- Wang, Hui;
- Feng, Xuefei;
- Chen, Ying;
- Liu, Yi-Sheng;
- Han, Kee Sung;
- Zhou, Mingxia;
- Engelhard, Mark H;
- Murugesan, Vijayakumar;
- Assary, Rajeev S;
- Liu, Tianbiao Leo;
- Henderson, Wesley;
- Nie, Zimin;
- Gu, Meng;
- Xiao, Jie;
- Wang, Chongmin;
- Persson, Kristin;
- Mei, Donghai;
- Zhang, Ji-Guang;
- Mueller, Karl T;
- Guo, Jinghua;
- Zavadil, Kevin;
- Shao, Yuyan;
- Liu, Jun
Conventional electrolytes made by mixing simple Mg2+ salts and aprotic solvents, analogous to those in Li-ion batteries, are incompatible with Mg anodes because Mg metal readily reacts with such electrolytes, producing a passivation layer that blocks Mg2+ transport. Here, we report that, through tuning a conventional electrolyte - Mg(TFSI)2 (TFSI- is N(SO2CF3)2-) - with an Mg(BH4)2 cosalt, highly reversible Mg plating/stripping with a high Coulombic efficiency is achieved by neutralizing the first solvation shell of Mg cationic clusters between Mg2+ and TFSI- and enhanced reductive stability of free TFSI-. A critical adsorption step between Mg0 atoms and active Mg cation clusters involving BH4- anions is identified to be the key enabler for reversible Mg plating/stripping through analysis of the distribution of relaxation times (DRT) from operando electrochemical impedance spectroscopy (EIS), operando electrochemical X-ray absorption spectroscopy (XAS), nuclear magnetic resonance (NMR), and density functional theory (DFT) calculations.