Iron Based Materials for Positive Electrodes in Li-ion Batteries: Electrode Dynamics, Electronic Changes, Structural Transformations
- Datum: 2017-04-28 kl 09:00
- Plats: Häggsalen, Lägerhyddsvägen 1, Uppsala
- Doktorand: Blidberg, Andreas
- Om avhandlingen
- Arrangör: Strukturkemi
- Kontaktperson: Blidberg, Andreas
In this thesis, three new iron based electrode materials for positive electrodes in Li-ion batteries were investigated.
Li-ion battery technology is currently the most efficient form of electrochemical energy storage. The commercialization of Li-ion batteries in the early 1990’s revolutionized the portable electronics market, but further improvements are necessary for applications in electric vehicles and load levelling of the electric grid. In this thesis, three new iron based electrode materials for positive electrodes in Li-ion batteries were investigated. Utilizing the redox activity of iron is beneficial over other transition metals due to its abundance in the Earth’s crust. The condensed phosphate Li2FeP2O7 together with two different LiFeSO4F crystal structures that were studied herein each have their own advantageous, challenges, and scientific questions, and the combined insights gained from the different materials expand the current understanding of Li-ion battery electrodes.
The surface reaction kinetics of all three compounds was evaluated by coating them with a conductive polymer layer consisting of poly(3,4-ethylenedioxythiophene), PEDOT. Both LiFeSO4F polymorphs showed reduced polarization and increased charge storage capacity upon PEDOT coating, showing the importance of controlling the surface kinetics for this class of compounds. In contrast, the electrochemical performance of PEDOT coated Li2FeP2O7 was at best unchanged. The differences highlight that different rate limiting steps prevail for different Li-ion insertion materials.
In addition to the electrochemical properties of the new iron based energy storage materials, also their underlying material properties were investigated. For tavorite LiFeSO4F, different reaction pathways were identified by in operando XRD evaluation during charge and discharge. Furthermore, ligand involvement in the redox process was evaluated, and although most of the charge compensation was centered on the iron sites, the sulfate group also played a role in the oxidation of tavorite LiFeSO4F. In triplite LiFeSO4F and Li2FeP2O7, a redistribution of lithium and iron atoms was observed in the crystal structure during electrochemical cycling. For Li2FeP2O7, and increased randomization of metal ions occurred, which is similar to what has been reported for other iron phosphates and silicates. In contrast, triplite LiFeSO4F showed an increased ordering of lithium and iron atoms. An electrochemically induced ordering has previously not been reported upon electrochemical cycling for iron based Li-ion insertion materials, and was beneficial for the charge storage capacity of the material.