Electrochemical Performance Research Articles

Unveiling the CoFe LDH generated by partial in situ conversion strategy: Synergistic effect of modified MXene and cationic vacancies for overall water splitting

It remains a challenge to utilize non-precious metal electrocatalysts to increase intrinsic activity and observe more active sites. Herein, we propose a simple partial in situ transformation strategy to form a novel MOF@CoFe LDH heterostructure by Co-MOF template-directed fabrication using modified MXene as substrate, and introduce metal cation vacancy defects on the as-prepared LDH surface to further enhance the performance of the catalysts. Density-functional theory calculations show that the electron transfer rate of a material can be tuned by modulating the electron diffusion phenomenon, thereby lowering the energy barrier of the catalytic reaction. Consistent with the expected results, the catalysts also showed excellent electrochemical performance with HER and OER reaching current densities of 10 mA cm−2 with overpotentials of only 201 mV and 197 mV, and Faraday efficiencies (FE) close to 100 %. Meanwhile, a cell overpotential of only 1.56 V is required to effectively drive a current density of 10 mA cm−2 in the two-electrode system, and the superior long-term stability of the material reveals its potential for cost reduction in large-scale industrial applications.

Engineering Oxygen Vacancies in In2O3 with Enhanced Polysulfides Immobilization and Selective Catalytic Capability.

Lithium-sulfur (Li-S) battery is identified as an ideal candidate for next-generation energy storage systems in consideration of its high theoretical energy density and abundant sulfur resources. However, the shuttling behavior of soluble polysulfides (LiPSs) and their sluggish reaction kinetics severely limit the practical application of the current Li-S battery. In this work, a series of In2O3 nanocubes with different oxygen vacancy concentrations are designed and prepared via a facile self-template method. The introduced oxygen vacancy on In2O3 can effectively rearrange the charge distribution and enhance sulfiphilic property. Moreover, the In2O3 with high oxygen vacancy concentration (H-In2O3) can slightly slow down the solid-liquid conversion process and significantly accelerate the liquid-solid conversion process, thus reducing the accumulation of LiPSs in electrolyte and inhibiting the shuttle effect. Contributed by the unique selective catalytic capability, the prepared H-In2O3 exhibits excellent electrochemical performance when used as sulfur host. For instance, a high reversible capacity of 609 mAh g-1 is obtained with only 0.044% capacity decay per cycle over 1000 cycles at 1.0C. This work presents a typical example for designing advanced sulfur hosts, which is crucial for the commercialization of Li-S battery.

Organosulfur Cathodes in Lithium Metal Batteries: Bridging the Gap between Fundamentals and Practical Applications

AbstractHigh‐specific energy sulfur‐based cathodes have attracted considerable interest in lithium batteries. Organosulfur cathodes offer inherent advantages of high element abundance and an extended cycling life, aligning with the evolving requirements of future energy storage devices. Over the past decade, research efforts have been devoted to optimizing electrochemical performance through the rich and tunable molecular structures of organosulfur compounds. To further advance the fundamental research and practical application of lithium‐organosulfur batteries, a systematical analysis of the correlation between the molecular structures and electrochemical mechanisms of organosulfur cathodes is imperative. This involves deriving the key parameters at the cell level and investigating the feasibility. In this review, the thermodynamics, reaction processes, and electrochemical kinetics of organosulfur cathodes, grounded in fundamental theories of electrochemistry and materials science are discussed. Expanding the insights, comparisons among elemental sulfur, organosulfur, and n‐type organic cathodes (e.g., carbonyl cathodes) are drawn. The gap between fundamentals and practical applications targeting 500 Wh kg−1 lithium organosulfur batteries is highlighted through energy density calculations and identification of key factors affecting pouch cells. Finally, potential strategies and prospects for the overall design of advanced lithium‐organosulfur batteries are proposed, considering both theoretical foundations and practical implementations.

