Fibrous polyaniline as positive active material in lithium secondary batteries

doi:10.1016/0378-7753(87)80119-2

Journal of Power Sources

Volume 20, Issues 3–4, July 1987, Pages 249-252

https://doi.org/10.1016/0378-7753(87)80119-2 Get rights and content

Abstract

Fibrous polyaniline (f-PANI) has displayed a maximum discharge capacity of 164 A h kg⁻¹, a low rate of self-discharge, and a long life as a positive active material in a secondary lithium battery.

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Cited by (51)

Constructing superhydrophilic CoRu-LDH/PANI nanowires with optimized electronic structure for hydrogen evolution reaction
2023, Electrochimica Acta
Citation Excerpt :
In addition, carbon-doped nanoporous cobalt phosphide (C-Co2P) synthesized by dealloying displays an overpotential of 30 mV at 10 mA cm−2 in alkaline media, which may be mainly attributed to the strong electronegativity and small atomic radii, thus C sites can tune the electronic structure of Co2P to weaken the Co-H bond [32]. Polyaniline (PANI), as one of the typical organic conductive polymer with high electrical conductivity and hydrophilicity, have been widely applied in catalysis and energy conversion areas, such as supercapacitors [33–35], lithium batteries [36,37], and HER catalysts [38,39]. The PANI surface with rich amine groups can act as bridging sites to form an strongly coupled interface, which is favourable for tuning the electronic structure and optimizing the position of valence state of active sites [40,41].
Promoting the dissociation of water and desorption of hydrogen are both crucial challenges for improving the hydrogen evolution reaction (HER) activity and stability in alkaline media, especially at large current densities. Herein, we demonstrate a polyaniline-coated CoRu-LDH (CoRu-LDH/PANI) nanowire array electrocatalyst for efficient and stable alkaline HER. Benefiting from the optimized electronic structure and surface properties, the as-prepared CoRu-LDH/PANI shows an excellent HER activity with low overpotentials of 250, and 275 mV, respectively, at large current densities of 500 and 1000 mA cm⁻² in 1.0 M KOH, superior to the benchmark 20% Pt/C and the pristine CoRu-LDH. Furthermore, CoRu-LDH/PANI exhibits an unprecedented stability at a large current density of 500 mA cm⁻² even after 50 h. The combined experimental and density functional theory (DFT) investigations reveal that PANI coating not only performs as an electronic regulator to lift the valence states and reduces the binding strength to hydrogen intermediates, leading to the superior HER performance, but also affords a superhydrophilic surface to promote the rapid transport of electrolytes and bubbles, which is crucial for the long-term stability at large current density. This work provides an effective guidance for engineering efficient alkaline HER eletrocatalysts towards practical water electrolysis.
Nanomaterials and nanotechnology for high-performance rechargeable battery
2020, Nanobatteries and Nanogenerators: Materials, Technologies and Applications: A Volume in Micro and Nano Technologies
Enormous developments have been performed in the progress of high-performance rechargeable batteries during last years, both in industry and research. The findings of innovative electrode materials and novel storage mechanisms have considerably enhanced the performances of rechargeable batteries. Particularly the architecture of nanostructured materials has occurred as a talented solution to overcome several basic difficulties in standard battery materials. Nanotechnology-based techniques have revealed plentiful benefits for enhanced safety, cyclability, power density, and energy. In the present chapter, we provide a report on nanomaterials, which are either available in commerce or near to be commercialized for various applications, along with those below progress with the aptitude to achieve the necessities for much more high-performance rechargeable batteries.
p-Dopable poly(4-cyano)triphenylamine: A high voltage organic cathode for lithium ion batteries
2015, Materials Letters
Citation Excerpt :
In recent years, organic cathodes attract growing attentions because of their abundant resources, easy recycling features and feasible rapid electrochemical kinetics [4–6]. Some redox-active organics, such as polyaniline (PAn) [7,8], poly(p-phenylene) (PPP) [9], polytriphenylamine (PTPAn) [10] have been intensively investigated as cathode materials for Li-ion batteries. Among them, PTPAn shows superior cycling stability and rate capability due to its conductive PPP backbone and electroactive PAn unit [11,12].
