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NASICON (sodium (Na) superionic conductor) compounds have attracted considerable attention as promising solid electrolyte materials for advanced Na-based batteries. In this study, we investigated the improvement in ionic conductivities of von-Alpen-type NASICON (vA-NASICON) ceramic electrolytes by introducing a magnesium ion (Mg2+) as a heterogeneous element. The optimal Mg-doped vA-NASICON exhibited a high ionic conductivity of 3.64×10−3 S·cm−1, which was almost 80% higher than that of un-doped vA-NASICON. The changes in physicochemical properties of the vA-NASICONs through the Mg introduction were systematically analyzed, and their effects on the ionic conductivities of the vA-NASICON were studied in detail. When the optimal ratio of Mg2+ was used in a synthetic process, the relative density (96.6%) and grain boundary ionic conductivity (σgb) were maximized, which improved the total ionic conductivity (σt) of the vA-NASICON. However, when Mg2+ was introduced in excess, the ionic conductivity decreased because of the formation of an undesired sodium magnesium phosphate (NaxMgyPO4) secondary phase. The results of this study are expected to be effectively applied in the development of advanced sodium-based solid electrolytes with high ionic conductivities.


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Improving ionic conductivity of von-Alpen-type NASICON ceramic electrolytes via magnesium doping

Show Author's information Il-Seop Janga,b,Wooseok Goc,Bo-Ye Songa,bHayoung Parka,bYun Chan Kangb( )Jinyoung Chuna( )
Emerging Materials R&D Division, Korea Institute of Ceramic Engineering and Technology (KICET), Jinju 52851, Republic of Korea
Department of Materials Science and Engineering, Korea University, Seoul 02841, Republic of Korea
Energy Storage and Distribution Resources Division, Lawrence Berkeley National Laboratory, Berkeley 94720, USA

† Il-Seop Jang and Wooseok Go contributed equally to this work.

Abstract

NASICON (sodium (Na) superionic conductor) compounds have attracted considerable attention as promising solid electrolyte materials for advanced Na-based batteries. In this study, we investigated the improvement in ionic conductivities of von-Alpen-type NASICON (vA-NASICON) ceramic electrolytes by introducing a magnesium ion (Mg2+) as a heterogeneous element. The optimal Mg-doped vA-NASICON exhibited a high ionic conductivity of 3.64×10−3 S·cm−1, which was almost 80% higher than that of un-doped vA-NASICON. The changes in physicochemical properties of the vA-NASICONs through the Mg introduction were systematically analyzed, and their effects on the ionic conductivities of the vA-NASICON were studied in detail. When the optimal ratio of Mg2+ was used in a synthetic process, the relative density (96.6%) and grain boundary ionic conductivity (σgb) were maximized, which improved the total ionic conductivity (σt) of the vA-NASICON. However, when Mg2+ was introduced in excess, the ionic conductivity decreased because of the formation of an undesired sodium magnesium phosphate (NaxMgyPO4) secondary phase. The results of this study are expected to be effectively applied in the development of advanced sodium-based solid electrolytes with high ionic conductivities.

Keywords: ionic conductivity, NASICON, solid electrolyte, von-Alpen-type, magnesium (Mg) doping

References(49)

