سنتز و بررسی خواص الکترولیت حالت جامد لیتیم آلومینیوم تیتانیوم فسفات هادی یون لیتیم

فصلنامه علمی - پژوهشی مواد نوین

مقاله 1، دوره 10، شماره 36 - شماره پیاپی 4، تیر 1398، صفحه 1-16   

نوع مقاله: مقاله پژوهشی

نویسندگان

ثمین طوفان^{* 1}؛ علی نعمتی²

¹کارشناس ارشد مهندسی مواد – سرامیک، دانشگاه صنعتی شریف

²دانشیار گروه سرامیک دانشگاه صنعتی شریف

تاریخ دریافت: 11 خرداد 1397،  تاریخ بازنگری: 10 اردیبهشت 1398،  تاریخ پذیرش: 02 تیر 1398 

چکیده

در دو دهه اخیر باتری‌های لیتیم-هوا به علت چگالی انرژی بالا بسیار مورد توجه قرار گرفته‌اند. الکترولیت‌های حالت جامد با هدایت یونی بالا یکی از مهم‌ترین چالش‌ها در ساخت این نوع‌ باتری‌ها به حساب می‌آیند. لیتیم آلومینیوم تیتانیوم فسفات (LATP) نوعی الکترولیت ناسیکونی است که به علت هدایت یونی بالا در باتری‌‌های لیتیم-هوا کاربرد یافته است. هدف از پژوهش حاضر ساخت غشاء هادی یون لیتیم LATP بوده است. به این ترتیب ابتدا پودر LATP به روش شیمیایی سنتز شده و دمای تبلور مناسب با بررسی الگوی پراش نمونه‌ها انتخاب گردید. پس از آن جهت ساخت غشاء نمونه‌ها در دو فشار پرس و دو زمان زینتر متفاوت و در دمای زینتز ℃850 تهیه شدند و اثر این عوامل بر هدایت یونی و دانسیته این نمونه‌ها بررسی گردید. بررسی‌ها نشان دادند که پودر LATP بدون فازهای ناخالصی با روش گفته شده با موفقیت سنتز شد و بهترین کریستالینیتی با آنیل کردن پودر در دمای ℃800 به دست آمد. همچنین بیشترین هدایت یونی به دست آمده مربوط به نمونه پرس شده با فشار Mpa50 و زمان زینتر 3 ساعت و برابر با S.cm-1 10-4×07/1 است. بیشترین دانسیته به دست آمده نیز مربوط به نمونه پرس شده با فشار Mpa50 و زمان زینتر 12 ساعت است.

کلیدواژه‌ها

هدایت یونی؛ ناسیکون؛ الکترولیت حالت جامد

عنوان مقاله [English]

synthesis and investigation of solid electrolyte ion conducting lithium aluminium titanium phosphate

نویسندگان [English]

samin toofan¹؛ Ali Nemati²

¹sharif university of technology

²Department of Materials Science & Engineering, Sharif University of Technology, Tehran, Iran

چکیده [English]

Lithium-air battery has been a focus of study for the past two decades due to their high theoretical energy density. Solid state electrolytes with high ion conuducting capability still remains a critical challenge in developing lithium-air batteries. Lithium aluminium titanium phosphate with high ion conducting properties and NASICON structure is a hopeful material as solid electrolyte. In this study we have prepared LATP powders by a solution based synthesis method continued by annealing to obtain convenient crystallinity without impurities. Preferred Crystallization temperature was determined to be 800 °C by x-ray diffraction analysis. . The milled powder was used to form pellets, which was then calcined 850 °C for two level of pressing pressure and sintering time. Highest ionic conductivity of 1.07×10-4 was abtained by pressing pressure of 50 Mpa and duel time of 3 hours. Although highest density refered to pressing pressure of 300 Mpa and 3 hours duel time.

کلیدواژه‌ها [English]

ionic conductivity, NASICON, solid state electrolyte

مراجع

 

