Effects of ion insertion on cycling performance of miniaturized electrochemical capacitor of carbon nanotubes array.

Capacity degradation and ion insertion of a miniaturized electrochemical capacitor are studied using ionic liquid [EMI] [TFSI] as the electrolyte. This capacitor is featured with two comb-like electrodes of vertical carbon nanotubes, ∼70 µm in height and 20 µm in interelectrode gap. We quantify the levels of ion insertion damage with Raman spectroscopy after the electrode experiences 120 consecutive voltammetric cycles to various potential limits. Distinct structural damage emerges due to [EMI] when the negative potential reaches -1.7 V, and those due to [TFSI] arise when the positive potential reaches 1.7 V vs. RHE. Judging from the peak broadenings, [EMI] is more detrimental than [TFSI]. When the voltage window ΔU is set as less than or equal to 2.8 V, both electrode potentials are within the two intercalation limits, little or no decay is observed in 10(4) charge/discharge cycles. When ΔU is 3.4 V, the positive potential exceeds the upper limit, but the negative potential stays within the lower limit, the cell capacitance decreases moderately. When ΔU increases to 3.8 V, both electrodes suffer from damages because of exceeding the intercalation limits. And the cell capacitance decreases substantially, even leading to a premature failure.

Li-Sb Alloy Formation Strategy to Improve Interfacial Stability of All-Solid-State Lithium Batteries.

The solid electrolyte is anticipated to prevent lithium dendrite formation. However, preventing interface reactions and the development of undesirable lithium metal deposition during cycling are difficult and remain unresolved. Here, to comprehend these occurrences better, this study reports an alloy formation strategy for enhanced interface stability by incorporating antimony (Sb) in the lithium argyrodite solid electrolyte Li6PS5Cl (LPSC-P) to form Li-Sb alloy. The Li-Sb alloy emergence at the anodic interface is crucial in facilitating uniform lithium deposition, resulting in excellent long-term stability, and achieving the highest critical current density of 14.5 mA cm-2 (among the reported sulfide solid electrolytes) without lithium dendrite penetration. Furthermore, Li-Sb alloy formation maintain interfacial contact, even, after several plating and stripping. The Li-Sb alloy formation is confirmed by XRD, Raman, and XPS. The work demonstrates the prospect of utilizing alloy-forming electrolytes for advanced solid-state batteries.

Miniature asymmetric ultracapacitor of patterned carbon nanotubes and hydrous ruthenium dioxide.

A symmetric ultracapacitor CNT_CNT and an asymmetric ultracapacitor CNT_hRuO(2) of mini size have been prepared with patterned carbon nanotubes (CNT) and hydrous ruthenium dioxide. Galvanostatic charge/discharge results indicate that CNT_hRuO(2) is the superior one in both power and energy densities. In a potential window 2.0 V, the CNT_hRuO(2) cell displays an energy density of 24.0 W h kg(-1) at a power density of 22.9 kW kg(-1). Its power density can be raised to 41.1 kW kg(-1) at the expense of the energy density, which drops to 6.8 W h kg(-1). On the other hand, CNT_CNT performs at a lower level, delivering 5.2 W h kg(-1) at 5.5 kW kg(-1). The favorable charge/discharge performance of CNT_hRuO(2) is attributed to hydrous RuO(2), whose pseudocapacitance drives the other electrode of the vertical CNT array to work harder and makes more use of its double-layer capacitance. The analysis of individual electrode capacitance indicates that the high capacitance of hRuO(2) also causes a disproportion in voltage partition, which restricts the low limit of cycling current in an extended potential window. On energy cycling, CNT_hRuO(2) demonstrates sufficient stability in 10,000 cycles, after an initial 13% drop in capacitance.

Solid-State Lithium Metal Battery of Low Capacity Fade Enabled by a Composite Electrolyte with Sulfur-Containing Oligomers.

