Data-Driven Viewpoint for Developing Next-Generation Mg-Ion Solid-State Electrolytes

Abstract

Magnesium (Mg) is a promising alternative to lithium (Li) as an anode material in solid-state batteries due to its abundance and high theoretical volumetric capacity. However, the sluggish Mg-ion conduction in the lattice of solid-state electrolytes (SSEs) is one of the key challenges that hamper the development of Mg-ion solid-state batteries. Though various Mg-ion SSEs have been reported in recent years, key insights are hard to be derived from a single literature report. Besides, the structure-performance relationships of Mg-ion SSEs need to be further unraveled to provide a more precise design guideline for SSEs. In this Viewpoint article, we analyze the structural characteristics of the Mg-based SSEs with high ionic conductivity reported in the last four decades based upon data mining - we provide big-data-derived insights into the challenges and opportunities in developing next-generation Mg-ion SSEs.

Keywords

Data mining / Magnesium-ion solid-state electrolytes / All-solid-state batteries / Magnesium-ion conductivity

References

[1] Armand M, Tarascon J M. Building better batteries[J]. Nature, 2008, 451(7179): 652-657.

[2] Ding Y L, Cano Z P, Yu A P, Lu J, Chen Z W. Automotive Li-ion batteries: Current status and future perspectives[J]. Electrochem. Energy Rev., 2019, 2(1): 1-28.

[3] Kamaya N, Homma K, Yamakawa Y, Hirayama M, Kanno R, Yonemura M, Kamiyama T, Kato Y, Hama S, Kawamoto K. A lithium superionic conductor[J]. Nature, 2011, 10(9): 682-686.

[4] Seino Y, Ota T, Takada K, Hayashi A, Tatsumisago M. A sulphide lithium super ion conductor is superior to liquid ion conductors for use in rechargeable batteries[J]. Energy Environ. Sci., 2014, 7(2): 627-631.

[5] Kim S, Oguchi H, Toyama N, Sato T, Takagi S, Otomo T, Arunkumar D, Kuwata N, Kawamura J, Orimo S I. A complex hydride lithium superionic conductor for high-energy-density all-solid-state lithium metal batteries[J]. Nat. Commun., 2019, 10(1): 1081.

[6] Li Y X, Song S B, Kim H, Nomoto K, Kim H, Sun X Y, Hori S, Suzuki K, Matsui N, Hirayama M. A lithium superionic conductor for millimeter-thick battery electrode[J]. Science, 2023, 381(6653): 50-53.

[7] Lu P S, Xia Y, Sun G C, Wu D X, Wu S Y, Yan W L, Zhu X, Lu J Z, Niu Q H, Shi S C. Realizing long-cycling all-solid-state Li-In||TiS₂ batteries using Li_6+xM_xAs_1-xS₅I (M = Si, Sn) sulfide solid electrolytes[J]. Nat. Commun., 2023, 14(1): 4077.

[8] Hu L, Wang J Z, Wang K, Gu Z Q, Xi Z W, Li H, Chen F, Wang Y X, Li Z Y, Ma C. A cost-effective, ionically conductive and compressible oxychloride solid-state electrolyte for stable all-solid-state lithium-based batteries[J]. Nat. Commun., 2023, 14(1): 3807.

[9] Kato Y, Hori S, Saito T, Suzuki K, Hirayama M, Mitsui A, Yonemura M, Iba H, Kanno R. High-power all-solid-state batteries using sulfide superionic conductors[J]. Nat. Energy, 2016, 1(4): 1-7.

[10] Dunn B, Kamath H, Tarascon J M. Electrical energy storage for the grid: a battery of choices[J]. Science, 2011, 334(6058): 928-935.

[11] Goodenough J B, Park K S. The Li-ion rechargeable battery: a perspective[J]. J. Am. Chem. Soc., 2013, 135(4): 1167-1176.

[12] Larcher D, Tarascon J M. Towards greener and more sustainable batteries for electrical energy storage[J]. Nat. Chem., 2015, 7(1): 19-29.

