Influence of preparation temperature on ionic conductivity of titanium-defective Li1+4xTi2−x(PO4)3 NASICON-type materials
Source abstract
Abstract
NASICON-type Li1+4xTi2−x(PO4)3 samples (0 ≤ x ≤ 0.2) have been synthesized by conventional solid-state reaction. Structural factors that affect Li conductivity were investigated with powder X-ray diffraction (XRD), scanning electron microscopy, nuclear magnetic resonance (NMR) and impedance spectroscopy techniques. The increment in lithium enhances Li–Li repulsions and increases Li conductivity of x = 0.1 samples with two orders of magnitude with respect to that of the stoichiometric x = 0 sample. In LiTi2(PO4)3 phase, Li ions mainly occupy sixfold M1 sites (CQ ~ 40 kHz), while in Li1+4xTi2−x(PO4)3 samples, Li ions are also allocated near triangular windows that connect M1 and M2 cavities (CQ ~ 60 kHz). T he Li rearrangement increases long-range motions of lithium. XRD and 31P MAS-NMR patterns showed variable amounts of secondary LiTiPO5, TiP2O7 and Li4P2O7 phases besides NASICON compounds. The formation of non-conducting secondary phases at the surface of NASICON particles decreases overall conductivity of x = 0.2 samples. The Li1.4Ti1.9(PO4)3 (x = 0.1 sample) prepared at 800 °C displays at room temperature high "bulk" conductivity, 1.6 × 10−4 S cm−1, low activation energy, 0.30 eV, and good overall DC conductivity, 2.7 × 10–6 S cm−1. The small amount of secondary phases detected in this sample makes it a good candidate for solid electrolyte in all solid-state batteries.
Source: openaire · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: Advancements in Battery Materials · Advanced Battery Materials and Technologies · Chemical Synthesis and Characterization
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (44)
Show source-provided references
1. Oudenhoven JFM, Baggetto L, Notten PHL (2011) All-solid-state lithium-ion microbatteries: a review of various three-dimensional concept. Adv Energy Mater 1:110–133
2. Kotobuki M, Suzuki Y, Kanamura K, Sato Y, Yamamoto K, Yoshida T (2011) A novel structure of ceramics electrolyte for future lithium battery. J Power Sources 196:9815–981910.1016/j.jpowsour.2011.07.005 ↗
3. Braga MH, Grundish NS, Murchison AJ, Goodenough JB (2017) Alternative strategy for a safe rechargeable battery. Energy Environ Sci 10:331–33610.1039/C6EE02888H ↗
4. Chen K, Huang M, Shen Y, Lin Y, Nan CW (2012) Enhancing ionic conductivity of Li0.35La0.55TiO3 ceramics by introducing Li7La3Zr2O12. Electrochim Acta 80:133–13910.1016/j.electacta.2012.06.115 ↗
5. Dumon A, Huang M, Shen Y, Nan CW (2013) High Li ion conductivity in strontium doped Li7La3Zr2O12 garnet. Solid State Ion 243:36–4110.1016/j.ssi.2013.04.016 ↗
6. Tsai CL, Roddatis V, Chandran CV, Ma Q, Uhlenbruck S, Bram M, Heitjans P, Guillon O (2016) Li7La3Zr2O12 interface modification for Li dendrite prevention. ACS Appl Mater Interfaces 8:10617–1062610.1021/acsami.6b00831 ↗
7. Wei J, Kim H, Lee DC, Hu R, Wu F, Zhao H, Alamgir F, Yushin G (2015) Influence of annealing on ionic transfer and storage stability of Li2S–P2S5 solid electrolyte. J Power Sources 294:494–50010.1016/j.jpowsour.2015.06.074 ↗
8. Arbi K, Hoelzel M, Kuhn A, García-Alvarado F, Sanz J (2013) Structural factors that enhance lithium mobility in fast-ion Li1+xTi2−xAlx(PO4)3 (0 ≤ x ≤ 0.4) conductors investigated by neutron diffraction in the temperature range 100–500 K. Inorgan Chem 52:9290–929610.1021/ic400577v ↗
9. Kahlaoui R, Arbi K, Sobrados I, Jimenez R, Sanz J, Ternane R (2017) Cation miscibility and lithium mobility in NASICON Li1+xTi2−xScx(PO4)3 (0 ≤ x ≤ 0.5) series: a combined NMR and impedance study. Inorgan Chem 56:1216–122410.1021/acs.inorgchem.6b02274 ↗
