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Addition of Calcined Na2B4O7 on the Synthesis of Li7La3Zr2O12

Department of Chemistry, Faculty of Mathematics and Natural Sciences, Sebelas Maret University, Surakarta, Indonesia

Received: 7 Dec 2020; Revised: 19 Mar 2021; Accepted: 22 Mar 2021; Published: 31 Mar 2021.
Open Access Copyright 2021 Jurnal Kimia Sains dan Aplikasi under http://creativecommons.org/licenses/by-sa/4.0.

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Abstract
Li7La3Zr2O12 (LLZO) is a garnet-type electrolyte for all-solid-state lithium-ion batteries (ASSB). It has good chemical and electrochemical stability against lithium and a relatively high ionic conductivity. However, the ionic conductivity needs to be further increased to provide a high specific capacity of the ASSB. Element doping into LLZO is an effort to increase molecular defect, known to enhance the conductivity. This research studied the effect of the Na2B4O7 addition on the LLZO synthesis, producing LLZBO(A). The investigation aims to understand whether the sodium ions dope into the LLZO structure during synthesis, or it is only B ions to enter into the structure. Therefore, another synthesis with B2O3 of B precursor was conducted for comparison (LLZBO(B)). The precursors were mixed stoichiometrically by following the formula of Li7-xLa3-xZr2-xBxNaxO12 (LLZBO, x= 0.15; 0.20; 0.30). XRD analysis equipped with Le Bail refinement found that LLZBO(A) and LLZBO(B) mainly consist of cubic and tetragonal LLZO with a %mol of 69.06 – 69.84 %, and the main secondary phase is La2Zr2O7. The surface morphology of LLZBO(A) and LLZBO(B) is almost similar to the irregular form of large aggregates. The particles become more dispersed when 0.3 %mol dopant was submitted. Impedance analysis found a high ionic conductivity of LLZBAO(A)0.3 1.042x10-3 Scm-1.
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Keywords: LLZO garnet; B-Al doping; zirconia; all-solid-state lithium battery
Funding: Sebelas maret University

Article Metrics:

  1. Zhenzhu Cao, Xueyan Cao, Xiaoting Liu, Weiyan He, Yanfang Gao, Jinrong Liu, Jiangtao Zeng, Effect of Sb-Ba codoping on the ionic conductivity of Li7La3Zr2O12 ceramic, Ceramics International, 41, 5, Part A, (2015), 6232-6236 https://doi.org/10.1016/j.ceramint.2015.01.030
  2. Kamil Burak Dermenci, Ahmet Furkan Buluç, Servet Turan, The effect of limonite addition on the performance of Li7La3Zr2O12, Ceramics International, 45, 17, Part A, (2019), 21401-21408 https://doi.org/10.1016/j.ceramint.2019.07.128
  3. Wenru Hou, Xianwei Guo, Xuyang Shen, Khali Amine, Haijun Yu, Jun Lu, Solid electrolytes and interfaces in all-solid-state sodium batteries: Progress and perspective, Nano Energy, 52, (2018), 279-291 https://doi.org/10.1016/j.nanoen.2018.07.036
  4. Minghui Hu, Yunxiao Li, Shuxian Li, Chunyun Fu, Datong Qin, Zonghua Li, Lithium-ion battery modeling and parameter identification based on fractional theory, Energy, 165, (2018), 153-163 https://doi.org/10.1016/j.energy.2018.09.101
