Person: De Porcellinis, Diana
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De Porcellinis
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Diana
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De Porcellinis, Diana
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Publication A High Voltage Aqueous Zinc–Organic Hybrid Flow Battery(Wiley, 2019-05-17) Aziz, Michael; Park, Minjoon; Kerr, Emily; De Porcellinis, Diana; Beh, Eugene S.; Fell, Eric M.; Jing, Yan; Wong, Andrew; Goulet, Marc-Antoni; Ryu, Jaechan; Gordon, Roy G.; Cho, JaephilWater‐soluble redox‐active organic molecules have attracted extensive attention as electrical energy storage alternatives to redox‐active metals that are low in abundance and high in cost. Here an aqueous zinc–organic hybrid redox flow battery (RFB) is reported with a positive electrolyte comprising a functionalized 1,4‐hydroquinone bearing four (dimethylamino)methyl groups dissolved in sulfuric acid. By utilizing a three‐electrolyte, two‐membrane configuration this acidic positive electrolyte is effectively paired with an alkaline negative electrolyte comprising a Zn/[Zn(OH)4]2− redox couple and a hybrid RFB is operated at a high operating voltage of 2.0 V. It is shown that the electrochemical reversibility and kinetics of the organic redox species can be enhanced by an electrocatalyst, leading to a cyclic voltammetry peak separation as low as 35 mV and enabling an enhanced rate capability.Publication Effect of Molecular Structure of Quinones and Carbon Electrode Surfaces on the Interfacial Electron Transfer Process(American Chemical Society (ACS), 2020-01-28) De Porcellinis, Diana; Jing, Yan; Kerr, Emily; Mejia-Mendoza, Luis Martin; Vazquez-Mayagoitia, Álvaro; Aspuru-Guzik, Alán; Sedenho, Graziela Cristina; Gordon, Roy; Crespilho, Frank; Aziz, MichaelQuinones can undergo thermodynamically reversible proton-coupled electron transfer reactions and are being applied as electroactive compounds in aqueous organic batteries. However, the electrochemical reversibility of these compounds is affected not only by their molecular structure but also by the properties of a carbon-based electrode surface. This study combines experimental and theoretical approaches to understand this dependence. We study the electron transfer kinetics of two synthesized quinone derivatives and two commercially available ones with a glassy carbon, a highly ordered pyrolytic graphite, and a high-edge-density graphite electrode (HEDGE). The electrochemical reversibility is notably improved on the HEDGE, which shows a higher density of defects and presents oxygenated functional groups at its surface. The electron transfer kinetics are controlled by adsorbed species onto the HEDGE. Molecular dynamics simulation and quantum mechanics calculations suggest defects with oxygen-containing functional groups, such as C–O and C═O, on HEDGE surfaces drive the interaction with the functional groups of the molecules, during physisorption from van der Waals forces. The presence of sulfonic acid side groups and a greater number of aromatic rings in the molecular structure may contribute to a higher stabilization of quinone derivatives on HEDGEs. We propose that high-performance carbon-based electrodes can be obtained without catalysts for organic batteries, by the engineering of carbon-based surfaces with edge-like defects and oxygenated functional groups.Publication Non-corrosive, Low-Toxicity Gel-based Microbattery from Organic and Organometallic Molecules(Royal Society of Chemistry (RSC), 2019) Crespilho, Frank; Sedenho, Graziela Cristina; De Porcellinis, Diana; Kerr, Emily; Granados-Focil, Sergio; Gordon, Roy; Aziz, MichaelMicrobatteries with safe, non-corrosive electrolyte chemistries can have an immediate positive impact on modern life applications, such as ingestible electronic pills and system-on-chip bioelectronics. Here a safe, non-corrosive and non-flammable microbattery is reported. A natural agarose hydrogel is the electrolyte-supporting matrix, and organic and organometallic molecules are the redox-active species. This device can safely meet the needs of ingestible medical microdevices as a primary battery. Additionally, this redox gel system can be used as a secondary battery for on-chip electronics applications, potentially enabling safe and cost-effective small-scale energy storage.Publication A Phosphonate‐Functionalized Quinone Redox Flow Battery at Near‐Neutral pH with Record Capacity Retention Rate(Wiley, 2019-02-06) Ji, Yunlong; Goulet, Marc-Antoni; Pollack, Daniel; Kwabi, David; Jin, Shijian; De Porcellinis, Diana; Kerr, Emily; Gordon, Roy; Aziz, MichaelA highly stable phosphonate‐functionalized anthraquinone is introduced as the redox‐active material in a negative potential electrolyte (negolyte) for aqueous redox flow batteries operating at nearly neutral pH. The design and synthesis of 2,6‐DPPEAQ, (((9,10‐dioxo‐9,10‐dihydroanthracene‐2,6‐diyl)bis(oxy))bis(propane‐3,1‐diyl))bis(phosphonic acid), which has a high solubility at pH 9 and above, is described. Chemical stability