The synthesis of Cu(II), Zn(II), and Co(II) metalloporphyrins and their improvement to the property of Li/SOCl2 battery

Zhang, Zengqi; Kong, Luyao; Xiong, Ying; Luo, Yun; Li, Jun

doi:10.1007/s10008-014-2571-3

Cited by 23 publications

(8 citation statements)

References 31 publications

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“…[ 13 ] The existence of transition metal compounds in the center of MPcs can result in auto‐O 2 ‐binding properties because transition metals easily oxidize or reduce to stably share electrons with O 2 molecules. [ 14 ] Moreover, it has been suggested that the overall MPc properties could be controlled by controlling the central transition‐metal atom in the molecular structure, which implies that well‐controlled MPcs can deliver excellent catalytic activities and high stability for application to LABs and exhibit a wide range of redox potentials by manipulating the central metal atom. [ 15 ] Thus, to discover effective and outstanding MPcs as promising RMs for application to LABs, we performed first‐principles calculations on various MPcs exhibiting different central transition‐metal atoms.…”

Section: Resultsmentioning

confidence: 99%

Auto‐Oxygenated Porphyrin‐Derived Redox Mediators for High‐Performance Lithium Air‐Breathing Batteries

Kim

Park

et al. 2022

Advanced Energy Materials

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Because of their distinct energy potentials, Li air‐breathing batteries have been highlighted as promising energy storage systems; however, the sluggish oxygen reduction and evolution reactions (ORR and OER) disturb the reversible cell operation during cycling. Therefore, catalyst materials should be tailored to mitigate the low efficiencies of air‐breathing batteries. A porphyrin‐derived catalyst is optimized by introducing different metal‐centered organometallic phthalocyanine (MPc) complexes and their potential application as redox mediators (RMs) for fabricating efficient Li–O2 cells is investigated. The feasibility of each MPc is determined as a potential RM by calculating its orbital levels. The electrochemical properties of the Li–O2 cells employing the diverse MPc‐RMs are compared. The MPc‐containing Li–O2 cells exhibit improved cell performance, reduced polarization, and stable cyclability with auto‐oxygenated properties as revealed by directly injecting superoxide species into the MPc‐containing electrolytes. The synergistic effects of blended MPcs—a mixture consisting of the two most effective MPcs—in both the OER and ORR regions in ambient air atmosphere are also elucidated. The reaction mechanism of the MPc‐containing cells is proposed based on first‐principles calculations and experimental results. The introduction of natural functional catalysts provides a basis for developing effective eco‐friendly catalysts for application to sustainable air‐breathing batteries.

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Section: Resultsmentioning

confidence: 99%

Auto‐Oxygenated Porphyrin‐Derived Redox Mediators for High‐Performance Lithium Air‐Breathing Batteries

Kim

Park

et al. 2022

Advanced Energy Materials

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“…The metal complexes (3−6) of H 2 -TCBD (2) were prepared using the literature method 40,42,43 and exhibited a marginal red shift in their electronic spectral features. The photophysical data are listed in Table 1 along with the quantum yield of H 2 -TCBD (2) and Zn-TCBD (6).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

β-Tetracyanobutadiene-Appended Porphyrins: Facile Synthesis, Spectral and Electrochemical Redox Properties, and Their Utilization as Excellent Optical Limiters