  5. Junhao Li, Zhongqi Liu, Wen Ma, Hongying Dong, Kefu Zhang, Ruigang Wang, Low-temperature synthesis of cubic phase Li7La3Zr2O12 via sol-gel and ball milling induced phase transition, Journal of Power Sources, 412, (2019), 189-196 https://doi.org/10.1016/j.jpowsour.2018.11.040
  6. E. A. Il’ina, A. A. Raskovalov, A. P. Safronov, The standard enthalpy of formation of superionic solid electrolyte Li7La3Zr2O12, Thermochimica Acta, 657, (2017), 26-30 https://doi.org/10.1016/j.tca.2017.09.019
  7. Jun Ma, Bingbing Chen, Longlong Wang, Guanglei Cui, Progress and prospect on failure mechanisms of solid-state lithium batteries, Journal of Power Sources, 392, (2018), 94-115 https://doi.org/10.1016/j.jpowsour.2018.04.055
  8. Juliane Franciele Nonemacher, Claas Hüter, Hao Zheng, Jürgen Malzbender, Manja Krüger, Robert Spatschek, Martin Finsterbusch, Microstructure and properties investigation of garnet structured Li7La3Zr2O12 as electrolyte for all-solid-state batteries, Solid State Ionics, 321, (2018), 126-134 https://doi.org/10.1016/j.ssi.2018.04.016
  9. Chunwen Sun, Jin Liu, Yudong Gong, David P. Wilkinson, Jiujun Zhang, Recent advances in all-solid-state rechargeable lithium batteries, Nano Energy, 33, (2017), 363-386 https://doi.org/10.1016/j.nanoen.2017.01.028
  10. Audric Neveu, Vincent Pelé, Christian Jordy, Valerie Pralong, Exploration of Li–P–S–O composition for solid-state electrolyte materials discovery, Journal of Power Sources, 467, (2020), 228250 https://doi.org/10.1016/j.jpowsour.2020.228250
  11. Jiayao Lu, Ying Li, Yushi Ding, Structure, stability, and ionic conductivity of perovskite Li2x-ySr1-x-yLayTiO3 solid electrolytes, Ceramics International, 46, 6, (2020), 7741-7747 https://doi.org/10.1016/j.ceramint.2019.11.277
  12. Sumaletha Narayanan, Samuel Reid, Shantel Butler, Venkataraman Thangadurai, Sintering temperature, excess sodium, and phosphorous dependencies on morphology and ionic conductivity of NASICON Na3Zr2Si2PO12, Solid State Ionics, 331, (2019), 22-29 https://doi.org/10.1016/j.ssi.2018.12.003
  13. Liwei Shen, Li Wang, Zhangjun Wang, Chao Jin, Lin Peng, Xiaowei Pan, Jiawen Sun, Ruizhi Yang, Preparation and characterization of Ga and Sr co-doped Li7La3Zr2O12 garnet-type solid electrolyte, Solid State Ionics, 339, (2019), 114992 https://doi.org/10.1016/j.ssi.2019.05.027
  14. Yali Luo, Yanli Zhang, Qixi Zhang, Yifeng Zheng, Han Chen, Lucun Guo, Effect of dual doping on the structure and performance of garnet-type Li7La3Zr2O12 ceramic electrolytes for solid-state lithium-ion batteries, Ceramics International, 45, 14, (2019), 17874-17883 https://doi.org/10.1016/j.ceramint.2019.06.002
  15. Jianli Gai, Erqing Zhao, Furui Ma, Deye Sun, Xiaodi Ma, Yongcheng Jin, Qingliu Wu, Yongjie Cui, Improving the Li-ion conductivity and air stability of cubic Li7La3Zr2O12 by the co-doping of Nb, Y on the Zr site, Journal of the European Ceramic Society, 38, 4, (2018), 1673-1678 https://doi.org/10.1016/j.jeurceramsoc.2017.12.002
  16. Chongyang Shao, Zhiyong Yu, Hanxing Liu, Zhenning Zheng, Nian Sun, Chunli Diao, Enhanced ionic conductivity of titanium doped Li7La3Zr2O12 solid electrolyte, Electrochimica Acta, 225, (2017), 345-349 https://doi.org/10.1016/j.electacta.2016.12.140
