A set of LiNi 0.5 Mn 0.3 Co 0.2 O 2 /graphite lithium-ion cells underwent 750 charge-discharge cycles during about 8 months at 55 • C to upper cutoff potentials of 4.0, 4.1, 4.2, 4.3, and 4.4 V. The electrolyte in these cells was extracted using a centrifuge method and studied using gas chromatography/mass spectrometry to determine the changes to the solvents and by inductively coupled plasma-mass spectrometry to determine the changes to the salt content in the electrolyte. The negative electrodes from the cells were harvested and studied by micro-X-ray fluorescence to quantify the amount of transition metals which migrated from the positive electrode to the negative electrode during the testing. Emphasis is given to a detailed description of the quantitative methods used in the hope that others will adopt them in similar studies of different types of aged lithium-ion cells. The cells studied here initially had 1.1 molal LiPF 6 ethylene carbonate (EC): ethyl methyl carbonate (EMC) (3:7 by weight) electrolyte. The aged cells showed increasing amounts of dimethyl carbonate and diethyl carbonate created by transesterification as the upper cutoff potential increased. Only extremely small amounts of Mn, less than 0.1% of the total Mn in the positive electrode, were found on the negative electrode after this aggressive testing. Lithium-ion batteries are currently used in a wide range of applications: cell phones, power tools, vehicles and even grid energy storage.
Optimizing the performance of the lithium metal anode is required to enable the next generation of high energy density batteries. Anode-free lithium metal cells are particularly attractive as they facilitate the highest energy density cell architecture. In this work, we investigate the performance of anode-free cells cycled under different protocols. We demonstrate the impact of charge and discharge current density with three different cycling conditions: a symmetric charge-discharge, an asymmetric faster charge and an asymmetric slower charge. We show that the relative rate of charge vs discharge is more important than the absolute current densities, and that cycling with an asymmetric slower charge protocol is optimal in agreement with previous studies on cells with lithium metal anodes. We also examine the effect of depth of discharge and demonstrate how the lower voltage cut-off can be chosen to form a lithium reservoir in situ. We show that the capacity of the lithium reservoir significantly benefits lifetime for cells cycled with a limited depth of discharge. Finally, we develop a specialized intermittent high depth of discharge cycling protocol optimized for anode-free lithium metal cells.
LiFePO4 (LFP) is an appealing cathode material for Li-ion batteries. Its superior safety and lack of expensive transition metals make LFP attractive even with the commercialization of higher specific capacity materials. In this work the performance of LFP/graphite cells is tested at various temperatures and cycling protocols. The amount of water contamination is controlled to study the impact of water on capacity fade in LFP. Further, several additive systems that have been effective in NMC/graphite chemistries are tested in LFP/graphite cells. The presence of excess water impacts cell performance severely when no electrolyte additives are used, or when the electrodes are poorly passivated. When effective additive systems are used, the existence of up to 500 ppm excess water in the cell is does not strongly affect cycle life and storage performance. Fe dissolution is studied in LFP with micro X-ray fluorescence spectroscopy (μXRF), and most electrolyte additives virtually eliminate Fe dissolution, even at high temperature and with water contamination. Removing excess water contamination suppresses Fe dissolution in cells without electrolyte additives. Finally, the capacity retention of LFP/graphite cells at high temperature is compared with long lifetime NMC/graphite cells, demonstrating challenges for LFP/graphite cells.
Inorganic surface coatings such as Al 2 O 3 are commonly applied on positive electrode materials to improve the cycling stability and lifetime of lithium-ion cells. The beneficial effects are typically attributed to the chemical scavenging of corrosive HF and the physical blockage of electrolyte components from reaching the electrode surface. The present work combines published thermochemistry data with new density functional theory calculations to propose a new mechanism of action: the spontaneous reaction of the LiPF 6 electrolyte salt with Al 2 O 3 -based surface coatings. Using 19 F and 31 P solution nuclear magnetic resonance spectroscopy, it is demonstrated that the storage of LiPF 6 -containing electrolyte solution with Al 2 O 3 produces LiPO 2 F 2 , a well-known electrolyte additive. The production of LiPO 2 F 2 is also observed for electrolyte solutions that were stored for 14 days at 40 °C with Al 2 O 3 -coated LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) and LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA) materials. Given the beneficial nature of this species for the lifetime and stability of lithium-ion cells, this reaction is here proposed to similarly benefit the performance of cells that use Al 2 O 3 -coated cathode materials.
