An Additive Incorporated Non-Nucleophilic Electrolyte for Stable Magnesium Ion Batteries

Abstract

Non-nucleophilic electrolytes are promising next-generation highly stable electrolytes for magnesium-ion batteries (MIBs). However, a passivation layer on Mg metal anode usually blocks Mg²⁺ diffusion, leading to poor reaction kinetics and low Coulombic efficiency of the Mg plating/stripping in these electrolytes. Here we explore the utilization of phenyl disulfide (PDF) as a film-forming additive for non-nucleophilic electrolytes to regulate the interfacial chemistry on Mg metal anode. Phenyl-thiolate generated from the PDF additive was found to suppress the unfavorable surface blocking layer, resulted in a high Coulombic efficiency of up to 99.5% for the Mg plating/stripping process as well as a remarkably decreased overpotential. The full battery consisting of Mg metal anode and Mo₆S₇Se cathode remained stable in the PDF additive-containing electrolyte at 0.1 C over 150 cycles at room temperature.

Keywords

magnesium-ion batteries / non-nucleophilic electrolyte / interface / additives / phenyl disulfide

References

[1] Goodenough J, Kim Y. Challenges for rechargeable Li batteries[J]. Chem. Mater., 2010,22(3):587-603.

[2] Li M, Lu J, Chen Z W, Amine K. 30 years of lithium-ion batteries[J]. Adv. Mater., 2018,30(33):1-24.

[3] Dusastre V. Materials for sustainable energy: A Collection of peer-reviewed research and review articles from nature publishing group[M]. World Scientific, 2010.

[4] Aurbach D, Lu Z, Schechter A, Gofer Y, Gizbar H, Turgeman R, Cohen Y, Moshkovich M, Levi E. Prototype systems for rechargeable magnesium batteries[J]. Nature, 2000,407:724-727.

[5] Niu J, Zhang Z, Aurbach D. Alloy anode materials for rechargeable Mg ion batteries[J]. Adv. Energy Mater., 2020,10(23):1-33.

[6] Choi J, Aurbach D. Promise and reality of post-lithium-ion batteries with high energy densities[J]. Nat. Rev. Mater., 2016,1(4):1-16.

[7] Aurbach D, Gofer Y, Lu Z, Schechter A, Chusid O, Gizbar H, Cohen Y, Ashkenazi V, Moshkovich M, Turgeman R. A short review on the comparison between Li battery systems and rechargeable magnesium battery technology[J]. J. Power Sources, 2001, 97-98:28-32.

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

[9] Mohtadi R, Mizuno F. Magnesium batteries: Current state of the art, issues and future perspectives[J]. Beilstein J. Nanotechnol., 2014,5(1):1291-1311.

[10] Deivanayagam R, Ingram B, Shahbazian-Yassar R. Progress in development of electrolytes for magnesium batteries[J]. Energy Storage Mater., 2019,21:136-153.

[11] Muldoon J, Bucur C B, Oliver A G, Sugimoto T, Matsui M, Kim H S, Allred G D, Zajicek J, Kotani Y. Electrolyte roadblocks to a magnesium rechargeable battery[J]. Energy Environ. Sci., 2012,5(3):5941-5950.

[12] Shi J, Zhang J, Guo J, Lu J. Interfaces in rechargeable magnesium batteries[J]. Nanoscale Horiz., 2020,5(11):1467-1475.

[13] Li Y, Guan S, Huo H, Ma Y, Gao Y, Zuo P, Yin G. A review of magnesium aluminum chloride complex electrolytes for Mg batteries[J]. Adv. Funct. Mater., 2021,31(24):1-22.

[14] Liu F, Wang T, Liu X, Fan L Z. Challenges and recent progress on key materials for rechargeable magnesium batteries[J]. Adv. Energy Mater., 2021,11(2):1-28.

[15] Wang F F, Guo Y S, Yang J, Nuli Y, Hirano S I. A novel electrolyte system without a Grignard reagent for recharge-able magnesium batteries[J]. Chem. Commun., 2012,48(87):10763-10765.

[16] Shuai H, Xu J, Huang K. Progress in retrospect of electrolytes for secondary magnesium batteries[J]. Coord. Chem. Rev., 2020,422:213478.