  17. Zhongli Hu, Hongdong Liu, Haibo Ruan, Rong Hu, Yongyao Su, Lei Zhang, High Li-ion conductivity of Al-doped Li7La3Zr2O12 synthesized by solid-state reaction, Ceramics International, 42, 10, (2016), 12156-12160 https://doi.org/10.1016/j.ceramint.2016.04.149
  18. Jianmeng Su, Xiao Huang, Zhen Song, Tongping Xiu, Michael E. Badding, Jun Jin, Zhaoyin Wen, Overcoming the abnormal grain growth in Ga-doped Li7La3Zr2O12 to enhance the electrochemical stability against Li metal, Ceramics International, 45, 12, (2019), 14991-14996 https://doi.org/10.1016/j.ceramint.2019.04.236
  19. R. H. Brugge, J. A. Kilner, A. Aguadero, Germanium as a donor dopant in garnet electrolytes, Solid State Ionics, 337, (2019), 154-160 https://doi.org/10.1016/j.ssi.2019.04.021
  20. Xiao Huang, Zhen Song, Tongping Xiu, Michael E. Badding, Zhaoyin Wen, Sintering, micro-structure and Li+ conductivity of Li7−xLa3Zr2−xNbxO12/MgO (x = 0.2–0.7) Li-Garnet composite ceramics, Ceramics International, 45, 1, (2019), 56-63 https://doi.org/10.1016/j.ceramint.2018.09.133
  21. Yu Gong, Zhan-Guo Liu, Yu-Jun Jin, Jia-Hu Ouyang, Lei Chen, Yu-Jin Wang, Effect of sintering process on the microstructure and ionic conductivity of Li7–xLa3Zr2–xTaxO12 ceramics, Ceramics International, 45, 15, (2019), 18439-18444 https://doi.org/10.1016/j.ceramint.2019.06.061
  22. Yiqiu Li, Zheng Wang, Yang Cao, Fuming Du, Cheng Chen, Zhonghui Cui, Xiangxin Guo, W-Doped Li7La3Zr2O12 Ceramic Electrolytes for Solid State Li-ion Batteries, Electrochimica Acta, 180, (2015), 37-42 https://doi.org/10.1016/j.electacta.2015.08.046
  23. Xishu Wang, Jie Liu, Rui Yin, Yichen Xu, Yonghua Cui, Liang Zhao, Xibin Yu, High lithium ionic conductivity of garnet-type oxide Li7+xLa3Zr2-xSmxO12 (x = 0–0.1) ceramics, Materials Letters, 231, (2018), 43-46 https://doi.org/10.1016/j.matlet.2018.08.006
  24. Amardeep, Sushobhan Kobi, Amartya Mukhopadhyay, Mg-doping towards enhancing the composition-phase-structural stability of Li-La-zirconate based cubic garnet upon exposure to air, Scripta Materialia, 162, (2019), 214-218 https://doi.org/10.1016/j.scriptamat.2018.11.026
  25. Shidong Song, Butian Chen, Yanli Ruan, Jian Sun, Limei Yu, Yan Wang, Joykumar Thokchom, Gd-doped Li7La3Zr2O12 garnet-type solid electrolytes for all-solid-state Li-Ion batteries, Electrochimica Acta, 270, (2018), 501-508 https://doi.org/10.1016/j.electacta.2018.03.101
  26. Yu Tang, Zhiwei Luo, Taoyong Liu, Piao Liu, Zhuo Li, Anxian Lu, Effects of B2O3 on microstructure and ionic conductivity of Li6.5La3Zr1.5Nb0.5O12 solid electrolyte, Ceramics International, 43, 15, (2017), 11879-11884 https://doi.org/10.1016/j.ceramint.2017.06.035
  27. Ramaswamy Murugan, Venkataraman Thangadurai, Werner Weppner, Fast Lithium Ion Conduction in Garnet-Type Li7La3Zr2O12, Angewandte Chemie International Edition, 46, 41, (2007), 7778-7781 https://doi.org/10.1002/anie.200701144
  28. Ran-Hee Shin, Sam Ick Son, Yoon Soo Han, Young Do Kim, Hyung-Tae Kim, Sung-Soo Ryu, Wei Pan, Sintering behavior of garnet-type Li7La3Zr2O12-Li3BO3 composite solid electrolytes for all-solid-state lithium batteries, Solid State Ionics, 301, (2017), 10-14 https://doi.org/10.1016/j.ssi.2017.01.005