A solid-state lithium metal battery of low capacity fade is acquired using the electrolyte membrane of a polyurethane-acrylate-thiocarbonate (PUAT) oligomer, macromolecules, lithium salt, and an oxide additive. Two types of composite electrolytes have been prepared: the free-standing electrolyte (PUAT-FS) and the electrode-coated electrolyte (PUAT-EC). Featuring a less PUAT content and a finer granular size, PUAT-FS is less ion-conductive than PUAT-EC; 0.44 mS cm-1 in contrast to 0.51 mS cm-1 at room temperature. Nonetheless, the lithium iron phosphate battery of PUAT-FS is far superior to that of PUAT-EC in terms of cycling stability. When cycled at 0.1C and room temperature, the PUAT-FS battery reaches a maximum discharge capacity of 169.7 mAh g-1 at its 20th cycle and decreases to 141.0 mAh g-1 at the 500th cycle, 83.1% retention. The capacity fading rate of the PUAT-FS battery is 0.034% per cycle at 0.1C, significantly less than that of the PUAT-EC battery, 0.138% per cycle. Other maximum capacities and fading rates of the PUAT-FS battery are 152.5 mAh g-1 and 0.050% per cycle at 0.2C in 800 cycles and 126.1 mAh g-1 and 0.051% per cycle at 0.5C in 1000 cycles. These features of a low fading rate and high capacity are attributed to a balanced ratio of oligomer to macromolecule (1:1 w/w) in the free-standing electrolyte and the sulfur-containing oligomer.

A nanostructured electrode of IrOx foil on the carbon nanotubes for supercapacitors.

IrO(x) nanofoils (IrO(x)NF) of high surface area are sputtered on multi-wall carbon nanotubes (CNT) in the preparation of a structured electrode on a stainless steel (SUS) substrate for supercapacitor applications. This IrO(x)/CNT/SUS electrode is featured with intriguing IrO(x) curved foils of 2-3 nm in thickness and 400-500 nm in height, grown on top of the vertically aligned CNT film with a tube diameter of ∼ 40 nm. These nanofoils are moderately oxidized during reactive sputtering and appeared translucent under the electron microscope. Detailed structural analysis shows that they are comprised of contiguous grains of iridium metal, iridium dioxide, and glassy iridium oxide. Considerable Raman line broadening is also evidenced for the attributed nanosized iridium oxides. Two capacitive properties of the electrode are significantly enhanced with addition of the curved IrO(x) foils. First, IrO(x)NF reduces the electrode Ohmic resistance, which was measured at 3.5 Ω cm(2) for the CNT/SUS and 2.5 Ω cm(2) for IrO(x)NF/CNT/SUS using impedance spectroscopy. Second, IrO(x)NF raises the electrode capacitance from 17.7 F g(-1) (CNT/SUS) to 317 F g(-1) (IrO(x)/CNT/SUS), measured with cyclic voltammetry. This notable increase is further confirmed by the galvanostatic charge/discharge experiment, measuring 370 F g(-1) after 2000 uninterrupted cycles between - 1.0 and 0.0 V (versus Ag/AgCl).

Phenylphenol-Derived Carbon and Antimony-Coated Carbon Nanotubes as the Electroactive Materials of Lithium-Ion Hybrid Capacitors.

Energy storage of the lithium-ion hybrid capacitor can be upgraded through adjusting the mismatched rate qualities between the positive and negative electrodes because the positive electrode of the electrical double layer (EDL) stores and releases electricity in a smaller quantity, yet much faster than the negative battery electrode. To increase the EDL capacity, nitrogen-doped carbon (KPN900) with a hollow-onion structure is prepared with phenylphenol, achieving a surface area above 3000 m2 g-1. The capacitance of KPN900 displays a diffusive component of 57 F g-1, exceeding its capacitive counterpart at 10 mV s-1. Moreover, its total capacitance reaches 168 F g-1 at 1 mV s-1 with a diffusive component of 112 F g-1. On the other hand, the power of the negative electrode is improved through electrodeposition of metallic antimony on carbon nanotubes, Sb/CNTs, evidenced by the capacity of ∼250 mA h g-1 at 1.0 A g-1. Hence, the capacitor, with a 2:1 mass ratio of KPN900 to Sb/CNT, exhibits an effective trade-off between energy and power, distinct from the one-sided dependence on the carbon electrode of most hybrid capacitors. This capacitor stores 97 W h kg-1 at a power level 0.12 kW kg-1 and 17.4 W h kg-1 at power 7.90 kW kg-1.

Particle Size Influences on the Coating Microstructure through Green Chromia Inclusion in Plasma Electrolytic Oxidation.

In an effort to color the aluminum alloy surface green via plasma electrolytic oxidation (PEO), two alkaline solutions have been employed with particulate inclusions and sodium aluminate. Electrolyte I comprises a self-made chromia pigment with a mean particle size 69 nm, whereas electrolyte II contains a commercially available pigment, GN-M, with a larger particle size 351 nm. Both pigments are oxygen deficient Cr2O3-δ of corundum-type structure before coating, the oxidative environment of PEO converts them into stoichiometric Cr2O3. In electrolyte I and II, the oxides of chromium and aluminum deposit simultaneously under analogous PEO conditions, yet resulting in very different microstructures. The GN-M inclusion of large size amasses on top of the coating, while the self-made inclusion goes deep, and closely associates with alumina and pores. The oxide coating, grown in electrolyte II, consists of a top Cr2O3-rich layer and a dense alumina layer underneath, delineated by the boundary marked with microdischarge burns. On the other hand, the self-made particulate inclusion appears to bring the electric microdischarges inside the coating and create inner pores and damages. The structure difference, caused by the difference in microdischarge locations, is attributed to shifting of the Cr2O3-Al2O3 interface where p-type and n-type semiconductors meet.

