Nonflammable Lithium Metal Full Cells with Ultra-high Energy Density Based on Coordinated Carbonate Electrolytes

Coupling thin Li metal anodes with high-capacity/high-voltage cathodes such as LiNi0.8Co0.1Mn0.1O2 (NCM811) is a promising way to increase lithium battery energy density. Yet, the realization of high-performance full cells remains a formidable challenge. Here, we demonstrate a new class of highly coordinated, nonflammable carbonate electrolytes based on lithium bis(fluorosulfonyl)imide (UFSI) in propylene carbonate/fluoroethylene carbonate mixtures. Utilizing an optimal salt concentr ation (4 M LiFSI) of the electrolyte results in a unique coordination structure of Li+-FSI-solvent cluster, which is critical for enabling the formation of stable interfaces on both the thin Li metal anode and high-voltage NCM811 cathode. Under highly demanding cell configuration and operating conditions (Li metal anode = 35 mu m, areal capacity/charge voltage of NCM811 cathode = 4.8 mAh cm(-2)/4 .6 V, and anode excess capacity [relative to the cathode] = 0.83), the Li metal-based full cell provides exceptional electrochemical performance (energy densities = 679 Wh kg(cell)(-1)/1,024 Wh L-cell(-1)) coupled with nonflammability

Tuning the stability of Electrochemical Interfaces by Electron Transfer reactions

The morphology of interfaces is known to play fundamental role on the efficiency of energy-related applications, such light harvesting or ion intercalation. Altering the morphology on demand, however, is a very difficult task. Here, we show ways the morphology of interfaces can be tuned by driven electron transfer reactions. By using non-equilibrium thermodynamic stability theory, we uncover the operating conditions that alter the interfacial morphology. We apply the theory to ion intercalation and surface growth where electrochemical reactions are described using Butler-Volmer or coupled ion-electron transfer kinetics. The latter connects microscopic/quantum mechanical concepts with the morphology of electrochemical interfaces. Finally, we construct non-equilibrium phase diagrams in terms of the applied driving force (current/voltage) and discuss the importance of engineering the density of states of the electron donor in applications related to energy harvesting and storage, electrocatalysis and photocatalysis.Comment: 10 pages, 6 figure

Perylene Diimide Aggregates on Sb-Doped SnO2: Charge Transfer Dynamics Relevant to Solar Fuel Generation

open14siThe project leading to this application has received funding from the European Union’s Horizon 2020 Research and Innovation Programme under the Marie Sklodowska-Curie grant agreement no. 705723.The deposition of perylene diimide-based aggregates (PDI) onto wide band gap n-type Sb-doped SnO2 (ATO) was investigated with the aim of finding efficient and versatile dye-sensitized platforms for photoelectrochemical solar fuel generation. These ATO-PDI photoanodes displayed hydrolytic stability in a wide range of pH (from 1 to 13) and revealed superior performances (up to 1 mA/cm2 net photocurrent at 1 V vs SCE) compared to both WO3-PDI and undoped SnO2-PDI when used in a photoelectrochemical setup for HBr splitting. Although ATO, SnO2, and WO3 are endowed with similar conduction band edge energetics, in ATO the presence of a significant density of intrabandgap states, whose occupancy varies with the applied potential, plays a substantial role in tuning the efficiency of photoinduced charge separation and collection. Furthermore, the investigation of the charge injection kinetics confirmed that, even in the absence of applied bias, ATO and WO3 are the best substrates for the oxidative quenching of poorly reducing PDI excited states, with at least a fraction of them injecting within <200 fs. The charge-separated states recombination occurs on longer time scales, allowing for their exploitation to drive demanding chemical reactions, as confirmed in photoelectrochemical water oxidation using IrO2-modified ATO-PDI photoanodes.openBerardi, Serena; Cristino, Vito; Canton, Martina; Boaretto, Rita; Argazzi, Roberto; Benazzi, Elisabetta; Ganzer, Lucia; Borrego Varillas, Rocio; Cerullo, Giulio; Syrgiannis, Zois; Rigodanza, Francesco; Prato, Maurizio; Bignozzi, Carlo Alberto; Caramori, StefanoBerardi, Serena; Cristino, Vito; Canton, Martina; Boaretto, Rita; Argazzi, Roberto; Benazzi, Elisabetta; Ganzer, Lucia; Borrego Varillas, Rocio; Cerullo, Giulio; Syrgiannis, Zois; Rigodanza, Francesco; Prato, Maurizio; Bignozzi, Carlo Alberto; Caramori, Stefan

Synthesis and characterization of silver vanadates thin films for photocatalytic applications

Silver vanadates thin films were deposited by a hybrid deposition system combining laser ablation and thermal evaporation. A high purity vanadium target was ablated using the third harmonic of a Nd:YAG laser whereas high purity silver pellets were evaporated. The as-deposited thin films were subjected to thermal treatments at 400 °C to obtain crystalline films. For films without Ag amorphous V2O5 thin films were deposited and as the Ag is incorporated in the material different silver vanadates were obtained. The effect of the silver load on the composition, structure, optical properties, surface morphology and photocatalytic response of the deposited films was studied. The film composition, determined by X-ray photoelectron spectroscopy, reveals Ag contents from 5.5 to 18.9 at.%. The crystalline phases formed were identified by micro-Raman Spectroscopy; the results indicate the formation of three silver vanadates depending on the silver content. The morphology was observed using scanning electron microscopy, the filmś surface changes from a smooth surface to belts covering the surface and finally Ag nanoparticles are observed at the higher Ag contens. Optical properties determined from UV–vis reveal the presence of the surface plasmon signal in films containing silver. The films were tested in the photocatalytic degradation of Malachite Green dye reaching maximum degradations degrees close to 53% under solar irradiation. Reactive species trapping experiments suggest that O2 − produced by the O2 reduction via the photogenerated electrons drives the photodegradation mechanismCB-168827 CB-240998 F. Gonzalez-Zavala thanks to CONACyT for the PhD and Beca Mixta grants, and also to the SIEA-UAEM for the beca movilidad para estudios avanzados 2016. E. Rodríguez-Castellón thanks to project CTQ2015-68951-C3-3-R of Ministerio de Economía y Competitividad (Spain) and FEDER funds

Implications of the formation of small polarons in Li2O2 for Li-air batteries

Lithium-air batteries (LABs) are an intriguing next-generation technology due to their high theoretical energy density of similar to 11 kWh/kg. However, LABs are hindered by both poor rate capability and significant polarization in cell voltage, primarily due to the formation of Li2O2 in the air cathode. Here, by employing hybrid density functional theory, we show that the formation of small polarons in Li2O2 limits electron transport. Consequently, the low electron mobility mu = 10(-10)-10(-9) cm(2)/Vs contributes to both the poor rate capability and the polarization that limit the LAB power and energy densities. The self-trapping of electrons in the small polarons arises from the molecular nature of the conduction band states of Li2O2 and the strong spin polarization of the O 2p state. Our understanding of the polaronic electron transport in Li2O2 suggests that designing alternative carrier conduction paths for the cathode reaction could significantly improve the performance of LABs at high current densities.open20