Unwanted redox shuttles can lead to self-discharge and inefficiency in lithium-ion cells. This study investigates the generation of a redox shuttle in LFP/graphite and NMC811/graphite pouch cells with common alkyl carbonate electrolyte. Visual inspection of the electrolyte extracted after formation at temperatures between 25 and 70°C reveals strong discoloration. Such extracted electrolytes with intense red and brown color show relatively large shuttling currents in Al/Li coin cells. Two weight percent of vinylene carbonate is effective at preventing the redox shuttle generation as indicated by the absence of electrolyte discoloration and shuttling current. Ultra-high precision coulometry demonstrates that the presence of the shuttle molecule during cycling of LFP/graphite and NMC811/graphite pouch cells leads to significant charge endpoint capacity slippage and coulombic inefficiency. A brief constant voltage hold at 4.2 V can eliminate the shuttle molecule.
Fast-charging lithium-ion cells require electrolyte solutions that balance high ionic conductivity and chemical stability. The introduction of an organic ester co-solvent is one route that can improve the rate capability of a cell. Several new co-solvent candidates were identified based on viscosity, permittivity (dielectric constant), and DFT-calculated electrochemical stability windows. Several formate, nitrile, ketone, and amide co-solvents are shown to increase the ionic conductivity of lithium hexafluorophosphate in conventional organic-carbonate-based solutions. Based on gas production during the first formation cycle in Li[Ni 1-x-y Co x Al y ]O 2 /graphite-SiO pouch cells, five candidates were identified: methyl formate (MF), ethyl formate (EF), propionitrile (PN), isobutyronitrile (iBN), and dimethyl formamide (DMF). High temperature storage (60 • C), long-term cycling, and ultrahigh-precision coulometry results indicate that MF offers the greatest balance between conductivity increase and cell lifetime. Future work is encouraged to develop more stable solution chemistries that incorporate MF. PN may prove useful for low temperature (< 40 • C) applications.
Novel polymer complexes of 8‐hydroxyquinoline‐5‐sulfonic acid hydrate (H2L) with Cu2+, Co2+ and Ni2+ chloride were prepared and characterized. Microanalysis, magnetic susceptibility, IR spectra, electron spin resonance, mass spectra, X‐ray, molar conductance, thermal, and UV–Vis spectra studies have been used to confirm the structure of the prepared polymer complexes. The molecular and electronic structures of the hydrogen bond conformers for ligand (H2L) were optimized theoretically and the quantum chemical parameters were calculated. On the basis of elemental and IR data, the chemical structure of metal chelates commensurate that the tri‐dentate (H2L) coordinate to metal chlorides through oxygen atom of phenolic OH and oxygen atom of SO3‐H group by replacing H atoms and nitrogen of the quinoline ring. The magnetic studies suggested the octahedral geometrical structure for all produced polymer complexes with general formula {[ML (OH2)3] .xH2O}n (M = Cu2+, x = 1.; Co2+, x = 2 and Ni2+, x = 2) in molar ratio (1:1). Coats–Redfern and Horowitz–Metzger methods have been used for calculating the activation thermodynamic parameters of the thermal decomposition for H2L and its polymer complexes. The interaction between H2L and its transition metal complexes with the calf thymus DNA (CT‐DNA) was determined by UV–Vis spectra. Binding efficiency between H2L with the receptors of the prostate cancer (PDB code 2Q7L Hormone) and the breast cancer (PDB code 1JNX Gene regulation) was studied by molecular docking. The inhibition behaviour of H2L against the corrosion of carbon steel/HCl (2 M) solution was studied by weight loss, Tafel polarisation, electrochemical impedance spectroscopy (EIS) and electrochemical frequency modulation (EFM) techniques. The adsorption isotherm was found to be Friendlish isotherm. The morphology of inhibited carbon steel̕ s surface was studied using scanning electron microscope (SEM) and energy dispersive X‐ray spectroscopy (EDS).
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