Disinfection effects of undoped and silver-doped ceria powders of nanometer crystallite size.

Being endowed with an ability of capturing and releasing oxygen, the ceria surface conventionally assumes the role of catalyzing redox reactions in chemistry. This catalytic effect also makes possible its cytotoxicity toward microorganisms at room temperature. To study this cytotoxicity, we synthesized the doped and undoped ceria particles of 8-9 nm in size using an inexpensive precipitation method and evaluated their disinfecting aptitudes with the turbidimetric and plate count methods. Among the samples being analyzed, the silver-doped ceria exhibits the highest sterilization ability, yet the undoped ceria is the most intriguing. The disinfection effect of undoped ceria is moderate in magnitude, demanding a physical contact between the ceria surface and bacteria cell wall, or the redox catalysis that can damage the cell wall and result in the cell killing. Evidently, this effect is short-range and depends strongly on dispersion of the nanoparticles. In contrast, the disinfection effects of silver-doped ceria reach out several millimeters since it releases silver ions to poison the surrounding microorganisms. Additionally, the aliovalent silver substitution creates more ceria defects. The synergetic combination, silver poisoning and heterogeneous redox catalysis, lifts and extends the disinfecting capability of silver-doped ceria to a superior level.

Cycle stability of the electrochemical capacitors patterned with vertically aligned carbon nanotubes in an LiPF6-based electrolyte.

The miniature ultracapacitors, with interdigitated electrodes of vertically aligned carbon nanotubes (VACNTs) and an inter-electrode gap of 20 µm, have been prepared in the LiPF6 organic electrolyte with and without PVdF-HFP gel. PVdF-HFP between two opposing electrodes enhances the device reliability, but lessens its power performance because of the extra diffusion resistance. Also noteworthy are the gel influences on the cycle stability. When the applied voltage is 2.0 or 2.5 V, both the LiPF6 and the gel capacitors exhibit excellent stability, typified by a retention ratio of ≥95% after 10,000 cycles. Their coulombic efficiencies quickly rise up, and hold steady at 100%. Nonetheless, when the applied voltage is 3.5 or 4.0 V, the cycle stability deteriorates, since the negative electrode potential descends below 0.9 V (vs. Li), leading to electrolyte decomposition and SEI formation. For the LiPF6 capacitor, its retention ratio could be around 60% after 10,000 cycles and the coulombic efficiency of 100% is difficult to reach throughout its cycle life. On the other hand, the gel capacitor cycles energy with a much higher retention ratio, >80% after 10,000 cycles, and a better coulombic efficiency, even though electrolyte decomposition still occurs. We attribute the superior stability of the gel capacitor to its extra diffusion resistance which slows down the performance deterioration.

Structures and catalytic properties of PtRu electrocatalysts prepared via the reduced RuO2 nanorods array.

Structures and properties of PtRu electrocatalyts, derived from the aligned RuO2 nanorods (RuO2NR), are investigated using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and cyclic voltammetry toward COads and methanol oxidation. The catalytic activity of methanol oxidation and the CO tolerance are promoted significantly by reducing RuO2 into Ru metal before decorating with Pt. Reduction of RuO2NR was carried out by either thermal decomposition at 650 degrees C in vacuum or H2-reduction at 130 degrees C in low-pressure hydrogen. Reduction assisted by hydrogen allows infiltrating decomposition at low temperature and produces an array of nanorods with rugged walls featuring small Ru nuclei and larger surface area. Pt-RuNR, whose surface Pt:Ru ratio=0.58:0.42 was prepared by decorating with 0.1 mg cm(-2) Pt on the H2-reduced array containing 0.39 mg cm(-2) Ru, demonstrates a favorable combination of CO tolerance and high methanol oxidation activity superior to other RuO2NR-derived catalysts. When compared with a commercial electrocatalyst of PtRu (1:1) alloy (<4 nm), the activity of Pt-RuNR in methanol oxidation is shown to be somewhat lower at potential<0.48 V and higher at potential>or=0.48 V.