| 1. |
- Palacin, M. R., et al.
(författare)
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Roadmap on multivalent batteries
- 2024
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Ingår i: JPhys Energy. - 2515-7655. ; 6:3
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Forskningsöversikt (refereegranskat)abstract
- Battery technologies based in multivalent charge carriers with ideally two or three electrons transferred per ion exchanged between the electrodes have large promises in raw performance numbers, most often expressed as high energy density, and are also ideally based on raw materials that are widely abundant and less expensive. Yet, these are still globally in their infancy, with some concepts (e.g. Mg metal) being more technologically mature. The challenges to address are derived on one side from the highly polarizing nature of multivalent ions when compared to single valent concepts such as Li+ or Na+ present in Li-ion or Na-ion batteries, and on the other, from the difficulties in achieving efficient metal plating/stripping (which remains the holy grail for lithium). Nonetheless, research performed to date has given some fruits and a clearer view of the challenges ahead. These include technological topics (production of thin and ductile metal foil anodes) but also chemical aspects (electrolytes with high conductivity enabling efficient plating/stripping) or high-capacity cathodes with suitable kinetics (better inorganic hosts for intercalation of such highly polarizable multivalent ions). This roadmap provides an extensive review by experts in the different technologies, which exhibit similarities but also striking differences, of the current state of the art in 2023 and the research directions and strategies currently underway to develop multivalent batteries. The aim is to provide an opinion with respect to the current challenges, potential bottlenecks, and also emerging opportunities for their practical deployment.
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| 2. |
- Forero-Saboya, Juan, et al.
(författare)
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Interfaces and Interphases in Ca and Mg Batteries
- 2022
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Ingår i: Advanced Materials Interfaces. - : Wiley. - 2196-7350. ; 9:8
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Forskningsöversikt (refereegranskat)abstract
- The development of high energy density battery technologies based on divalent metals as the negative electrode is very appealing. Ca and Mg are especially interesting choices due to their combination of low standard reduction potential and natural abundance. One particular problem stalling the technological development of these batteries is the low efficiency of plating/stripping at the negative electrode, which relates to several factors that have not yet been looked at systematically; the nature/concentration of the electrolyte, which determines the mass transport of electro-active species (cation complexes) toward the electrode; the possible presence of passivation layers, which may hinder ionic transport and hence limit electrodeposition; and the mechanisms behind the charge transfer leading to nucleation/growth of the metal. Different electrolytes are investigated for Mg and Ca, with the presence/absence of chlorides in the formulation playing a crucial role in the cation desolvation. From a R&D point-of-view, proper characterization alongside modeling is crucial to understand the phenomena determining the mechanisms of the plating/stripping processes. The state-of-the-art is here presented together with a short perspective on the influence of the cation solvation also on the positive electrode and finally an attempt to define guidelines for future research in the field.
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| 3. |
- Tchitchekova, D. S., et al.
(författare)
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On the Reliability of Half-Cell Tests for Monovalent (Li+, Na+) and Divalent (Mg2+, Ca2+) Cation Based Batteries
- 2017
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Ingår i: Journal of the Electrochemical Society. - : The Electrochemical Society. - 1945-7111 .- 0013-4651. ; 164:7, s. A1384-A1392
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Tidskriftsartikel (refereegranskat)abstract
- A comprehensive study is reported entailing a comparison of Li, Na, K, Mg, and Ca based electrolytes and an investigation of the reliability of electrochemical tests using half-cells. Ionic conductivity, viscosity, and Raman spectroscopy results point to the cationsolvent interaction to follow the polarizing power of the cations, i.e. Mg2+ > Ca2+ > Li+ > Na+ > K+ and to divalent cation based electrolytes having stronger tendency to form ion pairs - lowering the cation accessibility and mobility. Both increased temperature and the use of anions with delocalized negative charge, such as TFSI, are effective in mitigating this issue. Another factor impeding the divalent cations mobility is the larger solvation shells, as compared to those of monovalent cations, that in conjunction with stronger solvent - cation interactions contribute to slower charge transfer and ultimately a large impedance of Mg and Ca electrodes. An important consequence is the non-reliability of the pseudo-reference electrodes as these present both significant potential shifts as well as unstable behaviors. Finally, experimental protocols in order to achieve consistent results when using half-cell set-ups are proposed.
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