Dihydrophenazine‐Based Copolymers as Promising Cathode Materials for Dual‐Ion Batteries

Obrezkov, Filipp A.; Somova, Anna I.; Fedina, Elena S.; Васильев, С. Г.; Stevenson, Keith J.; Troshin, Pavel A.

doi:10.1002/ente.202000772

Cited by 19 publications

(23 citation statements)

References 25 publications

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“…After subtracting the considerable capacity contribution from KB in the composite electrode (22 mAh g −1 ; Figure S4), the accurate capacity from PPTZ (135 mAh g −1 ) was approached to its theoretical capacity based on 1 e reaction (137 mAh g −1 for the ideal structure or 122 mAh g −1 for the actual structure). PPTZ showed sloping voltage profiles with an average discharge voltage of approximately 3.5 V (Figure 2c), which was consistent to previously reported PTZ‐based polymers, [21,27–30] and also approximate to other N‐heteroaromatics, such as N ‐substituted phenazine [18] and phenoxazine [32] . For the cycling performance, the discharge capacity of PPTZ still remained 127 mAh g −1 (81 % retention relative to the first cycle) after 100 cycles, while the CE increased from 82.8 % at the first cycle to a stabilized value of 98.5 % after 50 cycles.…”

Section: Resultssupporting

confidence: 90%

“…Because of the insufficient solubility of PPTZ in common organic solvents including strong polar DMSO, we attempted to investigate the detailed chemical structure of PPTZ by solid‐state NMR (SS NMR) spectroscopy (see the Supporting Information, Figure S1). However, unfortunately, the results were not very informative due to serious overlapping of multiple peaks, which was also the case of a similar PTZ‐based conjugated polymer recently reported [18] . Compared to PTZ monomer, PPTZ showed smaller chemical shifts in either 1 H SS NMR or 13 C SS NMR spectra, probably due to the conjugation effect after polymerization.…”

Section: Resultsmentioning

confidence: 76%

“…The most well‐known p‐type organic cathode materials are conducting polymers (e. g., polyaniline, [11,12] polytriphenylamine, [13] and polypyrrole [14] ) and nitroxyl radical polymers (e. g., PTMA [15] ). In recent years, researchers’ interest also shifts to polymers based on various electroactive heteroaromatics, including N ‐substituted phenazine, [16–19] conjugated pyridine dimer, [20] phenothiazine, [18,21–31] phenoxazine, [32] and thianthrene [33,34] . A merit of these heteroaromatic units is that they are potentially able to deliver two electrons and thus achieve attractive capacity above 200 mAh g −1 .…”

Section: Introductionmentioning

confidence: 99%

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Facile Synthesis of Polyphenothiazine as a High‐Performance p‐Type Cathode for Rechargeable Lithium Batteries

Wang

Han

et al. 2021

ChemSusChem

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p‐Type electroactive polymers are promising cathodes for dual‐ion batteries but cost‐effective candidates are still lacking. In this study, the p‐type polymer polyphenothiazine (PPTZ) is synthesized by a facile one‐step oxidation polymerization from the low‐cost phenothiazine (PTZ) monomer. As a cathode for rechargeable lithium batteries, PPTZ shows superior electrochemical performance to previously reported PTZ‐based polymers with complicated structures and syntheses. For example, PPTZ has a high reversible capacity of 157 mAh g−1 within 2.5–4.3 V vs. Li+/Li with an average discharge voltage of 3.5 V, and a high capacity retention of 77 % after 500 cycles. The highly reversible one‐electron redox mechanism of PPTZ is also investigated in detail by electrochemical testing, ex situ FT‐IR and X‐ray photoelectron spectroscopy, and DFT calculations. PPTZ has the potential to serve as an attractive p‐type cathode material for practical applications and the facile synthesis may be also extended to other polymer cathodes based on N‐heteroaromatic units.

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Section: Resultssupporting

confidence: 90%

Section: Resultsmentioning

confidence: 76%

Section: Introductionmentioning

confidence: 99%

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Facile Synthesis of Polyphenothiazine as a High‐Performance p‐Type Cathode for Rechargeable Lithium Batteries

Wang

Han

et al. 2021

ChemSusChem

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“…The particular importance of this method is emphasized by the growing number of publications devoted to polymeric cathodes displaying outstanding electrochemical performance and obtained following nonoxidative procedures. 20,21,27,29,30 Additional exposure to oxidation with ferric chloride can significantly improve the operational characteristics of polymeric cathodes.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Facile Method for Cross-Linking Aromatic Polyamines to Engender beyond Lithium Ion Cathodes for Dual-Ion Batteries

Obrezkov

Fedina

Somova

et al. 2021

ACS Appl. Energy Mater.