[17] Zhao-Karger Z, Zhao X, Fuhr O, Fichtner M. Bisamide based non-nucleophilic electrolytes for rechargeable magnesium batteries[J]. RSC Adv., 2013,3(37):16330-16335.

[18] Mao M, Gao T, Hou S, Wang C S. A critical review of cathodes for rechargeable Mg batteries[J]. Chem. Soc. Rev., 2018,47(23):8804-8841.

[19] Tan S, Xiong F, Wang J, An Q, Mai L Q. Crystal regulation towards rechargeable magnesium battery cathode materials[J]. Mater. Horiz., 2020,7(8):1971-1995.

[20] Kim H S, Arthur T S, Allred G D, Zajicek J, Newman J G, Rodnyansky A E, Oliver A G, Boggess W C, Muldoon J. Structure and compatibility of a magnesium electrolyte with a sulphur cathode[J]. Nat. Commun., 2011,2(1):1-6.

[21] Xu K. Electrolytes and interphases in Li-ion batteries and beyond[J]. Chem. Rev., 2014,114(23):11503-11618.

[22] Sun Y, Zou Q, Wang W, Lu Y C. Non-passivating anion adsorption enables reversible magnesium redox in simple non-nucleophilic electrolytes[J]. ACS Energy Lett., 2021,6(10):3607-3613.

[23] Li X, Gao T, Han F, Ma Z, Fan X, Hou S, Eidson N, Li W, Wang C. Reducing Mg anode overpotential via ion conductive surface layer formation by iodine additive[J]. Adv. Energy Mater., 2018,8(7):1-6.

[24] Wu M, Bhargav A, Cui Y, Siegel A, Agarwal M, Ma Y, Fu Y. Highly reversible diphenyl trisulfide catholyte for rechargeable lithium batteries[J]. ACS Energy Lett., 2016,1(6):1221-1226.

[25] Pipes R, Bhargav A, Manthiram A. Phenyl disulfide additive for solution-mediated carbon dioxide utilization in Li-CO₂ batteries[J]. Adv. Energy Mater., 2019,9(21):1-8.

[26] Aurbach D, Suresh GS, Levi E, Mitelman A, Mizrahi O, Chusid O, Brunelli M. Progress in rechargeable magnesium battery technology[J]. Adv. Mater., 2007,19(23):4260-4267.

[27] Roux M V, Foces-Foces C, Notario R, Ribeiro da Silva M A, Ribeiro da Silva M, Santos A, Juaristi E. Experimental and computational thermochemical study of sulfur-containing Amino acids: L-Cysteine, L-Cystine, and L-Cysteine-derived radicals. S-S, S-H, and C-S bond dissociation enthalpies[J]. J. Phys. Chem. B, 2010,114(32):10530-10540.

[28] Scheriber F. Structure and growth of self-assembling monolayers[J]. Prog. Surf. Sci., 2000,65(5-8):151-257.

[29] Roberts J, Friend C. Spectroscopic identification of surface phenyl thiolate and benzyne on Mo(110)[J]. J. Chem. Phys., 1988,88(11):7172-7180.

[30] Lu J Y, Ke C Z, Gong Z L, Li D P, Ci L J, Zhang L, Zhang Q B. Application of in-situ characterization techniques in all-solid-state lithium batteries[J]. Acta Phys. Sin., 2021,70(19):198102.

[31] Zhang Q B, Gong Z L, Yang Y. Advance in interface and characterizations of sulfide solid electrolyte materials. Acta Phys. Sin., 2020,69(22):228803.

[32] Yang K, Chen L, Ma J, Lai C, Huang Y, Mi J, Biao J, Zhang D, Shi P, Xia H. Stable interface chemistry and multiple ion transport of composite electrolyte contribute to ultra-long cycling solid-state LiNi₀.₈Co_0.1Mn_0.1O₂/lithium metal batteries[J]. Angew. Chem. Int. Ed., 2021,60:24668-24675.

[33] Lei D, He Y B, Huang H, Yuan Y, Zhong G, Zhao Q, Hao X, Zhang D, Lai C, Zhang S. Cross-linked beta alumina nanowires with compact gel polymer electrolyte coating for ultra-stable sodium metal battery[J]. Nat. Comm., 2019,10:1-11.

[34] Yi R W, Mao Y Y, Shen Y B, Chen L W. Self-assembled monolayers for batteries[J]. J. Am. Chem. Soc., 2021,143(33):12897-12912.