Fabrication and electrochemical properties of Mn, N, and S co-doped carbon fiber composite bamboo-based woodceramics electrodes

Prepared in this study, Mn, N and S co-doped woodceramics electrodes (WC@Mn-N/S) were prepared using waste bamboo as the base material, carbon fiber as the reinforcement fiber, KMnO4 and CH4N2S as dopants and activators. Mechanical analysis revealed a 68 % increase in the flexural strength of the matrix material reinforced with carbon fibers. Scanning electron microscopy observation indicated that WC@Mn-N/S retained the original natural pore structure of bamboo. The specific surface area (BET) analysis revealed that WC@Mn-N/S exhibited a specific surface area of 861.7 m2/g, with its pore size structure mainly distributed in the range of 1.3–3.8 nm. Electrochemical performance tests showed that the introduction of Mn, N and S elements endowed the bamboo-based electrode with pseudocapacitance characteristics. Additionally, the synergistic effect between these three elements imparted pseudocapacitance to the electrode material. WC@Mn-N/S performent a specific capacitance of 615 F/g, at 0.2 A/g with excellent capacitance retention (99.4 % after 5000 cycles). In the practical assembled in symmetrical capacitor the material showed high power density 500 W/kg and energy density 57.9 Wh/kg, indicating its excellent electrochemical performance.

Bimetallic Nitride Ni3Mo3N Microrods with Abundant Catalytic Sites Used as Efficient Electrocatalysts for Hydrogen Evolution Reaction

Abstract The importance of efficient and stable hydrogen evolution reaction (HER) electrocatalysts for hydrogen production in alkaline conditions to energy crisis resolution and environmental pollution is immense. In general, the quantity of catalytic sites in the electrocatalyst limits the current density of HER. In response to such problems, the bimetallic effect of non-noble bimetallic nitrides has been shown to regulate the corresponding catalytic sites. Here, a microrod-like non-noble bimetallic nitride catalyst with Ni3Mo3N microrods uniformly modified on nickel foam was synthesized by hydrothermal and nitriding processes. The catalyst showed high catalytic activity for HER in 1M KOH solution. The overpotential was only 28 mV at a current density of 10 mA·cm-2, demonstrating exceptional electrochemical performance. Furthermore, it exhibited remarkable long-term stability under the same current density. This work will open up a low-cost and simple way for the synthesis of bimetallic nitrides as functional electrode materials for HER and electrochemical detection.

3D Printed P(VdF‐HFP)/SBA‐15 composite‐based gel polymer electrolyte versus commercial celgard: A comparative investigation on thermal stability and electrochemical performance for lithium‐ion battery application

AbstractThe current work reports on tailoring of 3D printed gel polymer electrolyte (GPE) employing poly(vinylidene fluoride‐co‐hexafluoropropylene) P(VdF‐HFP) as the host matrix and mesoporous Santa Barbara Amorphous‐15 (SBA‐15) mesoporous sieve as ceramic filler. Further, this work envisages an investigation on its physicochemical properties, thermal shrinkage behavior, and electrochemical performance. An effort has been undertaken to formulate 3D printable P(VdF‐HFP)/SBA‐15 composite‐based GPE ink with suitable rheological properties. The breath figure method is followed to investigate the influence of 1‐methyl‐2‐pyrrolidinone (NMP)/tetrahydrofuran (THF) mixture as a solvent on the porosity of 3D printed GPE, through which enhanced porosity is evident from scanning electron microscopy (SEM) analysis. The morphological analysis further confirms the hybrid porous structure facilitated by the addition of SBA‐15 into the P(VdF‐HFP) matrix. The 3D printed P(VdF‐HFP)/SBA‐15 (10%) composite‐based GPE shows promising ionic conductivity in the order of 0.2 × 10−4 S/cm at room temperature and demonstrates excellent dimensional thermal stability up to 175°C. The electrochemical measurement of 3D printed GPE is tested separately using 3D printed cathode half‐cell (3D printed LFP vs. Li+) and 3D printed anode half cell (3D printed LTO vs. Li+) with GPE as separator. Further, also tested with conventionally prepared electrode and the coin cell studies show discharge capacity of 3D printed P(VdF‐HFP)/SBA‐15 (10%) composite‐based GPE is comparable to commercial celgard separator. All these features speculate that the 3D printed fabricated in the current work may find potential application in lithium‐ion battery.

Rational Regulation of High-Voltage Stability in Potassium Layered Oxide Cathodes.

