Nickel‐rich layered oxide cathodes with the composition LiNi1−x−yCoxMnyO2 (NCM, (1−x−y) ≥ 0.6) are under intense scrutiny recently to contend with commercial LiNi0.8Co0.15Al0.05O2 (NCA) for high‐energy‐density batteries for electric vehicles. However, a comprehensive assessment of their electrochemical durability is currently lacking. Herein, two in‐house cathodes, LiNi0.8Co0.15Al0.05O2 and LiNi0.7Co0.15Mn0.15O2, are investigated in a high‐voltage graphite full cell over 1500 charge‐discharge cycles (≈5–10 year service life in vehicles). Despite a lower nickel content, NCM shows more performance deterioration than NCA. Critical underlying degradation processes, including chemical, structural, and mechanical aspects, are analyzed via an arsenal of characterization techniques. Overall, Mn substitution appears far less effective than Al in suppressing active mass dissolution and irreversible phase transitions of the layered oxide cathodes. The active mass dissolution (and crossover) accelerates capacity decline with sustained parasitic reactions on the graphite anode, while the phase transitions are primarily responsible for cell resistance increase and voltage fade. With Al doping, on the other hand, secondary particle pulverization is the more limiting factor for long‐term cyclability compared to Mn. These results establish a fundamental guideline for designing high‐performing Ni‐rich NCM cathodes as a compelling alternative to NCA and other compositions for electric vehicle applications.

A novel paradigm for the design of surfactants for water/CO 2 (W/C) microemulsions is presented. The paradigm focuses on the fractional free volume (FFV) available to CO 2 at the interface. The FFV is an unambiguous geometric parameter that is calculated directly from surfactant tail geometry and surface coverage. We present an analysis of recent experimental studies indicating that low FFV is a necessary, although not sufficient, condition for W/C microemulsion formation and that both microemulsion and macroemulsion stability correlate qualitatively with FFV. This correlation is understood by noting that a decrease in FFV tends to favor the factors that stabilize W/C microemulsions, namely, decreased interfacial tension, reduced overlap between tails (weakening attractive interdroplet interactions), and increased interfacial curvature. These factors are more challenging to achieve in CO 2 than in alkane solvents, implying that low FFV is especially important for W/C microemulsions.

Electrophoretic mobilities of TiO2 colloids in an apolar solvent, toluene, were measured by differential-phase optical coherence tomography (DP-OCT). An electrode spacing of 0.18 mm, made possible by optical coherence tomography with transparent electrodes, enables measurement of the electrophoretic mobility with small samples (20 μL) of highly turbid colloids at low applied electric potential to avoid electrohydrodynamic instability and electrochemical reactions. In the presence of Aerosol-OT reverse micelles, which stabilized the countercharges, the zeta potential was positive for hydrophilic TiO2 (13 mV at 90 mM AOT) and negative for hydrophobic TiO2. The magnitudes of the zeta potentials were very similar for these two types of TiO2 and decreased at the same rate with AOT concentration. For both hydrophilic and hydrophobic TiO2, a general mechanism is presented to describe the zeta potential in terms of preferential partitioning of cations and sulfosuccinate anions between the particle surface and reverse micelle cores in bulk. This preferential partitioning is governed by the hydrophilicities and extents of the particle surfaces and reverse micelle cores, as a function of surfactant and water concentration. The emerging understanding of the complex charging and stabilization mechanisms for colloids in apolar solvents will be highly beneficial for the design of novel materials.

Liquid and supercritical carbon dioxide swell potassium carboxylate perfluoropolyether (PFPE-K) cylindrical micelles in water to produce novel CO(2)-in-water (C/W) microemulsions. The swelling elongates the micelles significantly from 20 to 80 nm as the molar ratio of CO(2) in the micelles to surfactant (R(CO2)) reaches approximately 8. As the micelles swell to form microemulsions, the solubility of pyrene increases by a factor of ca. 10. Fluorescence spectra suggest that pyrene resides primarily in the low-polarity micelle core rather than in the palisade region. The results illustrate the ability of C/W microemulsions to solubilize both lipophilic and fluorophilic substances simultaneously.

