Spinel compounds as multivalent battery cathodes: A systematic evaluation based on ab initio calculations
By Mengxing Liu, Ziqin Rong, R. Malik, P. Canepa, Anubhav Jain, Gerbrand Ceder, Kristin A. Persson. 2014
362 citations recorded by the source corpus.
Batteries that shuttle multivalent ions such as Mg2+ and Ca2+ ions are promising candidates for achieving higher energy density than available with current Li-ion technology. Finding electrode materials that reversibly store and release these multivalent cations is considered a major challenge for enabling such multivalent battery technology. In this paper, we use recent advances in high-throughput first-principles calculations to systematically evaluate the performance of compounds with the spinel structure as multivalent intercalation cathode materials, spanning a matrix of five different intercalating ions and seven transition metal redox active cations. We estimate the insertion voltage, capacity, thermodynamic stability of charged and discharged states, as well as the intercalating ion mobility and use these properties to evaluate promising directions. Our calculations indicate that the Mn2O4 spinel phase based on Mg and Ca are feasible cathode materials. In general, we find that multivalent cathodes exhibit lower voltages compared to Li cathodes; the voltages of Ca spinels are ∼0.2 V higher than those of Mg compounds (versus their corresponding metals), and the voltages of Mg compounds are ∼1.4 V higher than Zn compounds; consequently, Ca and Mg spinels exhibit the highest energy densities amongst all the multivalent cation species. The activation barrier for the Al3+ ion migration in the Mn2O4 spinel is very high (∼1400 meV for Al3+ in the dilute limit); thus, the use of an Al based Mn spinel intercalation cathode is unlikely. Amongst the choice of transition metals, Mn-based spinel structures rank highest when balancing all the considered properties.
Subfields: Electrical and Electronic Engineering, Inorganic Chemistry
View Paper: https://www.semanticscholar.org/paper/6ca39e2ff1628b7df7da3e984af83d966db2f7fd
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Citations in the corpus
- Vanadium Oxide Pillared by Interlayer Mg2+ Ions and Water as Ultralong-Life Cathodes for Magnesium-Ion Batteries (2019, background): “This is because of the strong interaction between the host lattice and Mg, which results in sluggish solid-state diffusion and large potential polarization.(13,14) Thus, the ideal crystal structure must”
- Predicting the thermodynamic stability of perovskite oxides using machine learning models (2018, background): “vided composition space (e.g. all inorganic crystalline compounds comprising the La-Fe-O system) can be performed. The main parameter governing stability is the energy above the convex hull (E hull ).[21] The value of E hull is a measure of the decomposition energy of the compound into a linear comb”