Layered oxide cathode materials may undergo irreversible oxygen loss and severe phase transitions during high voltage cycling and may be susceptible to transition metal dissolution, adversely affecting their electrochemical performance. Here, to address these challenges, we propose synergistic doping of nonmetallic elements and in situ electrochemical diffusion as potential solution strategies. Among them, the distribution of the nonmetallic element fluorine within the material can be regulated by doping boron, thereby suppressing manganese dissolution through surface enrichment of fluorine. Furthermore, in situ electrochemical diffusion of fluorine from the surface into the bulk of the materials after charging reduces the energy barrier of potassium ion diffusion while effectively inhibiting irreversible oxygen loss under high voltage. The modified K0.5Mn0.83Mg0.1Ti0.05B0.02F0.1O1.9 layered oxide cathode exhibits a high capacity of 147 mAh g-1 at 50 mA g-1 and a long cycle life of 2200 cycles at 500 mA g-1. This work demonstrates the efficacy of synergistic doping and in situ electrochemical diffusion of nonmetallic elements and provides valuable insights for optimizing rechargeable battery materials.

Electro‐Induced Self‐Reduction TiO2 in Viologen‐Based Ionogels for Multi‐Color Electrochromic Displays

AbstractReflective electrochromic (EC) technology is expected to e‐paper display field, and integrating optical reflective electrolyte as the optical reflective layer is a common strategy for constructing reflective EC devices. Compositing inorganic particles and electrolytes is one of the simplest and most efficient composite methods, but these composite electrolytes usually cannot perform well together in terms of both optical and electrochemical properties. Herein, the TiO2 nanoparticles are added to the ethyl viologen‐based ionogel (T‐EVG, one typical kind of EC/electrolyte) to have the highest visible light reflectivity and the best electrochemical performance compared with SiO2, Al2O3, and ZnO nanoparticles, which is attributed to the electro‐induced self‐reduction TiO2 produced in T‐EVG during EC cycling. Meanwhile, the corresponding EC devices can display red, green, and blue, and have high optical contrast (CIE Lab: ΔE>38), fast switching spend (<4 s, the fastest is 5 Hz), ultra‐low power density (<4.0 mW cm−2), and excellent cycling stability (>85% retained after 10 000 cycles). Finally, a simple 3×3 pixelated EC display array is prepared, and single‐ and multi‐point (including diagonal points) multi‐color display effects are realized through active‐matrix driving and high‐frequency refresh, demonstrating its application value in the high‐performance e‐paper display.

Stabilizing High-Voltage Performance of Nickel-Rich Cathodes via Facile Solvothermally Synthesized Niobium-Doped Strontium Titanate.

Ni-rich layered ternary cathodes are promising candidates thanks to their low toxic Co-content and high energy density (∼800 Wh/kg). However, a critical challenge in developing Ni-rich cathodes is to improve cyclic stability, especially under high voltage (>4.3 V), which directly affects the performance and lifespan of the battery. In this study, niobium-doped strontium titanate (Nb-STO) is successfully synthesized via a facile solvothermal method and used as a surface modification layer onto the LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode. The results exhibited that the Nb-STO modification significantly improved the cycling stability of the cathode material even under high-voltage (4.5 V) operational conditions. In particular, the best sample in our work could provide a high discharge capacity of ∼190 mAh/g after 100 cycles under 1 C with capacity retention over 84% in the voltage range of 3.0-4.5 V, superior to the pristine NCM811 (∼61%) and pure STO modified STO-811-600 (∼76%) samples under the same conditions. The improved electrochemical performance and stability of NCM811 under high voltage should be attributed to not only preventing the dissolution of the transition metals, further reducing the electrolyte's degradation by the end of charge, but also alleviating the internal resistance growth from uncontrollable cathode-electrolyte interface (CEI) evolution. These findings suggest that the as-synthesized STO with an optimized Nb-doping ratio could be a promising candidate for stabilizing Ni-rich cathode materials to facilitate the widespread commercialization of Ni-rich cathodes in modern LIBs.

Centrifugal-Gravity-Enforced Deposition of MXene Electrodes for High-Performance and Ultrastable Microsupercapacitors.

