/j.ceramint.2017.02.110 ↗
30. Hao Y-Z, Yang H, Chen G-H, Zhang Q-L (2013) Microwave dielectric properties of Li2TiO3 ceramics doped with LiF for LTCC applications. J Alloy Compd 552:173–17910.1016/j.jallcom.2012.10.110 ↗
31. Naqash S, Ma Q, Tietz F, Guillon O (2017) Na3Zr2 (SiO4) 2 (PO4) prepared by a solution-assisted solid state reaction. Solid State Ionics 302:83–9110.1016/j.ssi.2016.11.004 ↗
32. Dashjav E et al (2018) The influence of water on the electrical conductivity of aluminum-substituted lithium titanium phosphates. Solid State Ionics 321:83–9010.1016/j.ssi.2018.04.010 ↗
33. de Boer GB, de Weerd C, Thoenes D, Goossens HW (1987) Laser diffraction spectrometry: Fraunhofer diffraction versus Mie scattering. Part Part Syst Charact 4(1–4):14–1910.1002/ppsc.19870040104 ↗
34. Yan G et al (2019) Anisotropy of the mechanical properties of Li1 3Al0 3Ti1 7 (PO4) 3 solid electrolyte material. J Power Sour 437:22694010.1016/j.jpowsour.2019.226940 ↗
35. Wang A-N, Nonemacher JF, Yan G, Finsterbusch M, Malzbender J, Krüger M (2018) Mechanical properties of the solid electrolyte Al-substituted Li7La3Zr2O12 (LLZO) by utilizing micro-pillar indentation splitting test. J Eur Ceram Soc 38(9):3201–320910.1016/j.jeurceramsoc.2018.02.032 ↗
36. Zou Y, Malzbender J (2016) Development and optimization of porosity measurement techniques. Ceram Int 42(2):2861–287010.1016/j.ceramint.2015.11.015 ↗
37. Schneider CA, Rasband WS, Eliceiri KW (2012) NIH Image to ImageJ: 25 years of image analysis. Nat Methods 9(7):671–67510.1038/nmeth.2089 ↗
38. Lauener CM, Petho L, Chen M, Xiao Y, Michler J, Wheeler JM (2018) Fracture of silicon: influence of rate, positioning accuracy, FIB machining, and elevated temperatures on toughness measured by pillar indentation splitting. Mater Des 142:340–34910.1016/j.matdes.2018.01.015 ↗
39. Kojima H, Whiteway S, Masson C (1968) Melting points of inorganic fluorides. Can J Chem 46(18):2968–297110.1139/v68-494 ↗
40. Catti M (2001) A mixed α/β superstructure in NASICON ionic conductors: Neutron diffraction study of Li2FeTi (PO4) 3 and Li2FeZr (PO4) 3. J Solid State Chem 156(2):305–31210.1006/jssc.2000.8999 ↗
41. Hirschorn B, Orazem ME, Tribollet B, Vivier V, Frateur I, Musiani M (2010) Determination of effective capacitance and film thickness from constant-phase-element parameters. Electrochim Acta 55(21):6218–622710.1016/j.electacta.2009.10.065 ↗
42. Naqash S, Sebold D, Tietz F, Guillon O (2019) Microstructure–conductivity relationship of Na3Zr2 (SiO4) 2 (PO4) ceramics. J Am Ceram Soc 102(3):1057–107010.1111/jace.15988 ↗
43. Rettenwander D et al (2016) A microcontact impedance study on NASICON-type Li 1+ x Al x Ti 2–x (PO 4) 3 (0≤ x≤ 0.5) single crystals. J Mater Chem A 4(4):1506–151310.1039/C5TA08545D ↗
44. Wolfenstine J, Allen JL, Sakamoto J, Siegel DJ, Choe H (2018) Mechanical behavior of Li-ion-conducting crystalline oxide-based solid electrolytes: a brief review. Ionics 24(5):1271–127610.1007/s11581-017-2314-4 ↗
45. Wang JC (1984) Young’s modulus of porous materials. J Mater Sci 19:801–808. https://doi.org/10.1007/BF0054045110.1007/BF00540451 ↗
46. Phani KK, Niyogi S (1987) Young’s modulus of porous brittle solids. J Mater Sci 22:257–263. https://doi.org/10.1007/BF0116058110.1007/BF01160581 ↗
47. Fryxell R, Chandler B (1964) Creep, strength, expansion, and elastic moduli of sintered BeO as a function of grain size, porosity, and grain orientation. J Am Ceram Soc 47(6):283–29110.1111/j.1151-2916.1964.tb14417.x ↗
48. Ramakrishnan N, Arunachalam V (1990) Effective elastic moduli of porous solids. J Mater Sci 25:3930–3937. https://doi.org/10.1007/BF0058246210.1007/BF00582462 ↗