Solid state batteries hold the promise of enhanced safety and higher energy density over conventional lithium‐ion batteries with flammable organic electrolytes. However, advancement of solid electrolyte materials has yet to translate into practical batteries due to the need to process the powders into thin sheets with high pressure compaction and high temperature sintering. Here, a new strategy is developed for synthesizing sulfide‐based solid electrolyte using low‐temperature solution processing, which is a simple and potentially cost‐effective way to make a thin solid electrolyte layer. By controlling the stoichiometric ratio of Li2S and S, soluble polysulfides are produced in diethylene glycol dimethyl ether, which are reacted with P2S5to form a conductive Li3PS4solid electrolyte. It is demonstrated that a dense solid electrolyte layer can be directly formed on Li metal with a high quality electrolyte/electrode interface, producing a solid electrolyte with promising electrochemical performance. Also, first‐principles calculations are conducted to elucidate the formation mechanisms behind the soluble intermediates and the solid electrolyte layers.
- NSF-PAR ID:
- 10420500
- Date Published:
- Journal Name:
- Frontiers in Energy Research
- Volume:
- 11
- ISSN:
- 2296-598X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
Abstract -
Abstract Polymer–ceramic composite electrolytes are emerging as a promising solution to deliver high ionic conductivity, optimal mechanical properties, and good safety for developing high‐performance all‐solid‐state rechargeable batteries. Composite electrolytes have been prepared with cubic‐phase Li7La3Zr2O12(LLZO) garnet and polyethylene oxide (PEO) and employed in symmetric lithium battery cells. By combining selective isotope labeling and high‐resolution solid‐state Li NMR, we are able to track Li ion pathways within LLZO‐PEO composite electrolytes by monitoring the replacement of7Li in the composite electrolyte by6Li from the6Li metal electrodes during battery cycling. We have provided the first experimental evidence to show that Li ions favor the pathway through the LLZO ceramic phase instead of the PEO‐LLZO interface or PEO. This approach can be widely applied to study ion pathways in ionic conductors and to provide useful insights for developing composite materials for energy storage and harvesting.
-
Solid polymer and perovskite-type ceramic electrolytes have both shown promise in advancing solid-state lithium metal batteries. Despite their favorable interfacial stability against lithium metal, polymer electrolytes face issues due to their low ionic conductivity and poor mechanical strength. Highly conductive and mechanically robust ceramics, on the other hand, cannot physically remain in contact with redox-active particles that expand and contract during charge-discharge cycles unless excessive pressures are used. To overcome the disadvantages of each material, polymer-ceramic composites can be formed; however, depletion interactions will always lead to aggregation of the ceramic particles if a homopolymer above its melting temperature is used. In this study, we incorporate Li 0.33 La 0.56 TiO 3 (LLTO) nanoparticles into a block copolymer, polystyrene- b -poly (ethylene oxide) (SEO), to develop a polymer-composite electrolyte (SEO-LLTO). TEMs of the same nanoparticles in polyethylene oxide (PEO) show highly aggregated particles whereas a significant fraction of the nanoparticles are dispersed within the PEO-rich lamellae of the SEO-LLTO electrolyte. We use synchrotron hard x-ray microtomography to study the cell failure and interfacial stability of SEO-LLTO in cycled lithium-lithium symmetric cells. Three-dimensional tomograms reveal the formation of large globular lithium structures in the vicinity of the LLTO aggregates. Encasing the SEO-LLTO between layers of SEO to form a “sandwich” electrolyte, we prevent direct contact of LLTO with lithium metal, which allows for the passage of seven-fold higher current densities without signatures of lithium deposition around LLTO. We posit that eliminating particle clustering and direct contact of LLTO and lithium metal through dry processing techniques is crucial to enabling composite electrolytes.more » « less
-
Abstract Ceramic–polymer composites are of interest for designing enhanced and unique properties. However, the processing temperature windows of sintering ceramics are much higher than that of compaction, extrusion, or sintering of polymers, and thus traditionally there has been an inability to cosinter ceramic–polymer composites in a single step with high amounts of ceramics. The cold sintering process is a low‐temperature sintering technology recently developed for ceramics and ceramic‐based composites. A wide variety of ceramic materials have now been demonstrated to be densified under the cold sintering process and therefore can be all cosintered with polymers from room temperature to 300 °C. Here, the status, understanding, and application of cold cosintering, with different examples of ceramics and polymers, are discussed. One has to note that these types of cold sintering processes are yet new, and a full understanding will only emerge after more ceramic–polymer examples emerge and different research groups build upon these early observations. The general processing, property designs, and an outlook on cold sintering composites are outlined. Ultimately, the cold sintering process could open up a new multimaterial design space and impact the field of ceramic–polymer composites.
-
Abstract The Cold Sintering Process (CSP) can provide opportunities to fabricate high-performance BaTiO3dielectric composites with polymer materials that are typically difficult to impossible to co-process under a conventional sintering process. Therefore, we investigated the preparation process of BaTiO3sintered body by CSP and integrated a well-dispersed intergranular polymer phase. In this study, we focused on preparing BaTiO3and Polytetrafluoroethylene (PTFE) composites. We considered the importance of the particle size of the PTFE phase, and correlated the impact on the composite dielectric properties. Through fitting a general-mixing-law to the dielectric properties as a function of volume fraction, we could deduce more homogeneous composites obtained in using the 200 nm PTFE powders. In addition, the temperature dependent dielectric properties and field dependent conductivity of the composites was investigated. It was found that with the good dispersion of the PTFE can suppress the leakage current density in the dielectric composites.