[1]
Chen RJ, Luo R, Huang YX, et al. Advanced high energy density secondary batteries with multi-electron reaction materials. Adv Sci 2016, 3: 1600051.
[2]
Lim WG, Kim S, Jo C, et al. A comprehensive review of materials with catalytic effects in Li–S batteries: Enhanced redox kinetics. Angew Chem 2019, 58: 18746–18757.
[3]
Lim E, Chun J, Jo C, et al. Recent advances in the synthesis of mesoporous materials and their application to lithium-ion batteries and hybrid supercapacitors. Korean J Chem Eng 2021, 38: 227–247.
[4]
Liu MQ, Wang YH, Wu F, et al. Advances in carbon materials for sodium and potassium storage. Adv Funct Mater 2022, 32: 2203117.
[5]
Yabuuchi N, Kubota K, Dahbi M, et al. Research development on sodium-ion batteries. Chem Rev 2014, 114: 11636–11682.
[6]
Vaalma C, Buchholz D, Weil M, et al. A cost and resource analysis of sodium-ion batteries. Nat Rev Mater 2018, 3: 18013.
[7]
Xu HY, Ruan JH, Liu FL, et al. Preparation of lithium-doped NaV6O15 thin film cathodes with high cycling performance in SIBs. J Korean Ceram Soc 2022, 59: 289–301.
[8]
Zhao CL, Liu LL, Qi XG, et al. Solid-state sodium batteries. Adv Energy Mater 2018, 8: 1703012.
[9]
Senthilkumar ST, Go W, Han J, et al. Emergence of rechargeable seawater batteries. J Mater Chem A 2019, 7: 22803–22825.
[10]
Xu XL, San Hui K, Dinh DA, et al. Recent advances in hybrid sodium–air batteries. Mater Horiz 2019, 6: 1306– 1335.
[11]
Yang HL, Zhang BW, Konstantinov K, et al. Progress and challenges for all-solid-state sodium batteries. Adv Energy Sustain Res 2021, 2: 2000057.
[12]
Lee C, Wi TU, Go W, et al. Unveiling interfacial dynamics and structural degradation of solid electrolytes in a seawater battery system. J Mater Chem A 2020, 8: 21804– 21811.
[13]
Wu JF, Zhang R, Fu QF, et al. Inorganic solid electrolytes for all-solid-state sodium batteries: Fundamentals and strategies for battery optimization. Adv Funct Mater 2021, 31: 2008165.
[14]
Jian ZL, Hu YS, Ji XL, et al. NASICON-structured materials for energy storage. Adv Mater 2017, 29: 1601925.
[15]
Rajagopalan R, Zhang ZN, Tang YG, et al. Understanding crystal structures, ion diffusion mechanisms and sodium storage behaviors of NASICON materials. Energy Storage Mater 2021, 34: 171–193.
[16]
Yu ZE, Lyu YC, Zou ZY, et al. Understanding the structural evolution and storage mechanism of NASICON-structure Mg0.5Ti2(PO4)3 for Li-ion and Na-ion batteries. ACS Sustainable Chem Eng 2021, 9: 13414–13423.
[17]
Gu ZY, Guo JZ, Sun ZH, et al. Air/water/temperature-stable cathode for all-climate sodium-ion batteries. Cell Rep Phys Sci 2021, 2: 100665.
[18]
Sun C, Zhao YJ, Ni Q, et al. Reversible multielectron redox in NASICON cathode with high energy density for low-temperature sodium-ion batteries. Energy Storage Mater 2022, 49: 291–298.
[19]
Yu H, Ruan XP, Wang JJ, et al. From solid-solution MXene to Cr-substituted Na3V2(PO4)3: Breaking the symmetry of sodium ions for high-voltage and ultrahigh-rate cathode performance. ACS Nano 2022, 16: 21174– 21185.
[20]
Wu YC, Meng XH, Yan LJ, et al. Vanadium-free NASICON-type electrode materials for sodium-ion batteries. J Mater Chem A 2022, 10: 21816–21837.
[21]
Li C, Li R, Liu KN, et al. NASICON: A promising solid electrolyte for solid-state sodium batteries. Interdiscip Mater 2022, 1: 396–416.
[22]
Hong HYP. Crystal structures and crystal chemistry in the system Na1+xZr2SixP3−xO12. Mater Res Bull 1976, 11: 173– 182.
[23]
Goodenough JB, Hong HYP, Kafalas JA. Fast Na+-ion transport in skeleton structures. Mater Res Bull 1976, 11: 203–220.
[24]
Jung JI, Kim D, Kim H, et al. Progressive assessment on the decomposition reaction of Na superionic conducting ceramics. ACS Appl Mater Interfaces 2017, 9: 304–310.
[25]
Hwang SM, Park JS, Kim Y, et al. Rechargeable seawater batteries—From concept to applications. Adv Mater 2019, 31: 1804936.
[26]
Pal SK, Saha R, Kumar GV, et al. Designing high ionic conducting NASICON-type Na3Zr2Si2PO12 solid-electrolytes for Na-ion batteries. J Phys Chem C 2020, 124: 9161–9169.
[27]
Zhao YJ, Wang CZ, Dai YJ, et al. Homogeneous Na+ transfer dynamic at Na/Na3Zr2Si2PO12 interface for all solid-state sodium metal batteries. Nano Energy 2021, 88: 106293.
[28]
Rao YB, Bharathi KK, Patro LN. Review on the synthesis and doping strategies in enhancing the Na ion conductivity of Na3Zr2Si2PO12 (NASICON) based solid electrolytes. Solid State Ion 2021, 366: 115671.
