Syntheses and Properties of Ta ⁵⁺ Doped Li₇La₃Zr₂O₁₂

Authors

Feng-feng PENG, College of Petrochemical Technology, Lanzhou University of Technology, Lanzhou 730050, China;
Shi-you LI, College of Petrochemical Technology, Lanzhou University of Technology, Lanzhou 730050, China;Follow
Tong-tong GENG, College of Petrochemical Technology, Lanzhou University of Technology, Lanzhou 730050, China;
Chun-lei LI, College of Petrochemical Technology, Lanzhou University of Technology, Lanzhou 730050, China;
Shuang-wei ZENG, College of Petrochemical Technology, Lanzhou University of Technology, Lanzhou 730050, China;

Corresponding Author

Shi-you LI(lishiyoulw@163.com)

Abstract

The tantalum ion (Ta ⁵⁺) doped garnet-type inorganic solid electrolyte Ta-LLZO was prepared by solid state reaction, and the effect of doping amount on the properties of the materials was investigated. The materials were characterized by X-ray diffraction (XRD), field emission electron scanning microscopy (FESEM) and electrochemical impedance spectroscopy (EIS). And the cycle stability was tested by assembly of LiFePO₄//LLZTO//Li all solid lithium battery. The results show that with the increase of Ta ⁵⁺ doping amount, the material appeared to form a single cubic phase structure. When the Ta ⁵⁺ doping content became 14.09wt.%, x=0.3, the room temperature ionic conductivity of the material reached the maximum (2.58×10 ^-4 S·cm ^-1), forming a stable cubic phase structure with a relatively high density (89.16%). In addition, the relatively stable cycle stability was obtained and the capacity retention rate remained at around 88.67% after 50 cycles.

Graphical Abstract

Keywords

Li7La3Zr2O12, Garnet-type, Ta 5+ doping, solid state reaction

DOI Link

https://doi.org/10.13208/j.electrochem.181105

Publication Date

2020-04-28

Online Available Date

2019-02-21

Revised Date

2019-02-16

Received Date

2018-11-05

Recommended Citation

Feng-feng PENG, Shi-you LI, Tong-tong GENG, Chun-lei LI, Shuang-wei ZENG. Syntheses and Properties of Ta ⁵⁺ Doped Li₇La₃Zr₂O₁₂[J]. Journal of Electrochemistry, 2020 , 26(2): 308-314.
DOI: 10.13208/j.electrochem.181105
Available at: https://jelectrochem.xmu.edu.cn/journal/vol26/iss2/16

References

[1] Nagata H, Chikusa Y . An all-solid-state lithium-sulfur battery using two solid electrolytes having different functions[J]. Journal of Power Sources, 2016,329:268-272.

[2] Whittingham M S . Introduction: batteries[J]. Chemical Reviews, 2014,114(23):11413.

[3] Kim T H, Park J S, Chang S K , et al. The current move of lithium ion batteries towards the next phase[J]. Advanced Energy Materials, 2012,2(7):860-872.
doi: 10.1002/aenm.201200028 URL

[4] Manthiram A, Yu X, Wang S . Lithium battery chemistries enabled by solid-state electrolytes[J]. Nature Reviews Materials, 2017,2(4):16103.

[5] Chung H, Kang B . Increase in grain boundary ionic conductivity of Li_1.5Al_0.5Ge_1.5(PO₄)₃ by adding excess lithium[J]. Solid State Ionics, 2014,263:125-130.

[6] Zhang M, Takahashi K, Uechi I , et al. Water-stable lithium anode with Li_1.4Al_0.4Ge_1.6(PO₄)₃-TiO₂ sheet prepared by tape casting method for lithium-air batteries[J]. Journal of Power Sources, 2013,235:117-121.

[7] Zhang M, Huang Z, Cheng J F , et al. Solid state lithium ionic conducting thin film Li_1.4Al_0.4Ge_1.6(PO₄)₃ prepared by tape casting[J]. Journal of Alloys and Compounds, 2014,590:147-152.
doi: 10.1016/j.jallcom.2013.12.100 URL

[8] Liu Z, Venkatachalam S, Van Wüllen L . Structure, phase separation and Li dynamics in sol-gel-derived Li_1+xAl_xGe_2-x-(PO₄)₃[J]. Solid State Ionics, 2015, 276: 47-55.
doi: 10.1016/j.ssi.2015.03.018 URL

[9] Jadhav H S, Cho M S, Kalubarme R S , et al. Influence of B₂O₃ addition on the ionic conductivity of Li_1.5Al_0.5Ge_1.5(PO₄)₃ glass ceramics[J]. Journal of Power Sources, 2013,241:502-508.
doi: 10.1016/j.jpowsour.2013.04.137 URL

[10] Morimoto H, Awano H, Terashima J , et al. Preparation of lithium ion conducting solid electrolyte of NASICON-type Li₁+_xAl_xTi₂-_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]. Journal of Power Sources, 2013,240:636-643.

[11] Illbeigi M, Fazlali A, Kazazi M , et al. Effect of simultaneous addition of aluminum and chromium on the lithium ionic conductivity of LiGe₂(PO₄)₃ NASICON-type glass-ceramics[J]. Solid State Ionics, 2016,289:180-187.
doi: 10.1016/j.ssi.2016.03.012 URL

[12] Yao X, Huang B, Yin J , et al. All-solid-state lithium batteries with inorganic solid electrolytes: Review of fundamental science[J]. Chinese Physics B, 2016,25(1):018802.
doi: 10.1088/1674-1056/25/1/018802 URL

[13] Kunshina G B, Efremov V V, Lokshin E P . Synjournal and study of ion conductivity of Li₃-_xLa_2/3-_xTiO₃[J]. Russian Journal of Electrochemistry, 2015,51(6):551-555.

