Operation Mechanism in Hybrid Mg-Li Batteries with TiNb2O7 Allowing Stable High-Rate Cycling.
We studied the structural evolution and cycling behavior of TiNb2O7 (TNO) as a cathode in a nonaqueous hybrid dual-salt Mg-Li battery. A very high fraction of pseudocapacitive contribution to the overall specific capacity makes the material suitable for ultrafast operation in a hybrid battery, composed of a Mg-metal anode, and a dual-salt APC-LiCl electrolyte with Li and Mg cations. Theoretical calculations show that Li intercalation is predominant over Mg intercalation into the TNO in a dual-salt electrolyte with Mg2+ and Li+, while experimentally up to 20% Mg cointercalation was observed after battery discharge. In hybrid Mg-Li batteries, TNO shows capacities which are about 40 mA h g-1 lower than in single-ion Li batteries at current densities of up to 1.2 A g-1. This is likely due to a partial Mg cointercalation or/and location of Li cations on alternative crystallographic sites in the TNO structure in comparison to the Li-intercalation process in Li batteries. Generally, hybrid Mg-Li cells show a markedly superior applicability for a very prolonged operation (above 1000 cycles) with 100% Coulombic efficiency and a capacity retention higher than 95% in comparison to conventional Li batteries with TNO after being cycled either under a low (7.75 mA g-1) or high (1.55 A g-1) current density. The better long-term behavior of the hybrid Mg-Li batteries with TNO is especially pronounced at 60 °C. The reasons for this are an appropriate cathode electrolyte interface containing MgCl2 species and a superior performance of the Mg anode in APC-LiCl electrolytes with a dendrite-free, fast Mg deposition/stripping. This stable interface stands in contrast to the anode electrolyte interface in Li batteries with a Li anode in conventional carbonate-containing electrolytes, which is prone to dendrite formation, thus leading to a battery shortcut.
['Maletti|Sebastian|S|http://orcid.org/0000-0001-5308-658X', 'Janson|Oleg|O|', 'Herzog-Arbeitman|Abraham|A|http://orcid.org/0000-0001-6238-7413', 'Gonzalez Martinez|Ignacio Guillermo|IG|', 'Buckan|Ronny|R|', 'Fischer|Johanna|J|', 'Senyshyn|Anatoliy|A|', 'Missyul|Alexander|A|http://orcid.org/0000-0002-0577-4481', 'Etter|Martin|M|', 'Mikhailova|Daria|D|http://orcid.org/0000-0002-8197-1807']
cathode electrolyte interface fast Mg deposition/stripping Li,Mg cointercalation Wadsley-Roth phase beyond lithium batteries concept dual-salt batteries pseudocapacitive storage