Two-dimensional (2D) transition metal carbides, known as MXenes, have captured much attention for their excellent electrical conductivity and electrochemical capability. However, the susceptibility of MXenes to oxidation, particularly Ti3C2Tx transforming into titanium dioxide upon exposure to ambient air, hinders their utilization for extended operational life cycles. This work introduces a simple and straightforward method for producing ultrathin MXene electrode films tailored for energy storage applications, employing centrifugal-gravity force. Our approach significantly suppresses the oxidation phenomenon that arises in MXene materials and also effectively prevents the recrystallization of potentially residual LiF during the film formation. Additionally, the utilization of this MXene electrode in an all-solid-state microsupercapacitor (MSC) with an interdigitated pattern demonstrates an exceptionally improved and stable electrochemical performance. This includes a high volumetric capacitance of approximately 467 F cm-3, an energy density of around 65 mWh cm-3, and impressive long-term cycle stability, retaining about 94% capacity after 10 000 cycles. Moreover, a downsized MSC device exhibits remarkable mechanical durability, retaining over 98% capacity even when folded and sustaining stability over extended periods. Therefore, we believe that this study provides valuable insights for advancing highly integrated energy storage devices, ensuring exceptional electrochemical efficiency and prolonged functionality in diverse environments, whether ambient or humid.

Boosting Supercapacitor Efficiency with Amorphous Biomass-Derived C@TiO2 Composites.

Carbon materials are readily available and are essential in energy storage. One of the routes used to enhance their surface area and activity is the decoration of carbons with semiconductors, such as amorphous TiO2, for application in energy storage devices. This work reports the preparation of amorphous TiO2 nanopowders, which were obtained through the anodization of titanium in ethaline media. The obtained amorphous TiO2 was used to obtain TiO2-decorated carbon (obtained through the carbonization of glycogen precursor from mussel cooking wastewater, under N2 atmosphere) composites through three different methods: electrochemical in-situ attachment of TiO2 nanopowders to the carbon matrix using ultrasounds and sonication in ethaline. Commercial TiO2 was used as the comparison material. Morphology, composition, and structure analysis were performed, followed by the electrochemical analysis in ethaline electrolyte. The in-situ attachment of amorphous TiO2 to the carbon matrix shows the most promising electrochemical performance of 956 F g-1 at 1 A g-1 for the three-electrode cell setup, with 100% and 98% capacitance retention after 1000 and 10000 cycles. On a two-electrode symmetric solid-state electrolyte cell, the gravimetric capacitance is 1251 F g-1, at 1 A g-1, with 90% and 78% capacitance retention after 1000 and 10000 cycles, respectively.

Multiple phase transformation of ZIF-L to LDH and Ag nanoparticles decorated on CoNi layered double hydroxides for high-performance supercapacitor and highly efficient hydrogen evolution reaction

ZIF-L-derived binary layered double hydroxide (LDH) established active catalysts have been shown to have potential as electrode materials in the development of high-performance supercapacitors (SCs) and hydrogen evaluation reactions (HER). This study uses conductive nano-silver (Ag) particles in hierarchically integrated CoNi-LDH nanosheets (NSs), which are described. The developed Ag@CoNi-LDH NSs electrode has a very high specific capacitance of 2878 F g−1 at 0.5 A g−1 and an impressive rate capability. This is due to consistent morphology, plentiful electroactive sites, homogeneous particle size, and decreased electronic/ionic impedance. The fabrication of solid-state hybrid supercapacitors (HSCs) using Ag@CoNi-LDH NSs as the positive electrode and activated carbon (AC) as the negative electrode in PVA/KOH polymer gel electrolytes has been described. The prepared supercapacitors achieve a maximum energy density of 105 Wh kg−1 at power densities of 1183 Wh kg−1, coupled with excellent initial capacitance retentions of 97 % after 20,000 cycles. Ag@CoNi-LDH NSs demonstrate effective electrocatalytic activity towards HER with an ultra-low overpotential of 26 mV at 10 mA cm−2 and the associated Tafel value of 35 mV dec−1 using 0.5 M acidic electrolyte. It is possible to attribute the extraordinary electrochemical performance to the thoughtful mixture of two electroactive materials in the future.

Cation-polymerized artificial SEI layer modified Li metal applied in soft-matter polymer electrolyte.

Li metal batteries with polymer electrolyte are of great interest for next-generation batteries for high safety and high energy density. However, uneven deposition on the lithium metal surface can greatly affect battery life. Therefore, surface modification on the Li metal become necessary to achieve good performance. Herein, an artificial solid electrolyte interface (SEI) modified lithium metal anode is prepared using cation-polymerization process, as triggered by PF5 generated from CsPF6. As a result, the polarization voltage of Li||Li symmetric battery assembled with artificial SEI-modified Li metal anode was stable with a small over-potential of 25 mV after 3000 h at current density of 1.5 mA cm-2. Electrochemical performance of Li||NCM 622 (LiNi0.6Co0.2Mn0.2O2) full cell with soft-matter polymer electrolyte is significantly improved than bare Li-metal, the capacity retention is 75% after 120 cycles with N/P=3:1 at a cut-off voltage of 4.3 V. Our work has shed lights on the commercialization of Li metal battery with polymer electrolyte.

