Lithium versus Mono/Polyvalent Ion Intercalation: Hybrid Metal Ion Systems for Energy Storage

Abstract

The energy storage by redox intercalation reactions is, nowadays, the most effective rechargeable ion battery. When lithium is used as intercalating agents, the high energy density is achieved at an expense of non-sustainability. The replacement of Li with cheaper monovalent ions enables to make greener battery alternatives. The utilization of polyvalent ions instead of Li permits to multiplying the battery capacity. Contrary to Li , the realization of quick and reversible intercalation of bigger monovalent and of polyvalent ions is a scientific challenge due to kinetic constraints, polarizing ion effects and Coulomb interactions. Herein we provide a vision how to make the intercalation of these ions feasible. The idea is to perform dual intercalation of ions having different charges, radii, preferred coordination and diffusion pathway topology. All these features are demonstrated by the recent knowledge on selective and non-selective intercalation properties of oxides and polyanion compounds with layered and tunnel structures. Based on dual intercalation properties, the fabrication of hybrid metal ion batteries is presented and discussed.

Focus on Spinel Li4Ti5O12 as Insertion Type Anode for High‐Performance Na‐Ion Batteries

“…Most recently, dual metal‐ion battery, i.e., hybrid Li–Na‐ion batteries are growing as a more attractive technology as it has the combination of high energy density LIB and cost‐effective SIB that offers high energy and power densities owing to different redox potentials for Li + and Na + as mentioned earlier . This novel kind of rechargeable device stores the energy via the intercalation of Li + and Na + which is not like a typical single ion intercalation process occurs in the LIB or SIB . However, it is mandatory to pick the appropriate electrode materials that can intercalate two different alkali ions at different potentials.…”

Storage performance of Mg2+ substituted NaMnPO4 with an olivine structure

“…6 The storage performance of phosphoolivines is analyzed in sodium and lithium half-ion cells, as well as in full-ion cells versus bio-mass derived activated carbon and spinel Li 4 Ti 5 O 12 as anodes. The spinel oxide is selected since it is able to intercalate reversibly both Li + and Na + ions, [12][13][14] while activated carbon intercalates more easily Na + ions than Li + . 15,16 The compatibility of phospho-olivines with electrolytes is assessed by utilization of several types of lithium and sodium carbonate-based solutions.…”

Hybrid Li/Na Ion Batteries: Temperature-Induced Reactivity of Three-Layered Oxide (P3-Na2/3Ni1/3Mg1/6Mn1/2O2) Toward Lithium Ionic Liquid Electrolytes

“…Nowadays, hybrid metal ion batteries (HMIBs) are perceived as competitive alternatives to lithium ion batteries (LiIBs) because they provide better balance between energy/power density, battery cost, and environmental requirements (Yao et al, 2016;Whittingham et al, 2018;Stoyanova et al, 2019). In comparison with LiIBs, two types of charge carriers (such as Li + /Na + , Li + /Mg 2+ , Na + /Mg 2+ , etc.)…”

“…In comparison with LiIBs, two types of charge carriers (such as Li + /Na + , Li + /Mg 2+ , Na + /Mg 2+ , etc.) participate in the electrochemical reaction at HIMBs instead of the single Li + ions (Yao et al, 2016;Stoyanova et al, 2019). There are two operating mechanisms, according to which the energy is stored either by two separate redox reactions occurring at the one and the other electrode, or by co-intercalation/co-deintercalation of two charge carriers at each electrode (Yagi et al, 2014;Yao et al, 2016;Zhang et al, 2018;Kravchyk et al, 2019;Stoyanova et al, 2019).…”

“…participate in the electrochemical reaction at HIMBs instead of the single Li + ions (Yao et al, 2016;Stoyanova et al, 2019). There are two operating mechanisms, according to which the energy is stored either by two separate redox reactions occurring at the one and the other electrode, or by co-intercalation/co-deintercalation of two charge carriers at each electrode (Yagi et al, 2014;Yao et al, 2016;Zhang et al, 2018;Kravchyk et al, 2019;Stoyanova et al, 2019). When the battery operation includes two separate redox reactions, the amount of electrolyte needs to be large in order to supply enough charge carriers upon cell charging and discharging, resulting in a penalty in energy density (Cheng et al, 2016).…”