[13] Goodenough J B. How we made the Li-ion rechargeable battery[J]. Nat. Electron., 2018, 1(3): 204-204.

[14] Whittingham M S. Lithium batteries and cathode materials[J]. Chem. Rev., 2004, 104(10): 4271-4302.

[15] Luo Y, Yang X F, Wang C H, Fraser A, Zhang H Z, Sun X L, Li X F. Advanced metal anodes and their interface design toward safe metal batteries: A comprehensive review[J]. Prog. Mater Sci., 2023: 101171.

[16] Liang Y L, Dong H, Aurbach D, Yao Y. Current status and future directions of multivalent metal-ion batteries[J]. Nat. Energy, 2020, 5(9): 646-656.

[17] Attias R, Salama M, Hirsch B, Goffer Y, Aurbach D. Anode-electrolyte interfaces in secondary magnesium batteries[J]. Joule, 2019, 3(1): 27-52.

[18] Zuo P J, Yin G P. Chelated electrolytes for divalent metal ions[J]. Science, 2021, 374(6564): 156-156.

[19] Rong Z, Malik R, Canepa P, Sai Gautam G, Liu M, Jain A, Persson K, Ceder G. Materials design rules for multivalent ion mobility in intercalation structures[J]. Chem. Mater., 2015, 27(17): 6016-6021.

[20] Wang Q, Li H J, Zhang R X, Liu Z Z, Deng H Y, Cen W L, Yan Y G, Chen Y G. Oxygen vacancies boosted fast Mg²⁺ migration in solids at room temperature[J]. Energy Storage Mater., 2022, 51: 630-637.

[21] Goodenough J B. Solid electrolytes[J]. Pure Appl. Chem., 1995, 67(6): 931-938.

[22] Ikeda S, Takahashi M, Ishikawa J, Ito K. Solid electrolytes with multivalent cation conduction. 1. Conducting species in MgZrPO₄ system[J]. Solid State Ionic, 1987, 23(1-2): 125-129.

[23] Jaschin P W, Gao Y, Li Y, Bo S H. A materials perspective on magnesium-ion-based solid-state electrolytes[J]. J. Mater. Chem. A, 2020, 8(6): 2875-2897.

[24] Anuar N K, Adnan S B, Mohamed N S. Characterization of Mg_0.5Zr₂(PO₄)₃ for potential use as electrolyte in solid state magnesium batteries[J]. Ceram. Int., 2014, 40(8): 13719-13727.

[25] Halim Z A, Adnan S B, Mohamed N S. Effect of sintering temperature on the structural, electrical and electrochemical properties of novel Mg_0.5Si₂(PO₄)₃ ceramic electrolytes[J]. Ceram. Int., 2016, 42(3): 4452-4461.

[26] Liang B, Keshishian V, Liu S, Yi E, Jia D, Zhou Y, Kieffer J, Ye B, Laine R M. Processing liquid-feed flame spray pyrolysis synthesized Mg_0.5Ce_0.2Zr_1.8(PO₄)₃ nanopowders to free standing thin films and pellets as potential electrolytes in all-solid-state Mg batteries[J]. Electrochim. Acta, 2018, 272: 144-153.

[27] Le Ruyet R, Fleutot B, Berthelot R, Benabed Y, Hautier G, Filinchuk Y, Janot R L. Mg₃(BH₄)₄(NH₂)₂ as inorganic solid electrolyte with high Mg²⁺ ionic conductivity[J]. ACS Appl. Energy Mater., 2020, 3(7): 6093-6097.

[28] Roedern E, Kühnel R S, Remhof A, Battaglia C. Magnesium ethylenediamine borohydride as solid-state electrolyte for magnesium batteries[J]. Sci. Rep., 2017, 7(1): 46189.

[29] Higashi S, Miwa K, Aoki M, Takechi K. A novel inorganic solid state ion conductor for rechargeable Mg batteries[J]. Chem. Commun., 2014, 50(11): 1320-1322.

