The synthesis and catalytic activity to Li/SOCl2 battery of two new porphyrins

doi:10.1016/j.catcom.2013.03.024

Catalysis Communications

Volume 37, 5 July 2013, Pages 23-26

https://doi.org/10.1016/j.catcom.2013.03.024 Get rights and content

Highlights

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Metal-free porphyrin as a catalyst was used in Li/SOCl₂ battery for the first time;
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Metal-free porphyrin exhibits higher efficient in Li/SOCl₂ battery than that metal phthalocyanine derivatives in some previous reports;
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Excellent catalytic performance is ascribed to promote SOCl₂ electroreduction.

Abstract

Two new porphyrins (3a, 3b) were synthesized and characterized by IR, UV–vis, ¹H NMR, MS and elementary analysis. The catalytic activity of the synthesized porphyrins to lithium/thionyl chloride (Li/SOCl₂) battery is evaluated by the relative energy of the battery whose electrolyte contains the porphyrins. The results indicate that the energy of Li/SOCl₂ battery catalyzed by porphyrins 3a and 3b is 101, 37% higher, respectively, than that of Li/SOCl₂ battery in the absence of the porphyrins. It can be used as a basis for the synthesis of more porphyrins with improved catalytic activity to Li/SOCl₂ battery in the future.

Graphical abstract

Introduction

Lithium/thionyl chloride (Li/SOCl₂) battery are considered promising power sources because of their high energy density, high operation voltage, long storage life and wide operation temperature range [1], [2], [3], [4], [5]. However, the energy of Li/SOCl₂ battery in practice is much lower than that in theory, which severely prohibits its wide application [6]. In addition, Li/SOCl₂ battery is mainly used as the primary battery to supply the power to the instruments operated in long time and in the rough-weather research, which makes the improvement of the practical energy of Li/SOCl₂ battery increasingly urgent. It has been reported that metal phthalocyanines can improve the performance of Li/SOCl₂ battery [6], [7], [8], [9], [10], [11].

Considering porphyrin derivatives have similar structure of phthalocyanine derivatives, high conjugated structure, good thermal stability, excellent electron conductivity and better solubility [15], [16], therefore, the porphyrin derivatives are applied in Li/SOCl₂ battery system to expect to improve its discharge voltage and battery energy. However, to the best of our knowledge, only a few works have demonstrated the catalytic activity of metal porphyrins to Li/SOCl₂ battery [12], [13], [14], and about the catalytic performance of metal-free porphyrins to Li/SOCl₂ battery have not be reported. Furthermore, metal-free porphyrins are much more environmental compatible compared with metal phthalocyanines and metal porphyrins. Herein we report the synthesis, characterization of two metal-free porphyrins and their catalytic activity to Li/SOCl₂ battery.

Section snippets

Materials and reagents

LiAlCl₄/SOCl₂ electrolyte (The concentration of LiAlCl₄ is 1.47 mol · L^− 1), lithium pieces and carbon films were provided by Xi'an Institute of Electromechanical Information Technology, and other reagents were purchased from Beijing Chemical Reagents Company. All solvents and reagents were used without further purification except pyrrole and DMF were distilled before using. 5-(4-hydroxyphenyl)-10,15,20-triphenyl porphyrin (1a) was synthesized according to literature [17]. All chromatographic

Synthesis of the porphyrins

The synthetic routes of the metal-free porphyrins 3a and 3b were illustrated in Scheme 1. The porphyrins 2a and 2b were obtained by displacement reaction of 1,2-dibromoethane and 1,4-dibromobutane with 1a in DMF respectively. Followed, the porphyrins 3a and 3b were synthesized by using porphyrins 2a and 2b reacting with imidazole in DMF in the presence of K₂CO₃ respectively.

The UV–vis spectra of the porphyrin 3a consist of a Soret band at 417 nm, and the Q bands at 515, 550, 590 and 646 nm. The

Conclusion

We have synthesized and characterized two metal-free porphyrins to be used as catalysts to Li/SOCl₂ battery. The results indicate that the battery's discharge time is 15 min for 3a and 12 min for 3b longer than that of Li/SOCl₂ battery in the absence of porphyrins. Simultaneously the battery's energy is increased 101, 37% respectively. In a word, the metal-free porphyrins show high efficiency as catalysts to Li/SOCl₂ battery and it is much more environmental compatibility compared with metal

Acknowledgements

We thank the financial support from National Nature Science Foundation (20971103 and 21271148). We are very grateful to Xi'an Institute of Electromechanical Information Technology for their kind assistance.