Binder-free all-carbon composite supercapacitors

Carbon-based electrode materials have widely been used in supercapacitors. Unfortunately, the fabrication of the supercapacitors includes a polymeric binding material that leads to an undesirable addition of weight along with an increased charge transfer resistance. Herein, binder-free and lightweight electrodes were fabricated using powder processing of carbon nanofibers (CNFs) and graphene nanoplatelets (GNPs) resulting in a hybrid all-carbon composite material. The structural, morphological, and electrochemical properties of the composite electrodes were studied at different concentrations of GNPs. The specific capacitance (Cs) of the CNFs/GNPs composite was improved by increasing the concentration of GNPs. A maximum Cs of around 120 F g−1 was achieved at 90 wt% GNPs which is around 5-fold higher in value than the pristine CNFs in 1 M potassium hydroxides (KOH), which then further increased to 189 F g−1 in 6 M KOH electrolyte. The energy density of around 20 Wh kg−1 with the corresponding power density of 340 W kg−1 was achieved in the supercapacitor containing 90 wt% GNPs. The enhanced electrochemical performance of the composite is related to the presence of a synergistic effect and the CNFs establishing conductive/percolating networks. Such binder-free all-carbon electrodes can be a potential candidate for next-generation energy applications.

Ultrafast and selective detection of dopamine by DC sputtered highly oriented CuO thin films: Effect of electroactive interfering agents and temperature

Dopamine and serotonin are two neurotransmitters that play critical role in human physiology. In this work, it has been aimed to synthesize a chip-based sensing platform that can detect dopamine precisely in a non-enzymatic way in presence of a series of electroactive interfering agents. Copper oxide (CuO), a p-type material with excellent surface and electrochemical properties, has been deposited through direct current (DC) sputtering technique on indium doped tin oxide (ITO) coated glass substrates as the sensing platform. The structure, phase purity and other essential properties of the modified electrode were established through x-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR) and ultraviolet – visible (UV–Vis) spectroscopy. Detailed electrochemical investigations with the modified electrode have also been carried out using cyclic voltammetry (CV), chronoamperometry (i – t) and electrochemical impedance spectroscopy (EIS) that revealed ultrafast response (10 ms), excellent sensitivity (5.41 µAµM-1cm−2) and low limit of detection (LoD) of 0.46 µM for the electrode towards dopamine. The electrode exhibited sensitivity of 0.37 µAµM-1cm−2 with average LoD of 19.2 µM towards serotonin, which is inferior to dopamine. The threshold response potential was also quite different for dopamine and serotonin. The modified electrode was also found to be nonresponsive to a series of electroactive interfering agents, making it dopamine selective. The role of p-type conductivity of the electrode material towards such selective detection of dopamine was also explained. The electrode was notably reliable from the point of view of electrochemical performance and structural stability. Real sample analysis was also carried out by taking urine sample from adult male human.

Layer‑by‑layer assembled binder-free hydrated vanadium oxide-acetylene black electrode for flexible aqueous zinc ion battery

Vanadium oxides are potential positive electrode materials for aqueous zinc ion batteries (ZIBs) owing to their advantages of high theoretical capacity, low cost, and so on. Developments of methods for preparing binder-free vanadium oxide electrodes on a large scale and further investigation of their Zn2+ storage mechanisms are essential for expanding their uses in large-scale energy storage systems and wearable electronics. In this work, binder-free electrodes with hydrated vanadium oxide (V2O5·nH2O, denoted as VOH)-acetylene black (AB) on carbon cloth (VOH-AB/CC) are fabricated by a simple and scalable method which combined low-temperature hydrothermal treatment with layer-by-layer drop/spray-coating process. The AB can greatly improve the electrical conductivity of VOH, thereby enhancing the electrochemical performance. The as-prepared electrode with 20 wt% of AB (VOH-AB2/CC) delivers a high capacity of 280 mA h g−1 at 1 A/g and a good rate capability of 205 mA h g−1 at 4 A/g, which is better than many of the reported binder-free vanadium base electrodes. Besides, excellent cycling performance with 89 % retention rate after 3000 cycles at 4 A/g is achieved on the VOH-AB2/CC electrode. Furthermore, a storage mechanism of Zn2+/H+/H2O insertion accompanied by the formation of basic zinc salt precipitate during the discharging process is proposed by the aid of ex-situ XRD and XPS techniques. Additionally, the flexible Quasi-Solid-State ZIB constructed using VOH-AB/CC as positive electrode can work well at different bending states and two ZIBs connected in series can lighten a light-emitting diode even under bending state. This work provides a low-cost, time-saving, environmental-friendly and scalable method to fabricate binder-free hydrated vanadium oxide electrodes for flexible aqueous ZIBs.