[29]
Yang ZD, Tang B, Xie ZJ, et al. NASICON-type Na3Zr2Si2PO12 solid-state electrolytes for sodium batteries. ChemElectroChem 2021, 8: 1035–1047.
[30]
Jolley AG, Taylor DD, Schreiber NJ, et al. Structural investigation of monoclinic–rhombohedral phase transition in Na3Zr2Si2PO12 and doped NASICON. J Am Ceram Soc 2015, 98: 2902–2907.
[31]
Samiee M, Radhakrishnan B, Rice ZE, et al. Divalent-doped Na3Zr2Si2PO12 natrium superionic conductor: Improving the ionic conductivity via simultaneously optimizing the phase and chemistry of the primary and secondary phases. J Power Sources 2017, 347: 229–237.
[32]
Sun F, Xiang YX, Sun Q, et al. Insight into ion diffusion dynamics/mechanisms and electronic structure of highly conductive sodium-rich Na3+xLaxZr2−xSi2PO12 (0 ≤ x ≤ 0.5) solid-state electrolytes. ACS Appl Mater Interfaces 2021, 13: 13132–13138.
[33]
Jolley AG, Cohn G, Hitz GT, et al. Improving the ionic conductivity of NASICON through aliovalent cation substitution of Na3Zr2Si2PO12. Ionics 2015, 21: 3031–3038.
[34]
Ruan YL, Song SD, Liu JJ, et al. Improved structural stability and ionic conductivity of Na3Zr2Si2PO12 solid electrolyte by rare earth metal substitutions. Ceram Int 2017, 43: 7810–7815.
[35]
Chen D, Luo F, Zhou WC, et al. Influence of Nb5+, Ti4+, Y3+ and Zn2+ doped Na3Zr2Si2PO12 solid electrolyte on its conductivity. J Alloys Compd 2018, 757: 348–355.
[36]
Lu Y, Alonso JA, Yi Q, et al. A high-performance monolithic solid-state sodium battery with Ca2+ doped Na3Zr2Si2PO12 electrolyte. Adv Energy Mater 2019, 9: 1901205.
[37]
Von Alpen U, Bell MF, Höfer HH. Compositional dependence of the electrochemical and structural parameters in the NASICON system (Na1+xSixZr2P3−xO12). Solid State Ion 1981, 3: 215–218.
[38]
Kuriakose AK, Wheat TA, Ahmad A, et al. Synthesis, sintering, and microstructure of NASICONs. J Am Ceram Soc 1984, 67: 179–183.
[39]
Ahmad A, Wheat TA, Kuriakose AK, et al. Dependence of the properties of NASICONs on their composition and processing. Solid State Ion 1987, 24: 89–97.
[40]
Go W, Kim J, Pyo J, et al. Investigation on the structure and properties of Na3.1Zr1.55Si2.3P0.7O11 as a solid electrolyte and its application in a seawater battery. ACS Appl Mater Interfaces 2021, 13: 52727–52735.
[41]
Valle JM, Huang C, Tatke D, et al. Characterization of hot-pressed von Alpen type NASICON ceramic electrolytes. Solid State Ion 2021, 369: 115712.
[42]
Shen L, Yang J, Liu G, et al. High ionic conductivity and dendrite-resistant NASICON solid electrolyte for all-solid-state sodium batteries. Mater Today Energy 2021, 20: 100691.
[43]
Sun F, Xiang YX, Sun Q, et al. Origin of high ionic conductivity of Sc-doped sodium-rich NASICON solid-state electrolytes. Adv Funct Mater 2021, 31: 2102129.
[44]
He SN, Xu YL, Ma XN, et al. Mg2+/F synergy to enhance the ionic conductivity of Na3Zr2Si2PO12 solid electrolyte for solid-state sodium batteries. ChemElectroChem 2020, 7: 2087–2094.
[45]
Berry KA, Harmer MP. Effect of MgO solute on microstructure development in Al2O3. J Am Ceram Soc 1986, 69: 143–149.
[46]
Cha JM, Liu LY, Lee HJ, et al. Crystallization kinetics of lithium–aluminum–germanium–phosphate glass doped with MgO using a non-isothermal method. J Korean Ceram Soc 2021, 58: 614–622.
[47]
Shao YJ, Zhong GM, Lu YX, et al. A novel NASICON-based glass–ceramic composite electrolyte with enhanced Na-ion conductivity. Energy Storage Mater 2019, 23: 514–521.
[48]
Ran LB, Baktash A, Li M, et al. Sc, Ge co-doping NASICON boosts solid-state sodium ion batteries’ performance. Energy Storage Mater 2021, 40: 282–291.
[49]
Wang XX, Chen JJ, Mao ZY, et al. Effective resistance to dendrite growth of NASICON solid electrolyte with lower electronic conductivity. Chem Eng J 2022, 427: 130899.
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Received: 22 December 2022
Revised: 09 February 2023
Accepted: 27 February 2023
Published: 15 April 2023
Issue date: May 2023

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© The Author(s) 2023.

Acknowledgements

This work was supported by Korea Institute of Energy Technology Evaluation and Planning (KETEP) grant funded by the Korea government (MOTIE) (20215610100040, Development of 20 Wh seawater secondary battery unit cell).

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