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Journal ArticleDOI

Redox-State-Dependent Interplay between Pendant Group and Conducting Polymer Backbone in Quinone-Based Conducting Redox Polymers for Lithium Ion Batteries

16 Sep 2019-Vol. 2, Iss: 10, pp 7162-7170
TL;DR: Conducting redox polymers (CRPs) have attracted increased interest in recent years because of the possibility of combining the favorable electron-transport properties of conducting polymers with th...
Abstract: Conducting redox polymers (CRPs) have attracted increased interest in recent years because of the possibility of combining the favorable electron-transport properties of conducting polymers with th...
Citations
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04 Mar 2019
TL;DR: In this paper, the Mg2+-storing organic cathodes were shown to deliver the same energy while using ∼10% of the amount of electrolyte needed for MgCl-based counterparts.
Abstract: Summary Magnesium batteries could offer high energy density and safety due to the non-dendritic Mg metal anode. However, Mg2+ ingress into and diffusion within cathode materials are kinetically sluggish. It is therefore intriguing that recently organic cathodes were shown to deliver high energy and power even at room temperature. Herein we reveal that previous organic cathodes likely all operated on a MgCl-storage chemistry sustained by a large amount of electrolyte that significantly reduces cell energy. We then demonstrate Mg batteries featuring a Mg2+-storage chemistry using quinone polymer cathodes, chloride-free electrolytes, and a Mg metal anode. Under lean electrolyte conditions, the Mg2+-storing organic cathodes deliver the same energy while using ∼10% of the amount of electrolyte needed for the MgCl-based counterparts. The observed specific energy (up to 243 Whr kg−1), power (up to 3.4 kW kg−1), and cycling stability (up to 87% at 2,500 cycles) of Mg-storage cells consolidate organic polymers as promising cathodes for high-energy Mg batteries.

30 citations

Journal ArticleDOI
TL;DR: This work shows that quinizarin (Qz)- and naphthoquinone (NQ)-based CRPs can reach their theoretical capacity through optimization of the polymerization conditions, and employs a solution-processable postdeposition polymerization (PDP) method.
Abstract: Rechargeable batteries that use redox-active organic compounds are currently considered an energy storage technology for the future. Functionalizing redox-active groups onto conducting polymers to make conducting redox polymers (CRPs) can effectively solve the low conductivity and dissolution problems of redox-active compounds. Here, we employ a solution-processable postdeposition polymerization (PDP) method, where the rearrangements ensured by partial dissolution of intermediated trimer during polymerization were found significant to produce high-performance CRPs. We show that quinizarin (Qz)- and naphthoquinone (NQ)-based CRPs can reach their theoretical capacity through optimization of the polymerization conditions. Combining the two CRPs, with the Qz-CRP as a cathode, the NQ-CRP as an anode, and a protic ionic liquid electrolyte, yields a 0.8 V proton rocking-chair battery. The conducting additive-free all-organic proton battery exhibits a capacity of 62 mAh/g and a capacity retention of 80% after 500 cycles using rapid potentiostatic charging and galvanostatic discharge at 4.5 C.

22 citations

Journal ArticleDOI
TL;DR: In this paper , the authors theoretically investigated five cyclohexanone derivatives (denoted as: H1, H2, H3, H4, and H5) and influence of functional groups on their electrochemical properties using advanced level density functional theory (DFT) with the Perdew-Burke-Ernzenhof hybrid functional at 6-31+G(d,p) basis set.

21 citations

Journal ArticleDOI
TL;DR: Quinones have a capacity for high energy storage and exhibit facile and reversible electrochemistry in several widely different electrolytes, and are therefore one of the most popular compounds.
Abstract: Quinones have a capacity for high energy storage and exhibit facile and reversible electrochemistry in several widely different electrolytes. They are, therefore, one of the most popular compounds ...

20 citations

Journal ArticleDOI
TL;DR: A conducting redox polymer (CRP) based on poly(3,4-ethylenedioxythiophene) with naphthoquinone pendant group, which is formed from a stable suspension of a trimeric precursor and an oxoammonium cation as oxidant, makes the CRP a promising candidate as anode-active material.
Abstract: Organic materials receive increasing attention as environmentally benign and sustainable electrode-active materials. We present a conducting redox polymer (CRP) based on poly(3,4-ethylenedioxythiophene) with naphthoquinone pendant group, which is formed from a stable suspension of a trimeric precursor and an oxoammonium cation as oxidant. This suspension allows us to easily coat the polymer onto a current collector, opening up use of roll-to-roll processing or ink-jet printing for electrode preparation. The CRP showed a full capacity of 76 mAh g-1 even at a high C rate of 100 C in acidic aqueous electrolyte. These properties make the CRP a promising candidate as anode-active material; a polymer-air secondary battery was fabricated with the CRP as anode, a conventional Pt/C catalyst as cathode, and sulfuric acid aqueous solution as electrolyte. This battery yielded a discharge voltage of 0.50 V and showed good cycling stability with 97 % capacity retention after 100 cycles and high rate capabilities up to 20 C.

