Project description:A robust solid-electrolyte interphase (SEI) enabled by electrolyte additive is a promising approach to stabilize Li anode and improve Li cycling efficiency. However, the self-sacrificial nature of SEI forming additives limits their capability to stabilize Li anode for long-term cycling. Herein, we demonstrate nanocapsules made from metal-organic frameworks for sustained release of LiNO3 as surface passivation additive in commercial carbonate-based electrolyte. The nanocapsules can offer over 10 times more LiNO3 than the solubility of LiNO3. Continuous supply of LiNO3 by nanocapsules forms a nitride-rich SEI layer on Li anode and persistently remedies SEI during prolonged cycling. As a result, lifespan of thin Li anode in 50 μm, which experiences drastic volume change and repeated SEI formation during cycling, has been notably improved. By pairing with an industry-level thick LiCoO2 cathode, practical Li-metal full cell demonstrates a remarkable capacity retention of 90% after 240 cycles, in contrast to fast capacity drop after 60 cycles in LiNO3 saturated electrolyte.
Project description:Anode-free lithium-metal batteries (AFLMBs) have the potential to double the energy density of Li-ion batteries, but face the challenges of mossy dendritic lithium plating and an unstable solid electrolyte interphase (SEI). Previous studies have shown that the AFLMBs with an electrolyte containing lithium difluoro(oxalato)borate (LiDFOB) salt outperform those with lithium hexafluorophosphate (LiPF6), but the mechanism behind this improvement is not fully understood. In this study, X-ray photoelectron spectroscopy (XPS) depth profile analysis and electrochemical impedance spectroscopy (EIS) were conducted to investigate the SEI on plated Li from the two conducting salts and their evolution in Cu‖NMC full cells during cycling. XPS results revealed that an inorganic-rich SEI layer is formed in the cell with LiDFOB-based electrolyte, with a low carbon/oxygen ratio of 0.56 compared to 1.42 in the LiPF6-based cell. With the inorganic-rich SEI, a dense electroplated Li with a shining surface on the Cu substrate can be retained after ten cycles. The inorganic-rich SEI enhances the reversibility of Li plating and stripping, with a high average CE of ∼98% and a stable charge/discharge voltage profile. The changes in SEI resistance and cathode electrolyte interphase resistance are more prominent compared to the changes in solution and charge transfer resistances, which further validate the role of the passivation films on Li deposits and NMC cathode surfaces in stabilizing AFLMB cycling performance.
Project description:Li metal batteries are being intensively investigated as a means to achieve higher energy density when compared with standard Li-ion batteries. However, the formation of dendritic and mossy Li metal microstructures at the negative electrode during stripping/plating cycles causes electrolyte decomposition and the formation of electronically disconnected Li metal particles. Here we investigate the use of a Cu current collector coated with a high dielectric BaTiO3 porous scaffold to suppress the electrical field gradients that cause morphological inhomogeneities during Li metal stripping/plating. Applying operando solid-state nuclear magnetic resonance measurements, we demonstrate that the high dielectric BaTiO3 porous scaffold promotes dense Li deposition, improves the average plating/stripping efficiency and extends the cycling life of the cell compared to both bare Cu and to a low dielectric scaffold material (i.e., Al2O3). We report electrochemical tests in full anode-free coin cells using a LiNi0.8Co0.1Mn0.1O2-based positive electrode and a LiPF6-based electrolyte to demonstrate the cycling efficiency of the BaTiO3-coated Cu electrode.
Project description:A Li-ion battery combines a cathode benefitting from Sn and MnO2 with high sulfur content, and a lithiated anode including fumed silica, few layer graphene (FLG) and amorphous carbon. This battery is considered a scalable version of the system based on lithium-sulfur (Li-S) conversion, since it exploits at the anode the Li-ion electrochemistry instead of Li-metal stripping/deposition. Sn and MnO2 are used as cathode additives to improve the electrochemical process, increase sulfur utilization, while mitigating the polysulfides loss typical of Li-S devices. The cathode demonstrates in half-cell a maximum capacity of ~1170 mAh gS -1, rate performance extended over 1 C, and retention of 250 cycles. The anode undergoes Li-(de)alloying with silicon, Li-(de)insertion into amorphous carbon, and Li-(de)intercalation through FLG, with capacity of 500 mAh g-1 in half-cell, completely retained over 400 cycles. The full-cells are assembled by combining a sulfur cathode with active material loading up to 3 mg cm-2 and lithiated version of the anode, achieved either using an electrochemical pathway or a chemical one. The cells deliver at C/5 initial capacity higher than 1000 mAh gS -1, retained for over ~40 % upon 400 cycles. The battery is considered a promising energy storage system for possible scaling-up in pouch or cylindrical cells.