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Numerous recent reports on organic-based batteries indicate an emerging interest in dual-ion batteries with polyaminebased cathodes, which are associated with outstanding rate capabilities, high specific capacities, and optimal operation voltages demonstrated by materials of this type. One of the most important and urgent tasks for this research field is the design of polyaminebased materials with advanced performance, as well as the development of methods for their preparation. In this work, a facile cross-linking approach for chemical modification of polymeric aromatic amines, which refines their cathode performance for dual-ion batteries, is presented. The precursor polymers NPDPA and PHTPA were exposed to an additional oxidative polymerization step with ferric chloride to obtain cross-linked (CL) CL-NPDPA and CL-PHTPA materials, respectively. The study of their electrochemical properties in lithium half-cells revealed improved capacities and cycling stabilities for cross-linked polymers, especially for CL-PHTPA; the values of 112.5, 102.6, and 81.1 mAh g −1 were reached under galvanostatic charging and discharging at current densities of 0.1, 1, and 10 A g −1 , respectively, thus indicating decent capacities and impressive rate capabilities. The capacity retention of 98 and 36% after 100 and 15 000 cycles, respectively, measured at a current density of 10 A g −1 showed the decent operational stability of lithium batteries. Furthermore, encouraging energy densities of 415, 425, and 211 Wh kg −1 were achieved for CL-PHTPA, while it was applied as a cathode for Na, K, and Mg half-cells, indicating the promise of polyamine materials and the presented cross-linking approach for the development of alternative battery chemistries.

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“…In 2017, we introduced poly(3-vinyl- N -methylphenothiazine) ( PVMPT ) as a positive electrode material . This was the third report of a phenothiazine-based polymer investigated as electrode material , and has been followed by other studies on different polymer architectures since then. − Phenothiazine can be reversibly oxidized to a radical cation during charge, which in PVMPT -based cells occurs at a potential of 3.5 V vs Li/Li + .…”

Section: Introductionmentioning

confidence: 99%

Bridging the Gap between Small Molecular π-Interactions and Their Effect on Phenothiazine-Based Redox Polymers in Organic Batteries

Otteny

Perner

Einholz

et al. 2021

ACS Appl. Energy Mater.

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Organic redox polymers are considered a “greener” alternative as battery electrode materials compared to transition metal oxides. Among these, phenothiazine-based polymers have attracted significant attention due to their high redox potential of 3.5 V vs Li/Li+ and reversible electrochemistry. In addition, phenothiazine units can exhibit mutual π-interactions, which stabilize their oxidized states. In poly(3-vinyl-N-methylphenothiazine) (PVMPT), such π-interactions led to a unique charge/discharge mechanism, involving the dissolution and redeposition of the polymer during cycling, and resulted in an ultrahigh cycling stability. Herein, we investigate these π-interactions in more detail and what effect their suppression by molecular design has on battery performance. Our study includes a dimeric reference compound for PVMPT, polymers with bulky tolyl or mesityl substituents on the phenothiazine units to inhibit π-interactions and alternating copolymers with maleimide groups to increase spatial distancing between phenothiazine groups. UV/vis- and electron paramagnetic resonance (EPR)-spectroscopic as well as electrochemical measurements in composite electrodes demonstrate how the unique structure of PVMPT is instrumental in obtaining a high cycling stability in poly(vinylene) derivatives of phenothiazine.

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Dihydrophenazine‐Based Copolymers as Promising Cathode Materials for Dual‐Ion Batteries

Cited by 19 publications

References 25 publications

Facile Synthesis of Polyphenothiazine as a High‐Performance p‐Type Cathode for Rechargeable Lithium Batteries

Facile Synthesis of Polyphenothiazine as a High‐Performance p‐Type Cathode for Rechargeable Lithium Batteries

Facile Method for Cross-Linking Aromatic Polyamines to Engender beyond Lithium Ion Cathodes for Dual-Ion Batteries

Bridging the Gap between Small Molecular π-Interactions and Their Effect on Phenothiazine-Based Redox Polymers in Organic Batteries

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