Active vs. Passive : The Role of Ceramic Particles in Solid Composite Polymer Electrolytes for Lithium Batteries

Since the state-of-the-art Li-ion batteries are close to reaching their theoretical limit in energy density, it becomes crucial to develop next-generation batteries that enable better safety, higher energy density, and longer lifetime. One such next-generation technology is solid-state batteries, employing solid-state electrolytes. Both polymer and inorganic electrolytes are well-explored in this context. While polymers are flexible and easily processable, their ionic conductivities are generally insufficient. Inorganic ceramics can be good ionic conductors, but display interfacial issues. Therefore, combining polymeric and ceramic material in composites polymer electrolytes (CPEs) can – in principle – be beneficial to merge the advantages of both categories. However, it is still unclear how to best construct such systems, and how the ions are actually transported in them. This thesis explores ionic transport in CPEs, both with ion-conducting (“active”) and non-ion-conducting (“passive”) ceramic fillers. The focus is on the amorphous polymer material poly(trimethylene carbonate) (PTMC), the active ceramic filler Li7La3Zr2O12 (LLZO), and the passive ceramic fillers LiAlO2 (LAO) and NaAlO2 (NAO). The ionic transport mechanism in PTMC:LLZO CPEs is determined to be dependent on two main factors: particle loading and surface chemistry. An increase in ionic conductivity up to 30 wt% of Li7La3Zr2O12 is seen due to formation of additional transport pathways along the polymer-ceramic interfaces, while higher loadings affect the ionic conductivity negatively. While this can partly be explained by particle agglomeration, the presence of Li2CO3 on the Li7La3Zr2O12 surface also contributes to retard the ionic movement along the interfaces. Therefore, boric acid treatment is explored as a strategy to enable a Li2CO3-free surface of Li7La3Zr2O12 particles, which renders improved ionic transport and battery performance. Boron-treated Li7La3Zr2O12 shows formation of LiBO2, which yields a negative zeta-potential, indicative of interactions between the ceramic particles and Li+ ions. That the surface chemistry – rather than the bulk – of the ceramic filler ultimately controls the overall transport, opens the door towards employment of passive fillers. It is shown that LiAlO2 particles can increase the ionic conductivity by one order of magnitude and the Li+ transference number to almost 1, effectively rendering the LiAlO2-based CPE a single-ion conductor. These enhanced io