[30] Canepa P, Bo S H, Sai Gautam G, Key B, Richards W D, Shi T, Tian Y, Wang Y, Li J, Ceder G. High magnesium mobility in ternary spinel chalcogenides[J]. Nat. Commun., 2017, 8(1): 1759.

[31] Mohtadi R, Orimo S I. The renaissance of hydrides as energy materials[J]. Nat. Rev. Mater., 2016, 2(3): 1-15.

[32] Guo H Y, Wang Q, Stuke A, Urban A, Artrith N. Accelerated atomistic modeling of solid-state battery materials with machine learning[J]. Front. Energy Res., 2021, 9: 695902.

[33] Yang F L, Campos D S, Jia X, Sato R, Kisu K, Hashimoto Y, Orimo S I, Li H. A dynamic database of solid-state electrolyte (DDSE) picturing all-solid-state batteries[J]. Nano Mater. Sci., 2023. DOI: 10.1016/j.nanoms.2023.08.002

[34] A dynamic database of solid-state electrolyte DDSE picturing all-solid-state batteries. https://doi.org/10.50974/00137195.

[35] Ferrari S, Falco M, Muñoz G, Ana Belén, Bonomo M, Brutti S, Pavone M, Gerbaldi C. Solid‐state post Li metal ion batteries: A sustainable forthcoming reality?[J]. Adv. Energy Mater., 2021, 11(43): 2100785.

[36] Blanchard D, Maronsson J B, Riktor M, Kheres J, Sveinbjörnsson D, Gil Bardají E, Léon A, Juranyi F, Wuttke J, Lefmann K. Hindered rotational energy barriers of BH₄^-tetrahedra in β-Mg(BH₄)₂ from quasielastic neutron scattering and DFT calculations[J]. J. Phys. Chem. C, 2012, 116(2): 2013-2023.

[37] Le Ruyet R, Berthelot R, Salager E, Florian P, Fleutot B, Janot R. Investigation of Mg(BH₄)(NH₂)-based composite materials with enhanced Mg²⁺ ionic conductivity[J]. J. Phys. Chem. C, 2019, 123(17): 10756-10763.

[38] Matsuo M, Oguchi H, Sato T, Takamura H, Tsuchida E, Ikeshoji T, Orimo S I. Sodium and magnesium ionic conduction in complex hydrides[J]. J. Alloys Compd., 2013, 580: S98-S101.

[39] Ikeshoji T, Tsuchida E, Takagi S, Matsuo M, Orimo S I. Magnesium ion dynamics in Mg(BH₄)_2(1-x)X_2x (X = Cl or AlH₄) from first-principles molecular dynamics simulations[J]. RSC Adv., 2014, 4(3): 1366-1370.

[40] Amdisen M B, Grinderslev J B, Skov L N, Jensen T R. Methylamine magnesium borohydrides as electrolytes for all-solid-state magnesium batteries[J]. Chem. Mater., 2023, 35(3): 1440-1448.

[41] Pang Y P, Nie Z F, Xu F, Sun L X, Yang J H, Sun D L, Fang F, Zheng S Y. Borohydride ammoniate solid electrolyte design for all-solid‐state mg batteries[J]. Energy Environ. Mater., 2022: e12527.

[42] Kisu K, Kim S, Inukai M, Oguchi H, Takagi S, Orimo S I. Magnesium borohydride ammonia borane as a magnesium ionic conductor[J]. ACS Appl. Energy Mater., 2020, 3(4): 3174-3179.

[43] Guo M, Yuan C, Zhang T, Yu X. Solid-state electrolytes for rechargeable magnesium-ion batteries: From structure to mechanism[J]. Small, 2022, 18(43): e2106981.

[44] Yan Y G, Dononelli W, Jørgensen M, Grinderslev J B, Lee Y S, Cho Y W, Černý R, Hammer B, Jensen T R. The mechanism of Mg2+ conduction in ammine magnesium borohydride promoted by a neutral molecule[J]. Phys. Chem. Chem. Phys, 2020, 22(17): 9204-9209.