1. I. Abrahams and E. Hadzifejzovic, “Lithium ion conductivity and thermal behaviour of glasses and crystallised glasses in the system Li 2 O – Al 2 O 3 – TiO 2 – P 2 O 5,” Solid State Ionics, vol. 134, pp. 249–257, 2000.
2. S. Soman, Y. Iwai, J. Kawamura, and A. Kulkarni, “Crystalline phase content and ionic conductivity correlation in LATP glass–ceramic,” J. Solid State Electrochem., vol. 16, no. 5, pp. 1761–1766, Nov. 2011.
3. J. L. Narváez-Semanate and a. C. M. Rodrigues, “Microstructure and ionic conductivity of Li1+xAlxTi2−x(PO4)3 NASICON glass-ceramics,” Solid State Ionics, vol. 181, no. 25–26, pp. 1197–1204, Aug. 2010.
4. T. Salkus, A. Dindune, Z. Kanepe, J. Ronis, A. Urcinskas, A. Kezionis, and A. Orliukas, “Lithium ion conductors in the system Li1+yGe2−x−yTixAly(PO4)3 (x=0.1÷0.3, y=0.07÷0.21),” Solid State Ionics, vol. 178, pp. 1282–1287, Jul. 2007.
5. H. Rusdi, A. A. Rahman, R. H. Y. Subban, and N. S. Mohamed, “Characterisation of Lithium Aluminium Titanium Phosphate as Solid Electrolytes Synthesized by Mechanical Milling Method,” Adv. Mater. Res., vol. 545, pp. 190–194, 2012.
6. H. Peng, H. Xie, and J. B. Goodenough, “Use of B2O3 to improve Li+-ion transport in LiTi2(PO4)3-based ceramics,” J. Power Sources, vol. 197, pp. 310–313, Jan. 2012.
7. A. K. et al. F. Orliukas , ⁎, T. Šalkus, “Structure and broadband impedance spectroscopy of Li1.3AlyYx−yTi1.7(PO4)3 ( x = 0 . 3 ; y = 0 . 1 , 0 . 2 ) solid electrolyte ceramics,” Solid State Ionics, vol. 225, pp. 620–625, 2012.
8. S. Branch, “Lithium Titanium Phosphate as Cathode , Anode and Electrolyte for Lithium Rechargeable Batteries,” Chem. Sustain. Dev., vol. 2, pp. 253–260, 2005.
9. N. V. Kosova, E. T. Devyatkina, a. P. Stepanov, and a. L. Buzlukov, “Lithium conductivity and lithium diffusion in NASICON-type Li1+xTi2–xAlx(PO4)3 (x= 0; 0.3) prepared by mechanical activation,” Ionics (Kiel)., vol. 14, no. 4, pp. 303–311, Jan. 2008.
10. Y. Yoon, J. Kim, C. Park, and D. Shin, “The relationship of structural and electrochemical properties of NASICON structure Li1.3Al0.3Ti1.7 (PO4)3 electrolytes by a sol-gel method,” J. Ceram. Process. Res., vol. 14, no. 4, pp. 563–566, 2013.
11. G. Vijayan, Lakshmi; Govindaraj, “ELECTRICAL RELAXATION STUDIES OF HIGH ENERGY BALL-MILLED NASICON TYPE MATERIALS,” J. Phys. Chem. Solids, vol. 72, no. 6, pp. 613–619, 2011.
12. S. Duluard, A. Paillassa, L. Puech, P. Vinatier, V. Turq, P. Rozier, P. Lenormand, P.-L. Taberna, P. Simon, and F. Ansart, “Lithium conducting solid electrolyte Li1.3Al0.3Ti1.7(PO4)3 obtained via solution chemistry,” J. Eur. Ceram. Soc., vol. 33, no. 6, pp. 1145–1153, Jun. 2013.
13. B. Key, D. J. Schroeder, B. J. Ingram, and J. T. Vaughey, “Solution-Based Synthesis and Characterization of Lithium-Ion Conducting Phosphate Ceramics for Lithium Metal Batteries,” Chem. Mater, vol. 24, pp. 287–293, 2012.
14. M. Kotobuki, “Preparation of Li-ion conductive ceramics through a sol-gel route,” in 2nd International Conference on Electrical, Electronics and Civil Engineering, 2012, vol. 3, pp. 165–167.
15. [P. Zhang, H. Wang, Q. Si, M. Matsui, Y. Takeda, O. Yamamoto, and N. Imanishi, “High lithium ion conductivity solid electrolyte of chromium and aluminum co-doped NASICON-type LiTi2(PO4)3,” Solid State Ionics, vol. 272, pp. 101–106, Apr. 2015.
16. Z. Xiao, S. Chen, and M. Guo, “Influence of Li3PO4 addition on properties of lithium ion-conductive electrolyte Li1.3Al0.3Ti1.7(PO4)3,” Trans. Nonferrous Met. Soc. China, vol. 21, no. 11, pp. 2454–2458, Nov. 2011.
17. K. Takahashi, J. Ohmura, D. Im, D. J. Lee, T. Zhang, N. Imanishi, a. Hirano, M. B. Phillipps, Y. Takeda, and O. Yamamoto, “A Super High Lithium Ion Conducting Solid Electrolyte of Grain Boundary Modified Li1.4Ti1.6 Al0.4(PO4)3,” J. Electrochem. Soc., vol. 159, no. 4, p. A342, 2012.
