Search

Developing a safe and long-lasting lithium (Li) metal battery is crucial for high-energy applications. However, its poor cycling stability due to Li dendrite formation and excessive Li pulverization is the major hurdle for its practical applications. Here, we present a silica (SiO 2 ) nanoparticle-dispersed colloidal electrolyte (NDCE) and its design principle for suppressing Li dendrite formation. SiO 2 nanoclusters in the NDCE play roles in enhancing the Li + transference number and increasing the Li + diffusivity in the vicinity of the Li-plating substrate. The NDCE enables less-dendritic Li plating by manipulating the nucleation-growth mode and extending Sand's time. Moreover, SiO 2 can interplay with the electrolyte components at the Li-metal surface, enriching fluorinated compounds in the solid electrolyte interface layer. The initial control of the Li plating morphology and SEI structure by the NDCE leads to a more uniform and denser Li deposition upon subsequent cycling, resulting in threefold enhancement of the cycle life. The efficacy of the NDCEs has been further demonstrated by the practical battery design, featuring a commercial-level cathode and thin Li-metal (40 μm) anode.

Using UV-vis spectroscopy in conjunction with various electrochemical techniques, we have developed a new effective operando methodology for investigating the oxygen reduction reactions (ORRs) and their mechanisms in nonaqueous solutions. We can follow the in situ formation and presence of superoxide moieties during ORR as a function of solvent, cations, anions, and additives in the solution. Thus, using operando UV-vis spectroscopy, we found evidence for the formation of superoxide radical anions during oxygen reduction in LiTFSI/diglyme electrolyte solutions. Nitro blue tetrazolium (NBT) was used to indicate the presence of superoxide moieties based on its unique spectral response. Indeed, the spectral response of NBT containing solutions undergoing ORR could provide a direct indication for the level of association of the Li cations with the electrolyte anions.

As a substitute for the current lithium-ion batteries, rechargeable lithium oxygen batteries have attracted much attention because of their theoretically high energy density, but many challenges continue to exist. For the development of these batteries, understanding and controlling the main discharge product Li 2 O 2 (lithium peroxide) are of paramount importance. Here, we comparatively analyzed the amount of Li 2 O 2 in the cathodes discharged at various discharge capacities and current densities in dimethyl sulfoxide (DMSO) and tetraethylene glycol dimethyl ether (TEGDME) solvents. The precise assessment entailed revisiting and revising the UV-vis titration analysis. The amount of Li 2 O 2 electrochemically formed in DMSO was less than that formed in TEGDME at the same capacity and even at a much higher full discharge capacity in DMSO than in TEGDME. On the basis of our analytical experimental results, this unexpected result was ascribed to the presence of soluble LiO 2 -like intermediates that remained in the DMSO solvent and the chemical transformation of Li 2 O 2 to LiOH, both of which originated from the inherent properties of the DMSO solvent.

Aprotic Li-O 2 battery is an exciting concept. The enormous theoretical energy density and cell assembly simplicity make this technology very appealing. Nevertheless, the instability of the cell components, such as cathode, anode, and electrolyte solution during cycling, does not allow this technology to be fully commercialized. One of the intrinsic challenges facing researchers is the use of lithium metal as an anode in Li-O 2 cells. The high activity toward chemical moieties and lack of control of the dissolution/deposition processes of lithium metal makes this anode material unreliable. The safety issues accompanied by these processes intimidate battery manufacturers. The need for a reliable anode is crucial. In this work we have examined the replacement of metallic lithium anode in Li-O 2 cells with lithiated hard carbon (HC) electrodes. HC anodes have many benefits that are suitable for oxygen reduction in the presence of solvated lithium cations. In contrast to lithium metal, the insertion of lithium cations into the carbon host is much more systematic and safe. In addition, with HC anodes we can use aprotic solvents such as glymes that are suitable for oxygen reduction applications. By contrast, lithium cations fail to intercalate reversibly into ordered carbon such as graphite and soft carbons using ethereal electrolyte solutions, due to detrimental co-intercalation of solvent molecules with Li ions into ordered carbon structures. The hard carbon electrodes were prelithiated prior to being used as anodes in the Li-O 2 rechargeable battery systems. Full cells containing diglyme based solutions and a monolithic carbon cathode were measured by various electrochemical methods. To identify the products and surface films that were formed during cells operation, both the cathodes and anodes were examined ex situ by XRD, FTIR, and electron microscopy. The HC anodes were found to be a suitable material for (Li-ion)-O 2 cell. Although there are still many challenges to tackle, this study offers a more practical direction for this promising battery technology and sets up a platform for further systematic optimization of its various components.