[45] Palumbo M, Kisu K, Gulino V, Nervi C, Maschio L, Casassa S, Orimo S I, Baricco M. Ion conductivity in a magnesium borohydride ammonia borane solid-state electrolyte[J]. J. Phys. Chem. C, 2022, 126(36): 15118-15127.

[46] Lu Z H, Ciucci F. Metal borohydrides as electrolytes for solid-state Li, Na, Mg, and Ca batteries: a first-principles study[J]. Chem. Mater., 2017, 29(21): 9308-9319.

[47] Kisu K, Dorai A, Kim S, Hamada R, Kumatani A, Horiguchi Y, Sato R, Sau K, Takagi S, Orimo S I. Fast divalent conduction in MB₁₂H₁₂·12H₂O (M= Zn, Mg) complex hydrides: effects of rapid crystal water exchange and application for solid-state electrolytes[J]. J. Mater. Chem. A, 2022, 10(46): 24877-24887.

[48] Skov L N, Grinderslev J B, Rosenkranz A, Lee Y S, Jensen T R. Towards solid‐state magnesium batteries: Ligand-assisted superionic conductivity[J]. Batteries Supercap, 2022, 5(9): e202200163.

[49] Yan Y G, Grinderslev J B, Jo̷rgensen M, Skov L N, Skibsted J R, Jensen T R. Ammine magnesium borohydride nanocomposites for all-solid-state magnesium batteries[J]. ACS Appl. Energy Mater., 2020, 3(9): 9264-9270.

[50] Yan Y G, Grinderslev J B, Burankova T, Wei S H, Embs J P, Skibsted J, Jensen T R. Fast room-temperature Mg²⁺ conductivity in Mg (BH₄)₂ 1.6NH₃-Al₂O₃ nanocomposites[J]. J. Phys. Chem. Lett., 2022, 13(9): 2211-2216.

[51] Wu D Z, Zhuang Y C, Wang F, Yang Y, Zeng J, Zhao J B. High-rate performance magnesium batteries achieved by direct growth of honeycomb-like V₂O₅ electrodes with rich oxygen vacancies[J]. Nano Res., 2023, 16(4): 4880-4887.

[52] Wu D Z, Wen Z P, Jiang H B, Li H, Zhuang Y C, Li J Y, Yang Y, Zeng J, Cheng J, Zhao J B. Ultralong-lifespan magnesium batteries enabled by the synergetic manipulation of oxygen vacancies and electronic conduction[J]. ACS Appl. Mater. Interface, 2021, 13(10): 12049-12058.

[53] Song Y L, Yang L Y, Li J, Zhang M Z, Wang Y H, Li S N, Chen S M, Yang K, Xu K, Pan F. Synergistic dissociation‐and‐trapping effect to promote Li‐ion conduction in polymer electrolytes via oxygen vacancies[J]. Small, 2021, 17(42): 2102039.

[54] Chen H, Adekoya D, Hencz L, Ma J, Chen S, Yan C, Zhao H, Cui G, Zhang S. Stable seamless interfaces and rapid ionic conductivity of Ca-CeO₂/LiTFSI/PEO composite electrolyte for high‐rate and high-voltage all-solid-state battery[J]. Adv. Energy Mater., 2020, 10(21): 2000049.

[55] Wang L P, Zhao K Z, Klein F, Chable J, Braun T, Schür A R, Wang C R, Guo Y G, Fichtner M. MgSc₂Se₄—A magnesium solid ionic conductor for all‐solid‐state mg batteries?[J]. ChemSusChem, 2019, 12(10): 2286-2293.

[56] Tang W S, Dimitrievska M, Stavila V, Zhou W, Wu H, Talin A A, Udovic T J. Order-disorder transitions and superionic conductivity in the sodium nido-undeca(carba)borates[J]. Chem. Mater., 2017, 29(24): 10496-10509.