et al. 2021

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A series of β-TCBD (1,1,4,4-tetracyano-buta-1,3diene)-appended porphyrins, M-TCBD (M = 2H, Co(II), Ni(II), Cu(II), and Zn(II)), was synthesized from 2,3-diphenylethynyl-12nitro-meso-tetraphenylporphyrin, H 2 -PE 2 , and characterized by various spectroscopic techniques and electrochemical studies. The reaction proceeds via [2 + 2] cycloaddition and retroelectrocyclization reactions of tetracyanoethylene (TCNE) with H 2 -PE 2 . The observed unusual reduction potentials in the cyclic voltammograms of the synthesized porphyrins in the range of −0.06 to −0.10 V are the consequence of the TCBD moiety present at the β-position of the porphyrin macrocycle. Notably, these porphyrins exhibited three porphyrin ring-centered reductions due to extended π-conjugation. The higher nonlinear optical response exhibited by the M-TCBD series as compared to the precursor (H 2 -PE 2 ) was attributed to the existence of intramolecular charge transfer and enhanced polarization in the M-TCBD series. The single-beam femtosecond Z-scan measurements were performed to elucidate the third-order nonlinear optical properties, and the temporal response of these porphyrin molecules was investigated using optical pump−probe spectroscopy to study the excited state absorption dynamics. Zscan measurements revealed that Co-TCBD exhibited a higher nonlinear optical response as compared to free base porphyrins. The two-photon absorption coefficient (β) and the imaginary part of third-order nonlinear optical susceptibility (χ (3) ) were obtained from the open aperture experiment, whereas the close aperture experiment delivered the magnitude and the sign of the nonlinear refractive index (n 2 ) and the real part of χ (3) . Furthermore, the femtosecond transient absorption spectroscopy revealed a faster relaxation dynamics of various absorption processes in a picosecond timescale. The excellent optical limiting threshold (1.90−2.33 × 10 15 W/m 2 ) of the synthesized porphyrins makes them good materials for laser protection and high-power laser operation.

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“…After discharging, the AC impedance spectrum shows that the Rs and R1 (semi-circular arc diameter in the high-frequency region) values of the different cathode carriers are similar, which indicates that the difference caused by the micropores has been lessened. It appears that the micropores are blocked by the reaction product LiCl (Zhang et al, 2018), so the resistance of the solution is dominated by the mesoporous holes, which are not completely blocked. The slope of the curve in the low-frequency region after discharging is lower than that before discharging.…”

Section: Electrochemical Performance Of the Batterymentioning

confidence: 99%

“…Lee et al (2001) pointed out that in the battery discharge reaction process, the reaction product, lithium chloride, will block the pores of the carbon cathode support and strongly hinder the diffusion of thionyl chloride in the support. Thus the SOCl 2 reduction rate control step changes from an "interface reaction between the cathode and electrolyte" to "diffusion of SOCl 2 through the porous layer, " thus affecting the electrical performance of the lithium-thionyl chloride battery (Lee et al, 2001;Kim and Pyun, 2003;Zhang et al, 2018). The discharge performance of lithium-thionyl chloride batteries has previously been improved by adding metal phthalocyanine compounds to the cathode support (Liu et al, 2016;Gao et al, 2017Gao et al, , 2018.…”

Section: Introductionmentioning

confidence: 99%

The Effects of Pore Size on Electrical Performance in Lithium-Thionyl Chloride Batteries

et al. 2019

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Lithium-thionyl chloride batteries possess the highest specific energies of the batteries that are commercially available. These batteries also have high operating voltages, stable outputs, wide operating temperature ranges, and long storage lives and are of low cost. The main limitation of lithium-thionyl chloride batteries is their low discharge capacity at high discharge rates, which limits their commercial uses. In this study, a porous cathode carbon support was prepared by introducing ammonia bicarbonate as a pore-forming agent. The porous cathode carbon support that formed was systematically characterized by BET, SEM, and XRD. The support was then assembled into an ER18505M battery system, and the electrochemical performance of the battery was characterized. The effect of pore structure on the electrochemical performance was determined and enabled the preparation of a high capacity lithium-thionyl chloride battery with a high discharge rate.

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The synthesis of Cu(II), Zn(II), and Co(II) metalloporphyrins and their improvement to the property of Li/SOCl2 battery

Cited by 23 publications

References 31 publications

Auto‐Oxygenated Porphyrin‐Derived Redox Mediators for High‐Performance Lithium Air‐Breathing Batteries

Auto‐Oxygenated Porphyrin‐Derived Redox Mediators for High‐Performance Lithium Air‐Breathing Batteries

β-Tetracyanobutadiene-Appended Porphyrins: Facile Synthesis, Spectral and Electrochemical Redox Properties, and Their Utilization as Excellent Optical Limiters

The Effects of Pore Size on Electrical Performance in Lithium-Thionyl Chloride Batteries

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