Project description:Electrode used in lithium-ion battery is invariably a composite of multifunctional components. The performance of the electrode is controlled by the interactive function of all components at mesoscale. Fundamental understanding of mesoscale phenomenon sets the basis for innovative designing of new materials. Here we report the achievement and origin of a significant performance enhancement of electrode for lithium ion batteries based on Si nanoparticles wrapped with conductive polymer. This new material is in marked contrast with conventional material, which exhibit fast capacity fade. In-situ TEM unveils that the enhanced cycling stability of the conductive polymer-Si composite is associated with mesoscale concordant function of Si nanoparticles and the conductive polymer. Reversible accommodation of the volume changes of Si by the conductive polymer allows good electrical contact between all the particles during the cycling process. In contrast, the failure of the conventional Si-electrode is probed to be the inadequate electrical contact.
Project description:New two-dimensional (2D) transition-metal borides have attracted considerable interest in research on electrode materials for Li-ion batteries (LIBs) owing to their promising properties. In this study, 2D molybdenum boride (Mo2B2) with and without transition metal (TM, TM=Mn, Fe, Co, Ni, Ru, and Pt) atom doping was investigated. Our results indicated that all TM-doped Mo2B2 samples exhibited excellent electronic conductivity, similar to the intrinsic 2D Mo2B2 metal behavior, which is highly beneficial for application in LIBs. Moreover, we found that the diffusion energy barriers of Li along paths 1 and 2 for all TM-doped Mo2B2 samples are smaller than 0.30 and 0.24 eV of the pristine Mo2B2. In particular, for 2D Co-doped Mo2B2, the diffusion energy barriers of Li along paths 1 and 2 are reduced to 0.14 and 0.11 eV, respectively, making them the lowest Li diffusion barriers in both paths 1 and 2. This indicates that TM doping can improve the electrochemical performance of 2D Mo2B2 and that Co-doped Mo2B2 is a promising electrode material for LIBs. Our work not only identifies electrode materials with promising electrochemical performance but also provides guidance for the design of high-performance electrode materials for LIBs.
Project description:TiO2 nanotube layers (TNTs) decorated with Al2O3/MoS2/Al2O3 are investigated as a negative electrode for 3D Li-ion microbatteries. Homogenous nanosheets decoration of MoS2, sandwiched between Al2O3 coatings within self-supporting TNTs was carried out using atomic layer deposition (ALD) process. The structure, morphology, and electrochemical performance of the Al2O3/MoS2/Al2O3-decorated TNTs were studied using scanning transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and chronopotentiometry. Al2O3/MoS2/Al2O3-decorated TNTs deliver an areal capacity almost three times higher than that obtained for MoS2-decorated TNTs and as-prepared TNTs after 100 cycles at 1C. Moreover, stable and high discharge capacity (414 µAh cm-2) has been obtained after 200 cycles even at very fast kinetics (3C).
Project description:Hierarchical carbon-rich materials have shown immense potential for various electrochemical applications. Metal-organic frameworks (MOFs) are well suited precursors for obtaining such templated carbon matrices. Usually these conversions are carried out by energy intensive processes and lead to the presence of toxic transition metal residues. Herein, we demonstrate the green, scalable, microwave-assisted synthesis of a three-dimensional s-block metal based MOF and its efficient transformation into a carbonaceous material. The MOF-derived solid functions as a negative electrode for lithium-ion batteries having moderate low-rate capacities and cycling stability.
Project description:Commercialized Vat Blue 4 (VB4) has attracted more attention as a promising anode for large-scale applications in Li-ion batteries (LIBs) due to its high electrochemical activity, low price, and large-scale production. However, its moderate solubility results in severe capacity decay and low utilization of active components. Herein, we present a graphene-supported VB4 composite (VB4/rGO) prepared by a facile sonication and hydrothermal process for long cycling stability and high-rate capability. This design can significantly enhance the Li-storage properties, including high capacity (1045 mA h g-1 at 0.1 A g-1), long cycling stability (537 mA h g-1 even over 1000 cycles at 1 A g-1), and rate capability (315 mA h g-1 at 5 A g-1). Strong π-π interaction derived from the aromatic rings within the π-conjugated system (graphene and VB4) and spatial confinement in-between graphene sheets both can suppress the high solubility of VB4 for superior capacity retention. Moreover, conductive graphene and channels in-between nanosheets can simultaneously facilitate the electron and Li+ transfer. This work demonstrates a simple and effective method to improve the electrochemical performance of commercialized Vat dyes and provides a low-cost and large-scale strategy to develop their practical application in the energy storage field.
Project description:Silicon is a worthy substitute anode material for lithium-ion batteries because it offers high theoretical capacity and low working potentials vs. Li+/Li. However, immense volume changes and the low intrinsic conductivity of Si hampers its practical applications. In this study, nano/micro silicon particles are achieved by ball milling silicon mesh powder as a scalable process. Subsequent metal (Cu/Fe/Mn) doping into nano/micro silicon by low-temperature annealing, followed by high-temperature annealing with graphite, gives a metal-doped silicon/graphite composite. The obtained composites were studied as anodes for Li-ion batteries, and they delivered high reversible capacities of more than 1000 mAh g-1 with improved Li+ diffusion properties. The full cells from these composite anodes vs. LiCoO2 cathodes delivered suitable energy densities for Li+ storage applications. The enhanced electrochemical properties are accredited to the synergistic effect of metal doping and graphite addition to silicon and exhibit potential for suitable Li+ energy storage applications.