[57] Brighi M, Murgia F, Černý R. Closo-hydroborate sodium salts as an emerging class of room-temperature solid electrolytes[J]. Cell Rep. Phys. Sci., 2020, 1(10): 100217.

[58] Liu H X, Zhou X, Ye M X, Shen J F. Ion migration mechanism study of hydroborate/carborate electrolytes for all-solid-state batteries[J]. Electrochem. Energy Rev., 2023, 6(1): 31.

[59] Sharma M, Sethio D, Lawson Daku L V M, Hagemann H. Theoretical study of halogenated B₁₂H_nX_(12-n)^2-(X= F, Cl, Br)[J]. J. Phys. Chem. A, 2019, 123(9): 1807-1813.

[60] Li S H, Qiu P T, Kang J X, Shi Z P, Zhang Y C, Ma Y M, Chen X N. Halogenated sodium/lithium monocarba-closo-decaborates: Synthese, characterization, and solid-state ionic conductivity[J]. Mater. Chem. Front., 2021, 5(22): 8037-8046.

[61] Fang H, Jena P. B₁₂(SCN)₁₂^-: An ultrastable weakly coordinating dianion[J]. J. Phys. Chem. C, 2017, 121(14): 7697-7702.

[62] Hansen B R, Paskevicius M, Jørgensen M, Jensen T R. Halogenated sodium-closo-dodecaboranes as solid-state ion conductors[J]. Chem. Mater., 2017, 29(8): 3423-3430.

[63] Zhang Z Z, Nazar L F. Exploiting the paddle-wheel mechanism for the design of fast ion conductors[J]. Nat. Rev. Mater., 2022, 7(5): 389-405.

[64] Berger A, Ibrahim A, Buckley C E, Paskevicius M. Divalent closo-monocarborane solvates for solid-state ionic conductors[J]. Phys. Chem. Chem. Phys, 2023, 25(7): 5758-5775.

[65] Kisu K, Kim S, Shinohara T, Zhao K, Züttel A, Orimo S I. Monocarborane cluster as a stable fluorine-free calcium battery electrolyte[J]. Sci. Rep., 2021, 11(1): 7563.

[66] Duchêne L, Kühnel R, S, Stilp E, Reyes E C, Remhof A, Hagemann H, Battaglia C. A stable 3 V all-solid-state sodium-ion battery based on a closo-borate electrolyte[J]. Nat. Commun., 2017, 10(12): 2609-2615.

[67] Sun J, Kang S, Kim J, Min K. Accelerated discovery of novel garnet-type solid-state electrolyte candidates via machine learning[J]. ACS Appl. Mater. Interfaces, 2023, 15(4): 5049-5057.

[68] Kim J, Kang S, Min K. Screening platform for promising Na superionic conductors for Na-ion solid-state electrolytes[J]. ACS Appl. Mater. Interfaces, 2023, 15(35): 41417-41425.

[69] Zhang Z W, Chu J C, Zhang H F, Liu X Y, He M G. Mining ionic conductivity descriptors of antiperovskite electrolytes for all-solid-state batteries via machine learning[J]. J. Energy Storage, 2024, 75: 109714.

[70] Wan Z J, Chen X Z, Zhou Z Q, Zhong X L, Luo X B, Xu D W. Atom substitution of the solid-state electrolyte Li₁₀GeP₂S₁₂ for stabilized all-solid-state lithium metal batteries[J]. J. Energy Chem., 2024, 88: 28-38.

[71] Keck J. Variational theory of reaction rates[J]. Adv. Chem. Phys., 1967, 13: 85-121.

[72] Henkelman G, Uberuaga B P, Jónsson H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths[J]. J. Chem. Phys., 2000, 113(22): 9901-9904.

[73] Chen H M, Wong L L, Adams S. SoftBV—a software tool for screening the materials genome of inorganic fast ion conductors[J]. Acta Crystallogr. Sect. B-Struct. Sci.Cryst. Eng. Mat., 2019, 75(1): 18-33.