10. Weiss M, Weber DA, Senyshyn A, Janek J, Zeier WG (2018) Correlating transport and structural properties in Li1+xAlxGe2−x(PO4)3 (LAGP) prepared from aqueous solution. ACS Appl Mater Interfaces 10(13):10935–1094410.1021/acsami.8b00842 ↗
11. Morin E, Angenault J, Couturier JC, Quarton M, He H, Klinowski J (1997) Phase transition and crystal structures of LiSn2(PO4)3. Eur J Solid State Inorgan Chem 34:947–958
12. Catti M, Stramare S, Ibberson R (1999) Lithium location in NASICON-type Li+ conductors by neutron diffraction I. Triclinic α′-LiZr2(PO4)3. Solid State Ionics 123:173–18010.1016/S0167-2738(99)00089-2 ↗
13. Losilla ER, Aranda MAG, Martinez-Lara M, Bruque S (1997) Reversible triclinic-rhombohedral phase transition in LiHf2(PO4)3: crystal structures from neutron powder diffraction. Chem Mater 9:1678–168510.1021/cm970078n ↗
14. Aono H, Sugimoto E, Sadaoka Y, Imanoka N, Adachi G (1990) Ionic conductivity of solid electrolytes based on lithium titanium phosphate. J Electrochem Soc 137:1023–102710.1149/1.2086597 ↗
15. Arbi K, Lazarraga MG, Ben Hassen Chehimi D, Ayadi-Trabelsi M, Rojo JM, Sanz J (2004) Lithium mobility in Li1.2Ti1.8R0.2(PO4)3 compounds (R = Al, Ga, Sc, In) as followed by NMR and impedance spectroscopy. Chem Mater 16:255–26210.1021/cm030422i ↗
16. Pérez-Estébanez M, Isasi-Marín J, Többens DM, Rivera Calzada A, León C (2014) A systematic study of Nasicon-type Li1+xMxTi2−x(PO4)3 (M: Cr, Al, Fe) by neutron diffraction and impedance spectroscopy. Solid State Ion 266:1–810.1016/j.ssi.2014.07.018 ↗
17. Catti M, Comotti A, Di Blas S, Ibberson RM (2004) Extensive lithium disorder in Li1.5Fe0.5Ti1.5(PO4)3 Nasicon by neutron diffraction, and the Li1+xFexTi2−x(PO4)3 phase diagram. J Mater Chem 14:835–83910.1039/B312865B ↗
18. Monchak M, Hupfer T, Senyshyn A, Boysen H, Chernyshov D, Hansen T, Schell KG, Bucharsky EC, Hoffmann MJ, Ehrenberg H (2016) Lithium diffusion pathway in Li(1.3)Al(0.3)Ti(1.7)(PO4)3 (LATP) superionic conductor. Inorgan Chem 55:2941–294510.1021/acs.inorgchem.5b02821 ↗
19. Arbi K, Tabellout M, Sanz J (2010) NMR and electric impedance study of lithium mobility in fast ion conductors LiTi2−xZrx(PO4)3 (0 ≤ x ≤ 2). Solid State Ion 180:1613–161910.1016/j.ssi.2009.11.010 ↗
20. Kahlaoui R, Arbi K, Jimenez R, Sobrados I, Sanz J, Ternane R (2018) Distribution and mobility of lithium in NASICON-type Li1−xTi2−xNbx(PO4)3 (0 ≤ x ≤ 0.5) compounds. Mater Res Bull 101:146–15410.1016/j.materresbull.2018.01.022 ↗
21. Orliukas AF, Venckutė V, Miškinis J, Kazlauskienė V, Petrulionis D, Šalkus T, Dindune A, Kanepe Z, Ronis J, Žukauskas T, Maneikis A, Kežionis A (2013) X-ray photoelectron and broadband impedance spectroscopy of Li1+4xTi2−x(PO4)3 solid electrolyte ceramics. Lith J Phys 53:244–25410.3952/physics.v53i4.2767 ↗
22. Best AS, Forsyth M, MacFarlane DR (2000) Stoichiometric changes in lithium conducting materials based on Li1+xTi2−xAlx(PO4)3: impedance, X-ray and NMR studies. Solid State Ion 136:339–34410.1016/S0167-2738(00)00493-8 ↗
23. Bhanja P, Senthil C, Patra AK, Sasidharan M, Bhaumik A (2017) NASICON type ordered mesoporous lithium–aluminium–titanium–phosphate as electrode material for lithium-ion batteries. Micropor Mesopor Mater 240:57–6410.1016/j.micromeso.2016.11.005 ↗
24. Rietveld HM (1969) A profile refinement method for nuclear and magnetic structures. J Appl Crystallogr 2:65–7110.1107/S0021889869006558 ↗
25. Rodríguez-Carvajal J (1993) Recent advances in magnetic structure determination by neutron powder diffraction. J Phys B 192:55–6910.1016/0921-4526(93)90108-I ↗