18 citations

References
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Journal ArticleDOI
TL;DR: The Hammett equation has been widely used for the study and interpretation of organic reactions and their mechanisms as mentioned in this paper, and it is astonishing that u constants, obtained simply from the ionization of organic acids in solution, can frequently predict successfully equilibrium and rate constants for a variety of families of reactions in solution.
Abstract: The Hammett equation (and its extended forms) has been one of the most widely used means for the study and interpretation of organic reactions and their mechanisms. Although the Hammett methodology has been criticized by theoreticians because of its empirical foundation, it is astonishing that u constants, obtained simply from the ionization of organic acids in solution, can frequently predict successfully equilibrium and rate constants for a variety of families of reactions in solution. Almost every kind of organic reaction has been treated via the Hammett equation, or its extended form. The literature is so voluminous and extensive that there is no complete review of all that has been accomplished. Hammett's success in treating the electronic effect of substituents on the rates and equilibria of organic reactions1P2 led Taft to apply the same principles to steric and inductive and resonance effects? Then, more recently, octanol/ water partition coefficients (P) have been used for rationalizing the hydrophobic effects of organic compounds interacting with biological systems? The use of log P (for whole molecules) or n (for substituents), when combined with electronic and steric parameters, has opened up whole new regions of biochemical and pharmacological reactions to study by the techniques of physical organic chemistry.sf3 The combination of electronic, steric, hydrophobic, hydrophilic, and hydrogen-bonding7 parameters has been used to derive quantitative structure-activity relationships (QSAR) for a host of interactions of organic compounds with living systems or parts thereof. The binding of organic compounds to proteins,8 their interaction with enzymess and with cellsloJ1 and tiasues,12 their inhibition of organelles,l' and as antimalarial^'^

6,870 citations

Journal ArticleDOI
TL;DR: This review provides a comprehensive overview of novel battery systems and discusses the numerous classes of organic, polymer-based active materials as well as auxiliary components of the battery, like additives or electrolytes.
Abstract: The storage of electric energy is of ever growing importance for our modern, technology-based society, and novel battery systems are in the focus of research. The substitution of conventional metals as redox-active material by organic materials offers a promising alternative for the next generation of rechargeable batteries since these organic batteries are excelling in charging speed and cycling stability. This review provides a comprehensive overview of these systems and discusses the numerous classes of organic, polymer-based active materials as well as auxiliary components of the battery, like additives or electrolytes. Moreover, a definition of important cell characteristics and an introduction to selected characterization techniques is provided, completed by the discussion of potential socio-economic impacts.

825 citations

Journal ArticleDOI
TL;DR: Three systems that coupled with industrially established cathodes and electrolytes exhibit long cycle life, fast kinetics, high anode specific capacity, and several examples of state-of-the-art specific energy/energy density are demonstrated.
Abstract: Aqueous rechargeable batteries are promising for grid storage and electric vehicles, but they suffer from poor cycle life due to anode instability. Exploiting stable ion-coordination charge storage and chemical inertness towards aqueous electrolytes, quinones are now reported as stable anodes.

546 citations

Journal ArticleDOI
TL;DR: The use of lithiated redox organic molecules containing electrochemically active C=O functionalities, such as lithiated oxocarbon salts, is proposed to represent alternative electrode materials to those used in current Li-ion battery technology that can be synthesized from renewable starting materials.
Abstract: The use of lithiated redox organic molecules containing electrochemically active C═O functionalities, such as lithiated oxocarbon salts, is proposed. These represent alternative electrode materials to those used in current Li-ion battery technology that can be synthesized from renewable starting materials. The key material is the tetralithium salt of tetrahydroxybenzoquinone (Li4C6O6), which can be both reduced to Li2C6O6 and oxidized to Li6C6O6. In addition to being directly synthesized from tetrahydroxybenzoquinone by neutralization at room temperature, we demonstrate that this salt can readily be formed by the thermal disproportionation of Li2C6O6 (dilithium rhodizonate phase) under an inert atmosphere. The Li4C6O6 compound shows good electrochemical performance vs Li with a sustained reversibility of ∼200 mAh g−1 at an average potential of 1.8 V, allowing a Li-ion battery that cycles between Li2C6O6 and Li6C6O6 to be constructed.

417 citations

Journal ArticleDOI
TL;DR: In this paper, the performance of a polyaniline (PANI) based supercapacitor where electroactive PANI films were prepared on carbon paper electrodes from a nonaqueous solution with an organic acid (CF 3 COOH) as the proton source was investigated.
Abstract: In this study, the performance of a polyaniline (PANI) based supercapacitor where electroactive PANI films were prepared on carbon paper electrodes from a nonaqueous solution with an organic acid (CF 3 COOH) as the proton source was investigated. The use of nonaqueous media as electrolyte led to an increase of the electroactivity window from 0.75 V in aqueous media up to 1.0 V. Low frequency capacitance, evaluated by electrochemical impedance spectroscopy, of about 150 F/g is reported. Scanning electron microscopy indicated a highly porous material for deposited charges greater than 1 C/cm 2 . Constant current charge/discharge cycling of a symmetric supercapacitor based on PANI in nonaqueous medium was performed in a two-electrode cell configuration and a loss of about 60% of the discharge capacity was demonstrated after 1000 cycles. Tetramethylammonium methanesulfonate (Me 4 NCF 3 SO 3 ) was also used instead of tetraethylammonium tetrafluoborate (Et 1 NBF 4 ) as supporting electrolyte in acetonitrile for the charge/discharge testing of the PANI-PANI capacitor. Energy and power densities of approximately 3.5 Wh/kg and 1300 W/kg, respectively, were developed by this supercapacitor for a cell voltage of I V and a discharge time of 20 s. On the other hand, an asymmetrical supercapacitor with polypyrrole and polyaniline used as positive and negative electrodes, respectively, displayed slightly improved performance. Indeed, an energy density of 5 Wh/kg and a power density of 1200 W/kg were reported for discharge time of about 20 s with 1 M Me 4 NCF 3 SO 3 /acetonitrile as electrolyte.

283 citations