[74] Campos D S E, Sato R, Kisu K, Sau K, Jia X, Yang F, Orimo S I, Li H. Explore the ionic conductivity trends on B12H12 divalent closo-type complex hydride electrolytes[J]. Chem. Mater., 2023, 35(15): 5996-6004.

[75] Mori K, Enjuji K, Murata S, Shibata K, Kawakita Y, Yonemura M, Onodera Y, Fukunaga T. Direct observation of fast lithium-ion diffusion in a superionic conductor: Li₇P₃S₁₁ metastable crystal[J]. Phys. Rev. Appl., 2015, 4(5): 054008.

[76] Soloninin A V, Dimitrievska M, Skoryunov R V, Babanova O A, Skripov A V, Tang W S, Stavila V, Orimo S I, Udovic T J. Comparison of anion reorientational dynamics in MCB₉H₁₀ and M₂B₁₀H₁₀ (M = Li, Na) via nuclear magnetic resonance and quasielastic neutron scattering studies[J]. J. Phys. Chem. C, 2017, 121(2): 1000-1012.

[77] Duchêne L, Lunghammer S, Burankova T, Liao W-C, Embs J P, Copéret C, Wilkening H M R, Remhof A, Hagemann H, Battaglia C. Ionic conduction mechanism in the Na₂(B₁₂H₁₂)_0.5(B₁₀H₁₀)_0.5 closo-borate solid-state electrolyte: interplay of disorder and ion-ion interactions[J]. Chem. Mater., 2019, 31(9): 3449-3460.

[78] Payandeh S H, Asakura R, Avramidou P, Rentsch D, Łodziana Z, Cerny R, Remhof A, Battaglia C. Nido-Borate/Closo-Borate mixed-anion electrolytes for all-solid-state batteries[J]. Chem. Mater., 2020, 32(3): 1101-1110.

[79] Lundberg S M, Lee S I. A unified approach to interpreting model predictions[M]// Advances in Neural Information Processing Systems, Neural Information Processing Systems (NIPS), California 92037 USA 2017, 30.

[80] Friedman J H. Multivariate adaptive regression splines[J]. Ann. Stat., 1991, 19(1): 1-67.

[81] Raschka S. MLxtend: Providing machine learning and data science utilities and extensions to Python’s scientific computing stack[J]. Journal of Open Source Software, 2018, 3(24): 638.

[82] Kim J H, Jun B, Jang Y J, Choi S H, Choi S H, Cho S M, Kim Y G, Kim B H, Lee S U. Highly reliable and large-scale simulations of promising argyrodite solid-state electrolytes using a machine-learned moment tensor potential[J]. Nano Energy, 2024, 124: 109436.

[83] Li J, Zhou M S, Wu H H, Wang L F, Zhang J, Wu N T, Pan K M, Liu G L, Zhang Y G, Han J J, Liu X M, Chen X, Wan J Y, Zhang Q B. Machine learning-assisted property prediction of solid-state electrolyte[J]. Adv. Energy Mater., 2024: 2304480.

[84] Zheng Z Y, Zhou J, Zhu Y S. Computational approach inspired advancements of solid-state electrolytes for lithium secondary batteries: from first-principles to machine learning[J]. Chem. Soc. Rev., 2024, 53: 3134-3166.

[85] Sendek A D, Yang Q, Cubuk E D, Duerloo K A N, Cui Y, Reed E. Holistic computational structure screening of more than 12000 candidates for solid lithium-ion conductor materials[J]. Energy Environmental Science, 2017, 10(1): 306-320.

[86] Heere M, Hansen A L, Payandeh S H, Aslan N, Gizer G, Sørby M H, Hauback B C, Pistidda C, Dornheim M, Lohstroh W. Dynamics of porous and amorphous magnesium borohydride to understand solid state Mg-ion-conductors[J]. Sci. Rep., 2020, 10(1): 9080.