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The first is tandem batteries to form a battery pack, but the disadvantage is that it takes up large space [13–15]. The second method is to add the catalysts in the electrolyte, such as carbon nanotubes [16,17], graphene [18], metal phthalocyanine [19–22] and porphyrin [23,24], while the catalysts clog pores of the carbon cathode. Furthermore, the carbon cathode was added carbon nanotubes [25] and graphene [26] to regulate the porosity.
Primary batteries based on lithium metal anodes have been attracting increasing attention due to their high capacity and energy density, but the implementation high-current of battery still faces many challenges, such as low reaction rate of SOCl₂ and large impedance. Space-confined construction of nitrogen-rich cobalt porphyrin-derived nanoparticulates anchored on functional-activated carbon (NCA) composites were prepared by in situ solid phase synthesis as catalysts of carbon cathode to address these issues. On the molecular level, the π-π conjugate system is further enhanced by forming C–O–Co bond between the Co atoms of cobalt porphyrin derivatives and the oxygen-containing functional groups of functional-activated carbon. Significantly, the resulting NCA composites exhibit the longest high-current (above 25 mA/cm²) discharge time, up to 37 min, and the capacity is about 19.18 mAh, accounting for 88.5% of its total capacity. Meanwhile, the internal resistance of the battery catalyzed by the NCA composites (24.06 Ω) is 0.40 times lower than that without catalysts, and the reduction peak of cyclic voltammetry is the largest about 2.357 V, showing that the electrode with NCA composites has good catalytic activity. All this is due to the fact that the carrier activated carbon of the NCA composites reduces the internal resistance of the battery by regulating the porosity of the carbon cathode, and the loaded CoTAP nanoparticulates improve the reduction rate of SOCl₂.
Porphyrin decorated Bi<inf>2</inf>O<inf>2</inf>CO<inf>3</inf> nanocomposites with efficient difunctional properties of photocatalysis and optical nonlinearity
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Considerable attention has been paid to design multifunctional hybrid materials for developing novel optoelectronic systems. Here, a series of novel porphyrin decorated Bi₂O₂CO₃ nanocomposites (BOC/TPP) loaded with different porphyrin contents was prepared by a facile solvothermal technique to maximize the photocatalysis and optical nonlinearity. The photoresponsive range of the BOC/TPP nanocomposites can be extended from UV to visible light, and the band gap can be continuously tuned. The wide absorption of the as-prepared nanocomposites in the visible light region makes them suitable for photocatalytic and nonlinear transmission studies. The associated photocatalysis and optical nonlinearity for the BOC/TPP nanocomposites are shown to be dependent on the contents of porphyrin. Compared to BOC, TPP and other prepared nanocomposites with different TPP loadings, the BOC/0.03TPP nanocomposite with 3 wt% TPP exhibits the highest photocatalytic performance and nonlinear optical absorption effect, due to the efficient interfacial charge transfer and the strong interfacial electronic interactions between TPP and BOC. These findings provide an ideal scientific platform to guide the rational design of difunctional nanomaterials with desired optoelectronic performances.
Improved performance of Li/SOCl<inf>2</inf> batteries using binuclear metal azaphthalocyanines as electrocatalysts
2016, Electrochimica Acta
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Much efforts on these problems have been studied to improve practical energy density of Li/SOCl2 battery [9–11]. According to the previous researches, macromolecular compounds such as phthalocyanines and porphyrins can effectively catalyze electrolyte reaction [12–15]. It has been proved that phthalocyanine compounds can improve the battery capacity involved in a catalytic two-electron step that is verified by cyclic voltammetry (CV) [16].
A total of twenty four binuclear metal azaphthalocyanine compounds in four series of M₂(azaPc)₂Me, M₂(azaPc)₂SO₂, M₂(azaPc)₂, M₂(azaPc)₂CO (M = Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺) were synthesized by solid phase method, which were applied for Li/SOCl₂ battery as electrocatalysts to enhance its capacity and discharge voltage. In all cases, the electrochemical performances of Li/SOCl₂ batteries were improved compared with controls. It is worth mentioning that Mn₂(azaPc)₂SO₂ increased the discharge voltage to 3.3485 V, rising by 0.1570 V compared with that of the blank. Co₂(azaPc)₂CO lengthened the discharge time to 1821 s, rising by 75.80%. And Co₂(azaPc)₂ raised battery capacity to 35.24 mA h, increasing by 79.56%. Based on cyclic voltammetry measurements, the reaction mechanism was found to involve an irreversible two-step electron transfer process and a hypothesis was conjectured. All the azaphthalocyanine compounds were characterized by element analysis, IR analysis, and UV-Vis absorption.
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The discharge profiles are as Fig. 6. Compared with the AB cathode without the catalyst, the cathodes with either CoPc or Co-N-G-800 exhibited substantial increases in discharge voltage and capacity, indicating that CoPc and Co-N-G-800 effectively catalyzed the reduction of SOCl2 [7,10], and that the catalytic effects of the two catalysts were comparable. However, as the content of the catalyst increased, the discharge capacities of the CoPc and Co-N-G-800 batteries exhibited dissimilar trends (Insert in Fig. 6a and b, respectively).
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Nitrogen-doped graphene (N-G) catalysts, synthesized by mixing nitrogen from urea with graphene and subsequent high temperature pyrolysis, have significantly increased the discharge voltage and capacity of Li/SOCl₂ batteries. The cyclic voltammetry (CV) curves and the battery discharge profiles demonstrated that the synthesis temperature of the N-G catalysts had a significant effect on the catalytic performance. A comparison of the catalytic performance of the N-G catalysts at various synthesis temperatures (600 °C, 800 °C, 900 °C) exhibited the following results: N-G-900 > N-G-800 > N-G-600. However, the X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, thermogravimetric analysis (TGA) and cyclic voltammetry results suggest that the N elements incorporated in the molecular structure of graphene in the form of a “pyridinic-N” cyclic substructure at high synthesis temperatures is the critical factor in enhancing the catalytic performance of graphene, rather than “high synthesis temperatures” alone.

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Short CommunicationThe synthesis and catalytic activity to Li/SOCl2 battery of two new porphyrins

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Materials and reagents

Synthesis of the porphyrins

Conclusion

Acknowledgements

Carbon

Carbon

Applied Catalysis A

Journal of Power Sources

Journal of Power Sources

Journal of Molecular Catalysis A: Chemical

Electrochimica Acta

Journal of Power Sources

Short Communication
The synthesis and catalytic activity to Li/SOCl₂ battery of two new porphyrins