Coulombic
efficiency (CE) and cycle life of metal anodes (lithium,
sodium, zinc) are limited by dendritic growth and side reactions in
rechargeable metal batteries. Here, we proposed a concept for constructing
an anion concentration gradient (ACG)-assisted solid–electrolyte
interphase (SEI) for ultrahigh ionic conductivity on metal anodes,
in which the SEI layer is fabricated through an in situ chemical reaction
of the sulfonic acid polymer and zinc (Zn) metal. Owing to the driving
force of the sulfonate concentration gradient and high bulky sulfonate
concentration, a promoted Zn2+ ionic conductivity and inhibited
anion diffusion in the SEI layer are realized, resulting in a significant
suppression of dendrite growth and side reaction. The presence of
ACG-SEI on the Zn metal enables stable Zn plating/stripping over 2000
h at a high current density of 20 mA cm–2 and a
capacity of 5 mAh cm–2 in Zn/Zn symmetric cells,
and moreover an improved cycling stability is also observed in Zn/MnO2 full cells and Zn/AC supercapacitors. The SEI layer containing
anion concentration gradients for stable cycling of a metal anode
sheds a new light on the fundamental understanding of cation plating/stripping
on metal electrodes and technical advances of rechargeable metal batteries
with remarkable performance under practical conditions.
The oxygen reduction reaction (ORR) in aprotic electrolyte is the essential reaction in metal−oxygen batteries. Capturing and shifting the absorbed metal superoxide intermediates/products from a cathode surface is a long-standing challenge to clarify the ORR mechanism, accelerate the ORR, and improve the stability and energy density of metal−oxygen batteries. Herein, a bioinspired pathway in which cathode solid catalysts and soluble anthraquinone (AQ) molecules initiate an "enzyme−coenzyme" cooperative catalysis mechanism is developed to greatly boost the ORR activity of solid catalysts over 10-fold, in which AQ acts as a scavenger to capture and shift the absorbed superoxide species from the cathode surface to the aprotic electrolyte. Taking the lithium−oxygen (Li−O 2 ) battery as a model system, the cell discharge ORR mechanism is well illustrated and capacities are significantly improved over 3 times in the presence of AQ molecules. This concept represents the first demonstration of stabilizing and solvating superoxide species to substantially accelerate ORR catalysis of solid catalysts and enhance the performance of metal− O 2 batteries through biomimicking coenzyme-assisted reactions.
Nylon 11 (PA11)/clay nanocomposites have been prepared by melt-blending, followed by melt-extrusion through a capillary. Transmission electron microscopy shows that the exfoliated clay morphology is dominant for low nanofiller content, while the intercalated one is prevailing for high filler loading. Melt rheological properties of PA11 nanocomposites have been studied in both linear and nonlinear viscoelastic response regions. In the linear regime, the nanocomposites exhibit much higher storage modulus (GЈ) and loss modulus (GЉ) values than neat PA11. The values of GЈ and GЉ increase steadily with clay loading at low concentrations, while the GЈ and GЉ for the sample with 5 wt % clay show an inverse dependence and lie between the modulus values of the samples with 1 and 2 wt % of clay. This is attributed to the alignment/orientation of nanoclay platelets in the intercalated nanocomposite induced by capillary extrusion. In the nonlinear regime, the nanocomposites show increased shear viscosities when compared with the neat resin. The dependence of the shear viscosity on clay loading has analogous trend to that of GЈ and GЉ. Finally, a comparison has been made between the complex and steady viscosities to verify the applicability of the empirical CoxMerz rule.
A proof‐of‐concept study on a liquid/liquid (L/L) two‐phase electrolyte interface is reported by using the polarity difference of solvent for the protection of Li‐metal anode with long‐term operation over 2000 h. The L/L electrolyte interface constructed by non‐polar fluorosilicane (PFTOS) and conventionally polar dimethyl sulfoxide solvents can block direct contact between conventional electrolyte and Li anode, and consequently their side reactions can be significantly eliminated. Moreover, the homogeneous Li‐ion flow and Li‐mass deposition can be realized by the formation of a thin and uniform solid‐electrolyte interphase (SEI) composed of LiF, LixC, LixSiOy between PFTOS and Li anode, as well as the super‐wettability state of PFTOS to Li anode, resulting in the suppression of Li dendrite formation. The cycling stability in a lithium–oxygen battery as a model is improved 4 times with the L/L electrolyte interface.
ABSTRACT:The nanocomposites of polyamide1010 (PA1010) filled with carbon nanotubes (CNTs) were prepared by melt mixing techniques. The isothermal meltcrystallization kinetics and nonisothermal crystallization behavior of CNTs/PA1010 nanocomposites were investigated by differential scanning calorimetry. The peak temperature, melting point, half-time of crystallization, enthalpy of crystallization, etc. were measured. Two stages of crystallization are observed, including primary crystallization and secondary crystallization. The isothermal crystallization was also described according to Avrami's approach. It has been shown that the addition of CNTs causes a remarkable increase in the overall crystallization rate of PA1010 and affects the mechanism of nucleation and growth of PA1010 crystals. The analysis of kinetic data according to nucleation theories shows that the increment in crystallization rate of CNTs/PA1010 composites results from the decrease in lateral surface free energy.
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