With high-pressure pendant-drop tensiometry, the interfacial tension (γ) and surface excess (Γ∞) for a family of ionic surfactants with identical phosphate headgroups and varying fluorocarbon and hydrocarbon tail structures were examined at the water−CO2 interface. To compensate for the unusually weak CO2−surfactant tail interactions, we designed hydrocarbon tails with weak tail−tail interactions to achieve a more favorable hydrophilic−CO2-philic balance. Branching of hydrocarbon surfactant tails is shown to lead to more favorable adsorption at the interface, closer to that of fluorocarbon surfactants. γ for a double-tail hydrocarbon phosphate surfactant with a relatively high degree of tail branching was lowered from the water−CO2 binary interface value of about 20 mN/m at 25 °C and 340 bar to 3.7 mN/m. This reduction in γ is attributed to both a decrease in the free volume between tails at the interface and reduced tail−tail interactions. In addition to tail structure, the effects of surfactant counterion, salt concentration, temperature, and CO2 density on γ and Γ∞ were investigated. The hydrophilic−CO2-philic balances of these surfactants are mapped by investigating changes in interfacial tension with these formulation variables. Low-molecular-weight branched hydrocarbon ionic surfactants are shown to stabilize concentrated CO2-in-water emulsions for greater than 1 h.

No abstract

We report electrostatic stabilization of micrometer-sized TiO(2) particles at long range (several micrometers) in liquid and supercritical CO(2) despite the ultralow dielectric constant, as low as 1.5. The counterions were solubilized in dry reverse micelles, formed with a low-molecular weight cationic perfluoropolyether trimethylammonium acetate surfactant, to prevent ion pairing with the particle surface. Dynamic light scattering and settling velocities indicate a particle diameter of 620-740 nm. The electrophoretic mobility of -2.3 x 10(-8) m(2)/V s indicated a particle charge on the order of -1.7 x 10(-17) C, or 105 elementary negative charges per particle. The balance of particle compression by an electric field versus electrostatic repulsion generated an amorphous arrangement of particles with 5-9 mum spacing, indicating Debye lengths greater than 1 mum. Scattering patterns also indicate that chains of particles may be achieved in CO(2) by dielectrophoresis with alternating fields. The electrostatic stabilization has been achieved by solubilizing a small concentration of counterions in only a small fraction of the reverse micelles in the double layer. Whereas many low-molecular weight surfactants have been shown to form reverse micelles in CO(2), very few polymers are able to stabilize micrometer-sized colloids sterically. Thus, electrostatic stabilization has the potential to expand markedly the domain of colloid science in apolar supercritical fluids.

We report the use of differential-phase optical coherence tomography (DP-OCT) for measurement of electrophoretic mobility in low-conductivity solvents. Weakly charged particles are common in low-permittivity solvents, particularly in practical applications that contain water as a result of ambient humidity. Use of DP-OCT with transparent electrodes enables close electrode spacing (0.18 mm) and thus high electric fields despite low applied electric potential, to avoid electrohydrodynamic instability and electrochemical interference. Further advantages include small sample volume requirement (20 μL), the ability to analyze highly turbid colloids, and avoidance of electro-osmosis. This phase-sensitive method is demonstrated on weakly charged TiO2 particles dispersed in toluene with Aerosol-OT surfactant at a relatively high water content (50 mM), with small mobility of 2.8−3.0 × 10-10 m2/V s (ζ potential 11−13 mV). Mobility is independent of applied field strength (28−56 kV/m). Measurement reproducibility is comparable to that by phase analysis light scattering (PALS) for dispersions in low-permittivity media. Capabilities of DP-OCT, including high sensitivity, high spatial resolution, and small detection volume, offer potential for significant expansion of the field of charged colloids in low-permittivity media.