  29. E. A. Il'ina, S. V. Pershina, B. D. Antonov, A. A. Pankratov, E. G. Vovkotrub, The influence of the glass additive Li2O-B2O3-SiO2 on the phase composition, conductivity, and microstructure of the Li7La3Zr2O12, Journal of Alloys and Compounds, 765, (2018), 841-847 https://doi.org/10.1016/j.jallcom.2018.06.154
  30. Dong Ok Shin, Kyungbae Oh, Kwang Man Kim, Kyu-Young Park, Byungju Lee, Young-Gi Lee, Kisuk Kang, Synergistic multi-doping effects on the Li7La3Zr2O12 solid electrolyte for fast lithium ion conduction, Scientific Reports, 5, 1, (2015), 18053 https://doi.org/10.1038/srep18053
  31. Yedukondalu Meesala, Yu-Kai Liao, Anirudha Jena, Nai-Hsuan Yang, Wei Kong Pang, Shu-Fen Hu, Ho Chang, Chia-Erh Liu, Shih-Chieh Liao, Jin-Ming Chen, Xiangxin Guo, Ru-Shi Liu, An efficient multi-doping strategy to enhance Li-ion conductivity in the garnet-type solid electrolyte Li7La3Zr2O12, Journal of Materials Chemistry A, 7, 14, (2019), 8589-8601 https://doi.org/10.1039/C9TA00417C
  32. William M. Haynes, CRC Handbook of Chemistry and Physics, 97th ed., CRC Press, 2016
  33. Karima Apriany, Ita Permadani, Dani G. Syarif, Syoni Soepriyanto, Fitria Rahmawati, Electrical conductivity of zirconia and yttrium-doped zirconia from Indonesian local zircon as prospective material for fuel cells, IOP Conference Series: Materials Science and Engineering, 107, (2016), 012023 https://doi.org/10.1088/1757-899X/107/1/012023
  34. Ömer Şahin, A Nusret Bulutcu, Evaluation of Thermal Decomposition Kinetics of Borax Pentahydrate Using Genetic Algorithm Method by Isothermal Analysis, Turkish Journal of Chemistry, 27, 2, (2003), 197-208
  35. Junji Awaka, Norihito Kijima, Hiroshi Hayakawa, Junji Akimoto, Synthesis and structure analysis of tetragonal Li7La3Zr2O12 with the garnet-related type structure, Journal of Solid State Chemistry, 182, 8, (2009), 2046-2052 https://doi.org/10.1016/j.jssc.2009.05.020
  36. Liuliu Feng, Ling Li, Yunqiang Zhang, Hongjian Peng, Yingping Zou, Low temperature synthesis and ion conductivity of Li7La3Zr2O12 garnets for solid state Li ion batteries, Solid State Ionics, 310, (2017), 129-133 https://doi.org/10.1016/j.ssi.2017.08.016
  37. Beena Tyagi, Kalpesh Sidhpuria, Basha Shaik, Raksh Vir Jasra, Synthesis of Nanocrystalline Zirconia Using Sol−Gel and Precipitation Techniques, Industrial & Engineering Chemistry Research, 45, 25, (2006), 8643-8650 https://doi.org/10.1021/ie060519p
  38. Pradyot Patnaik, Handbook of Inorganic Chemicals, McGraw-Hill, 2003
  39. I. Waclawska, Thermal decomposition of borax, Journal of thermal analysis, 43, 1, (1995), 261-269 https://doi.org/10.1007/BF02635993
  40. Fitria Rahmawati, Bambang Prijamboedi, Syoni Soepriyanto, Ismunandar, SOFC composite electrolyte based on LSGM-8282 and zirconia or doped zirconia from zircon concentrate, International Journal of Minerals, Metallurgy, and Materials, 19, 9, (2012), 863-871 https://doi.org/10.1007/s12613-012-0640-0

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