In this work, p-dopable poly(4-cyano)triphenylamine is prepared simply by grafting electron-withdrawing cyano group onto triphenylamine chains through a chemical oxidative polymerization. The electrochemical tests show that the organic cathode has a high average discharge voltage of 3.9 V (vs. Li⁺/Li), and delivers a reversible capacity of ~80 mAh g⁻¹with stable cycling, also a capacity of 55 mAh g⁻¹ is retained even cycled at a high current density of 400 mA g⁻¹.The superior electrochemical performances of this organic cathode may enable it to be an alternative cathode material for future green and sustainable organic-based batteries.
Polytriphenylamine: A high power and high capacity cathode material for rechargeable lithium batteries
2008, Journal of Power Sources
Polytriphenylamine (PTPAn) was chemically synthesized and tested as a cathode material for high-rate storage and delivery of electrochemical energy. It is found that the polymer has not only superior high power capability but also high energy density at prolonged cycling. At a moderate rate of 0.5C, PTPAn gives a high average discharge voltage of 3.8 V and quite a high capacity of 103 mAh g⁻¹, which is very close to the theoretical capacity (109 mAh g⁻¹) as expected from one electron transfer per triphenylamine monomer. Even cycled at a very high rate of 20C, the polymer can still deliver a capacity of 90 mAh g⁻¹ at 1000th cycle with a nearly 100% coulombic efficiency. The excellent electrochemical performances of PTPAn are explained from the structural specificity of the polymer where the radical redox centers are stabilized and protected by conductive polymeric backbone, making the radical redox and charge-transporting processes kinetically facile for high-rate charge and discharge.
Preparation of polyaniline nanofibers and their use as a cathode of aqueous rechargeable batteries
2006, Electrochimica Acta
Normal pulse voltammetric method was used to synthesize nanofibers of polyaniline (PANi) in HCl solution on a platinum electrode. The influences of the synthesis parameters, such as potential increment, pulse duration and monomer concentration on the electrochemical properties of the PANi films were investigated. Scanning electron microscopic micrographs clearly revealed the formation a nanofiber structure with average diameter in range 70–100 nm under optimum experimental conditions. The electrochemical properties of PANi films were studied with the impedance analysis, cyclic voltammetry and charge/discharge capacities. FT-IR results revealed that the PANi nanofibers were in emeraldine salt form. The film was employed as a positive electrode (cathode) for a PANi-Zn secondary battery containing 1.0 M ZnCl₂ and 0.5 M NH₄Cl as electrolyte. The cells were charged and discharged under a pulse current of 0.31 mA cm⁻². It was found that the maximum capacity of the PANi-Zn battery is 235.60 Ah kg⁻¹ with a columbic efficiency of 97–100% over a wide range of current density of 0.3–5.6 mA cm⁻². The specific energy was 287.43 Wh kg⁻¹ and the PANi cathode exhibited good recycleability.
A rechargeable Zn- poly(aniline-co-m-aminophenol) battery
2006, Journal of Power Sources
Based on the cyclic voltammograms and impedance spectra of poly(aniline-co-m-aminophenol) in the electrolyte solution containing ZnCl₂ and NH₄Cl, a solution consisting of 2.0 M ZnCl₂ and 3.0 M NH₄Cl with pH 4.70 was employed as an electrolyte solution of a Zn-poly(aniline-co-m-aminophenol) battery. The battery was charged and discharged between 0.75 and 1.45 V at different current densities. The average charge voltage is about 1.15 V and the average discharge voltage is about 1.05 V, slightly depending on the charge–discharge current density. The capacity and energy densities of poly(aniline-co-m-aminophenol) are 137.5 A h kg⁻¹ and 152.5 W h kg⁻¹ for discharge process, respectively, which are much better than those of polyaniline at the same solution. After the test of the charge–discharge at different current densities, the battery was successively charged and discharged for 120 cycles. At one-hundred and twentieth cycle, the coulombic efficiency is 100% and the energy density of poly(aniline-co-m-aminophenol) only decreases by 9.2%, compared with the first cycle of the successive charge–discharge processes.

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Fibrous polyaniline as positive active material in lithium secondary batteries

Abstract

J. Chem. Soc., Chem. Commun.

J. Chem. Soc., Chem. Commun.