18. M. Schroeder, S. Glatthaar, and J. R. Binder, “Influence of spray granulation on the properties of wet chemically synthesized Li1.3Ti1.7Al0.3(PO4)3 (LATP) powders,” Solid State Ionics, vol. 201, no. 1, pp. 49–53, Oct. 2011.
19. [M. Kotobuki, M. Koishi, and Y. Kato, “Preparation of Li1.5Al0.5Ti1.5(PO4)3 solid electrolyte via a co-precipitation method,” Ionics (Kiel)., vol. 19, no. 12, pp. 1945–1948, Oct. 2013.
20. M. Kotobuki and M. Koishi, “Preparation of Li1.5Al0.5Ti1.5(PO4)3 solid electrolyte via a sol–gel route using various Al sources,” Ceram. Int., vol. 39, no. 4, pp. 4645–4649, May 2013.
21. G. B. Kunshina, O. G. Gromov, E. P. Lokshin, and V. T. Kalinnikov, “Preparation of powders and films of the lithium ion conducting solid electrolyte Li1.3Al0.3Ti1.7(PO4)3,” Inorg. Mater., vol. 49, no. 1, pp. 95–100, Dec. 2012.
22. S. Breuer, D. Prutsch, Q. Ma, V. Epp, F. Preishuber-Pflügl, F. Tietz, and M. Wilkening, “Separating bulk from grain boundary Li ion conductivity in the sol–gel prepared solid electrolyte Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3,” J. Mater. Chem. A, vol. 3, no. 42, pp. 21343–21350, 2015.
23. B.O. Linova , S.D. Kobylianska , A.G. Bilous , А.V. Ragulya , I.O. Dulina, "SYNTHESIS OF Li1.3Al0.3Ti1.7(PO4)3 FILMS WITH NASICON STRUCTURE BY «TАPE CASTING» METHOD," Chemistry, Physics and Technology of Surface, vol. 7, no. 4, pp. 389-394, 2016.
24. Leopold Hallopeau, Damien Bregiroux,, Gwenaëlle Rousse, David Portehault, Philippe Stevens, Gwenaëlle Toussaint, Christel Laberty-Robert, "Microwave-assisted reactive sintering and lithium ion conductivity of Li1.3Al0.3Ti1.7(PO4)3 solid electrolyte," Journal of Power Sources, no. 378, p. 48–52, 2018.
25. Shicheng Yu, Andreas Mertens, Xin Gao, Deniz Cihan Gunduz, "Influence of microstructure and AlPO4 secondary-phase on the ionic conductivity of Li1.3Al0.3Ti1.7(PO4)3 solid-state electrolyte," Functional Materials Letters, vol. 9, no. 5, pp. 1650066-6, 2016.
26. M. Gellert, K. I. Gries, C. Yada, F. Rosciano, K. Volz, and B. Roling, “Grain Boundaries in a Lithium Aluminum Titanium Phosphate-Type Fast Lithium Ion Conducting Glass Ceramic: Microstructure and Nonlinear Ion Transport Properties,” J. Phys. Chem., vol. 116, pp. 22675–22678, 2012.
27. E. C. Bucharsky, K. G. Schell, a. Hintennach, and M. J. Hoffmann, “Preparation and characterization of sol–gel derived high lithium ion conductive NZP-type ceramics Li1+x AlxTi2−x(PO4)3,” Solid State Ionics, vol. 274, pp. 77–82, Jun. 2015.
28. Qianli Ma, Qi Xu, Chih-Long Tsai, Frank Tietz, Olivier Guillon, "A Novel Sol–Gel Method for Large-Scale Production of Nanopowders: Preparation of Li1.5Al0.5Ti1.5(PO4)3 as an Example," Journal of the American Ceramic Society, vol. 99, no. 2, pp. 410-414, 2016.
29. J. YANG, "Synthesis and Characterizations of Lithium Aluminum Titanium Phosphate (Li1+xAlxTi2-x(PO4)3) Solid Electrolytes for All-Solid-State Li-ion Batteries," Wright State University, Dayton, 2017.
30. B. Le Gorrec and C. Montella, Handbook of Electrochemical Impedance Spectroscopy ELECTRICAL CIRCUITS. 2013, p. 5.
31. V. T. Gromov, O.G., Kunshina, G.B., Kuz’min, A.P., Kalinnikov, “Ionic conductivity of solid electrolytes based on Li1.3Al0.3Ti1.7(PO4)3,” Russ. J. Appl. Chem., vol. 69, no. 3, pp. 385–388, 1996.
32. [C.-M. Chang, Y. Il Lee, S.-H. Hong, and H.-M. Park, “Spark Plasma Sintering of LiTi2(PO4)3-Based Solid Electrolytes,” J. Am. Ceram. Soc., vol. 88, no. 7, pp. 1803–1807, Jul. 2005.
33. S.-J. L.Kang, Sintering Densification,GrainGrowth, and Microstructure. Burlington: Elsevier, 2005, pp. 39–74.
34. S.-J. L. Kang, “Normal and Abnormal Grain Growth in Polycrystals,” DAEJEON, 2009.