[14] Zhong S W( 钟盛文), Huang B( 黄冰 ). Effect of excess lithium on properties of perovskite Li_3/8Sr_7/16Ta_3/4Hf_1/4O₃ solid electrolyte[J]. Nonferrous Metal Science and Engineering( 有色金属科学与工程), 2017,8(1):70-74.

[15] Murugan R, Thangadurai V, Weppner W . Fast lithium ion conduction in garnet-type Li₇La₃Zr₂O₁₂[J]. Angewandte Chemie International Edition, 2007,46(41):7778-7781.
doi: 10.1002/(ISSN)1521-3773 URL

[16] Lee C H, Park G J, Choi J H , et al. Low temperature synjournal of garnet type solid electrolyte by modified polymer complex process and its characterization[J]. Materials Research Bulletin, 2016,83:309-315.
doi: 10.1016/j.materresbull.2016.02.040 URL

[17] Baek S W, Lee J M, Kim T Y , et al. Garnet related lithium ion conductor processed by spark plasma sintering for all solid state batteries[J]. Journal of Power Sources, 2014,249:197-206.
doi: 10.1016/j.jpowsour.2013.10.089 URL

[18] Howard M A, Clemens O, Kendrick E , et al. Effect of Ga incorporation on the structure and Li ion conductivity of La₃Zr₂Li₇O₁₂[J]. Dalton Transactions, 2012,41(39):12048-12053.
doi: 10.1039/c2dt31318a URL

[19] Rettenwander D, Geiger C A, Amthauer G . Synjournal and crystal chemistry of the fast Li-ion conductor Li₇La₃Zr₂O₁₂ doped with Fe[J]. Inorganic Chemistry, 2013,52(14):8005-8009.
doi: 10.1021/ic400589u URL

[20] Deviannapoorani C, Dhivya L, Ramakumar S , et al. Lithium ion transport properties of high conductive tellurium substituted Li₇La₃Zr₂O₁₂ cubic lithium garnets[J]. Journal of Power Sources, 2013,240:18-25.

[21] Geng H, Chen K, Yi D , et al. Formation mechanism of Garnet-like Li₇La₃Zr₂O₁₂ powder prepared by solid state reaction[J]. Rare Metal Materials and Engineering, 2016,45(3):612-616.

[22] Xu Y Y( 许阳阳), Li Q G( 李全国), Liang C D( 梁成都 ), et al. Research progress of sulfide solid electrolyte[J]. Energy Storage Science and Technology( 储能科学与技术), 2016,5(5):503-512.

[23] Minami K, Mizuno F, Hayashi A , et al. Lithium ion conductivity of the Li₂S-P₂S₅ glass-based electrolytes prepared by the melt quenching method[J]. Solid State Ionics, 2007,178(11/12):837-841.

[24] Liu Z C, Fu W J, Payzant E A , et al. Anomalous high ionic conductivity of nanoporous beta-Li₃PS₄[J]. Journal of the American Chemical Society, 2013,135(3):975-978.

[25] Kanno R, Murayama M . Lithium ionic conductor thio-LISICON - The Li₂S-GeS₂-P₂S₅ system[J]. Journal of The Electrochemical Society, 2001,148(7):A742-A746.
doi: 10.1149/1.1379028 URL

[26] Kamaya N, Homma K, Yamakawa Y , et al. A lithium superionic conductor[J]. Nature Materials, 2011,10(9):682-686.

[27] Kuhn A, Gerbig O, Zhu C , et al. A new ultrafast superionic Li-conductor: ion dynamics in Li₁₁Si₂PS₁₂ and comparison with other tetragonal LGPS-type electrolytes[J]. Physical Chemistry Chemical Physics, 2014,16(28):14669-14674.

[28] Gong Y, Fu K, Xu S , et al. Lithium-ion conductive ceramic textile: A new architecture for flexible solid-state lithium metal batteries[J]. Materials Today, 2018,21(6):594-601.

[29] Liu X T, Li Y, Yang T T , et al. High lithium ionic conductivity in the Garnet-type oxide Li_7-2xLa₃Zr₂-_xMo_xO₁₂ (x=0-0.3) ceramics by sol-gel method[J]. Journal of the American Ceramic Society, 2017,100(4):1527-1533.
doi: 10.1111/jace.2017.100.issue-4 URL

[30] Gai J, Zhao E, Ma F , et al. Improving the Li-ion conductivity and air stability of cubic Li₇La₃Zr₂O₁₂ by the co-doping of Nb, Y on the Zr site[J]. Journal of the European Ceramic Society, 2018,38(4):1673-1678.

[31] Thompson T, Wolfenstine J, Allen J L , et al. Tetragonal vs. cubic phase stability in Al-free Ta doped Li₇La₃Zr₂O₁₂ (LLZO)[J]. Journal of Materials Chemistry A, 2014,2(33):13431-13436.

[32] Basappa R H, Ito T, Yamada H . Contact between Garnet-type solid electrolyte and lithium metal anode: influence on charge transfer resistance and short circuit prevention[J]. Journal of The Electrochemical Society, 2017,164(4):666-671.

[33] Sharafi A, Haslam C G, Kerns R D , et al. Controlling and correlating the effect of grain size with the mechanical and electrochemical properties of Li₇La₃Zr₂O₁₂ solid-state electrolyte[J]. Journal of Materials Chemistry A, 2017,5(40):21491-21504.
doi: 10.1039/C7TA06790A URL