26. Bruker WINFIT Program (1994) Bruker Rep. 140:43–46
27. Kosova NV, Osintsev DI, Uvarov NF, Devyatkina ET (2005) Lithium titanium phosphate as cathode, anode, and electrolyte for lithium rechargeable batteries. Chem Sustain Dev 13:253–26010.1002/sd.283 ↗
28. Johnson D (2003) ZView2 2.810.1016/S1359-6128(03)00126-5 ↗
29. Bucheli W, Jiménez R, Sanz J (2012) The log(σ) vs. log(ω) derivative plot used to analyze the AC conductivity. Application to fast Li+ ion conductors with perovskite structure. Solid State Ion 227:113–11810.1016/j.ssi.2012.09.018 ↗
30. Shannon RD (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr Sect A Cryst Phys Diffr Theor Gen Crystallogr A32:757–767
31. Roberson A, Fletcher JG, Skakle JMS, West AR (1993) Synthesis of LiTiPO5 and LiTiAsO5 with the α-FePO5 structure. J Solid State Chem 109:53–5910.1006/jssc.1994.1070 ↗
32. Daidouh A, Veiga ML, Pico C, Martinez-Ripoll M (1997) A new polymorph of Li4P2O7. Acta Cryst C53:167–169
33. Arbi K, Jimenez R, Šalkus T, Orliukas AF, Sanz J (2015) On the influence of the cation vacancy on lithium conductivity of Li1+xRxTi2−x(PO4)3 Nasicon type materials. Solid State Ion 271:28–3310.1016/j.ssi.2014.10.016 ↗
34. Kahlaoui R, Arbi K, Jimenez R, Sobrados I, Mehnaoui M, Sanz J, Ternane R (2017) Synthesis, structural characterization and ionic conductivity of NASICON-type Bax/2Li1−xTi2(PO4)3 (0.4 ≤ x ≤ 1) materials. Ionics 23:837–84610.1007/s11581-016-1898-4 ↗
35. Sanz J, Iglesias JE, Soria J, Losilla ER, Aranda MAG, Bruque S (1997) Structural disorder in the cubic 3 × 3 × 3 superstructure of TiP2O7. XRD and NMR Study. Chem Mater 9:996–100310.1021/cm970057t ↗
36. Schröder C, Ren J, Candida A, Rodrigues M, Eckert H (2014) Glass-to-crystal transition in Li1+xAlxGe2−x(PO4)3: structural aspects studied by solid state NMR. J Phys Chem C 118:9400–941110.1021/jp502265h ↗
37. Kazakevicius E, Urcinskas A, Bagdonas B, Kežionis A, Orliukas AF, Dindune A, Kanepe Z, Ronis J (2005) Electrical properties of Li1.3M1.4Ti0.3Al0.3(PO4)3 (M = Ge, Zr) superionics ceramics. Lith J Phys 45:267–27210.3952/lithjphys.45407 ↗
38. Kwatek K, Nowiński JL (2018) Solid lithium ion conducting composites based on LiTi2(PO4)3 and Li2.9B0.9S0.1O3.1 glass. Solid State Ion 322:93–9910.1016/j.ssi.2018.05.007 ↗
39. Arbi K, Bucheli W, Jimenez R, Sanz J (2015) High lithium ion conducting solid electrolytes based on NASICON Li1+xAlxM2−x(PO4)3 materials (M = Ti, Ge and 0 ≤ x ≤ 0.5). J Eur Ceram Soc 35:1477–148410.1016/j.jeurceramsoc.2014.11.023 ↗
40. Rettenwander D, Welzl A, Pristat S, Tietz F, Taibl S, Redhammer GJ, Fleig J (2016) A microcontact impedance study on NASICON-type Li1+xAlxTi2−x(PO4)3 (0 ≤ x ≤ 0.5) single crystals. J Mater Chem A 4:1506–151310.1039/C5TA08545D ↗
41. Kazakevicious E, Dindunde A, Kanepe Z, Ronis J, Orliukas A, Keizonis A, Salkus T (2005) Impedance spectra of Li1.3Sc0.15Y0.15Ti1.7(PO4)3 solid electrolyte ceramics in a broad frequency range. Solid State Ion 176:1743–174610.1016/j.ssi.2005.04.026 ↗
42. Venckutė V, Dobrovolskis P, Šalkus T, Kežionis A, Dindune A, Kanepe Z, Ronis J, Fung KZ, Orliukas AF (2015) Preparation and characterization of solid electrolytes based on TiP2O7 pyrophosphate. Ferroelectrics 479(1):101–10910.1080/00150193.2015.1012026 ↗
43. Mertens A, Schön SYN, Gunduz DC, Tempel H, Schierholz R, Hausen F, Kungl H, Granwehr J, Eichel RA (2017) Superionic bulk conductivity in Li1.3Al0.3Ti1.7(PO4)3 solid electrolyte. Solid State Ion 309:180–18610.1016/j.ssi.2017.07.023 ↗
44. Kleitz M, Dessemond L, Steil MC (1995) Model for ion-blocking at internal interfaces in zirconias. Solid State Ion 75:107–11510.1016/0167-2738(94)00143-G ↗