Synthesis of monodisperse hollow carbon spheres and their electrochemical performance as anodes in potassium-ion batteries

Synthesis of monodisperse hollow carbon spheres and their electrochemical performance as anodes in potassium-ion batteries

Gaining insight into lithium-ion battery degradation by a calorimetric approach

With the growing demand for lithium-ion batteries (LIBs) in transportation and renewable energy sectors, ensuring reliability and mitigating degradation are crucial challenges for their widespread deployment. This study investigates the relationship between thermal characteristics and degradation/reliability by developing an in-situ heat measurement methodology for LIBs operating under grid services. Using adiabatic mode-based calorimetry, we determine the thermal behavior of two commercial cells with distinct cathode chemistries (Ni-rich layered oxide and olivine) before and after two years of peak shaving operation and demonstrate a strong correlation between thermal characteristics and electrochemical performance and its degradation. By further analyzing the heat sources separation and differentiating between irreversible and reversible heat, we disclose the underlying degradation mechanisms of LIBs. These findings emphasize the critical role of thermal characteristics in determining LIB reliability and degradation, while the obtained heat data can aid in the development and calibration of LIB state-of-health models for grid applications.

Zn-Doped MnO2 microflake pseudocapacitive cathode on Ni(OH)2/Ni-Foam substrate as a promising charge storage material

Zn-doped MnO2 microflakes cathode material on Ni(OH)2/Ni foam has been synthesized and characterized as well as tested its electrochemical performances in 3 M KOH solution. The present work varies the amounts of Zn dopant in MnO2 system to improve its capability in energy storage. Material identification has been simply confirmed with XRD, SEM, TEM, and XPS analysis. It is expected the Zn dopant will induce surface defects such as ZnMn2- or ZnMn0 and oxygen vacancy, leading to enhanced charge storage efficiency. In addition, XPS analysis reveals the existence of positively charged oxygen vacancy and the surface charge of ZnMn2- or ZnMn0 induce different surface oxidation states of Mn2+ and Mn4+. The oxidation states of Mn could accommodate the redox reactions involving ion adsorption and intercalation during pseudocapacitive charge and discharge processes. Substituting Zn into Mn sites is optimized with MnZn-1.5 which reaches a specific capacitance of 1601F/g at a 0.4 VAg/AgCl in KOH solution. This work demonstrates a promising material system for supercapacitor applications using Zn doping with a simple preparation process to support a large-scale application.

Multifaceted effects of ring fusion on the stability of charged dialkoxyarene redoxmers

Due to their almost unlimited scalability, redox flow batteries can make versatile and affordable energy storage systems. Redox active materials (redoxmers) in these batteries largely define their electrochemical performance, including the life span of the battery that depends on the stability of charged redoxmers. In this study, we examine the effects of expanding the π-system in the arene rings on the chemical stability of dialkoxyarene redoxmers that are used to store positive charge in RFBs. When 1,4-dimethoxybenzene is π-extended to 1,4-dimethoxynaphthalene, a lower redox potential, improved kinetic stability, and longer cycling life are observed. However, when an additional ring is fused to make 9,10-dimethoxyanthracene, the radical cation undergoes rapid O-dealkylation possibly due to increased steric strain that drives methoxy out of the arene plane thus breaking the π-conjugation with O 2p orbitals. On the other hand, the planar structure of 1,4-dimethoxynaphthalene may facilitate second-order reactions of radical cations leading to their neutralization in the bulk. Our study suggests that extending the π-system changes reactivity in multiple (sometimes, opposite) ways, so lowering the oxidation potential through π-conjugation to improve redoxmer stability should be pursued with caution.