studies demonstrate high stability at both pH 9 and 12. By pairing 2,6‐DPPEAQ with a potassium ferri/ferrocyanide positive electrolyte across an inexpensive, nonfluorinated permselective polymer membrane, this near‐neutral quinone flow battery exhibits an open‐circuit voltage of 1.0 V and a capacity fade rate of 0.00036% per cycle and 0.014% per day, which is the lowest ever reported for any flow battery in the absence of rebalancing processes. It is further demonstrated that the negolyte pH drifts upward upon atmospheric oxygen penetration but, when oxygen is excluded, oscillates reversibly between 9 and 12 during cycling. These results enhance the suitability of aqueous‐soluble redox‐active organics for use in large‐scale energy storage, potentially enabling massive penetration of intermittent renewable electricity.Publication A High Voltage Aqueous Zinc–Organic Hybrid Flow Battery(Wiley, 2019-05-17) Park, Minjoon; Beh, Eugene S.; Fell, Eric; Jing, Yan; Kerr, Emily; De Porcellinis, Diana; Goulet, Marc‐Antoni; Ryu, Jaechan; Wong, Andrew A.; Gordon, Roy; Cho, Jaephil; Aziz, MichaelWater‐soluble redox‐active organic molecules have attracted extensive attention as electrical energy storage alternatives to redox‐active metals that are low in abundance and high in cost. Here an aqueous zinc–organic hybrid redox flow battery (RFB) is reported with a positive electrolyte comprising a functionalized 1,4‐hydroquinone bearing four (dimethylamino)methyl groups dissolved in sulfuric acid. By utilizing a three‐electrolyte, two‐membrane configuration this acidic positive electrolyte is effectively paired with an alkaline negative electrolyte comprising a Zn/[Zn(OH)4]2− redox couple and a hybrid RFB is operated at a high operating voltage of 2.0 V. It is shown that the electrochemical reversibility and kinetics of the organic redox species can be enhanced by an electrocatalyst, leading to a cyclic voltammetry peak separation as low as 35 mV and enabling an enhanced rate capability.Publication Alkaline Quinone Flow Battery with Long Lifetime at pH 12(Elsevier BV, 2018-09) Kwabe, David G.; Ji, Yunlong; Lin, Kaixiang; Kerr, Emily F.; Goulet, Marc-Antoni; De Porcellinis, Diana; Tabor, Daniel P.; Pollack, Daniel A.; Aspuru-Guzik, Alán; Gordon, Roy; Aziz, MichaelWe demonstrate a long-lifetime, aqueous redox-flow battery that can operate at a pH as low as 12 while maintaining an open-circuit voltage of over 1 V. We functionalized 2,6-dihydroxyanthraquinone (2,6-DHAQ) with highly alkali-soluble carboxylate terminal groups. The resulting negative electrolyte material 4,4′-((9,10-anthraquinone-2,6-diyl)dioxy)dibutyrate (2,6-DBEAQ) was six times more soluble than 2,6-DHAQ at pH 12. Symmetric cell cycling with 2,6-DBEAQ on both sides of the cell demonstrates a capacity fade rate of <0.01%/day and <0.001%/cycle. By pairing 2,6-DBEAQ with a potassium ferri-/ferrocyanide positive electrolyte and utilizing a non-fluorinated membrane, this near-neutral flow battery shows a capacity fade rate that is the lowest of any quinone and rivals the lowest ever reported for any flow battery in the absence of rebalancing processes. This result adds the important attribute of long calendar life to quinone-based redox-flow batteries, which may enable massive penetration of intermittent renewable electricity.Publication Flow Batteries: Alkaline Benzoquinone Aqueous Flow Battery for Large-Scale Storage of Electrical Energy(Wiley-Blackwell, 2018) Yang, Zhengjin; Tong, Liuchuan; Tabor, Daniel; Beh, Eugene S.; Goulet, Marc-Antoni; De Porcellinis, Diana; Aspuru-Guzik, Alan; Gordon, Roy; Aziz, MichaelWe introduce an aqueous flow battery based on low-cost, non-flammable, non-corrosive and Earth-abundant elements. During charging, electrons are stored in a concentrated water solution of 2,5-dihydroxy-1,4-benzoquinone (DHBQ), which rapidly receives electrons with inexpensive carbon electrodes without the assistance of any metal electro-catalyst. Electrons are withdrawn from a second water solution of a food additive, potassium ferrocyanide (K4Fe(CN)6). When these two solutions flow along opposite sides of a cation-conducting membrane, this flow battery delivers a cell potential of 1.21 V, a peak galvanic power density of 300 mW/cm2 and a coulombic efficiency exceeding 99%. Continuous cell cycling at 100 mA/cm2 shows a capacity retention rate of 99.76%/cycle over 150 cycles. Various molecular modifications involving substitution for hydrogens on the aryl ring were implemented to block decomposition by nucleophilic attack of hydroxide ions in solution. These modifications resulted in increased capacity retention rates of up to 99.962%/cycle over 400 consecutive cycles, accompanied by changes in voltage, solubility, kinetics and cell resistance. Quantum chemistry calculations of a large number of organic compounds predicted a number of related structures that should have even higher performance and stability. Flow batteries based on alkaline-soluble dihydroxybenzoquinones and derivatives are promising candidates for large-scale, stationary-storage of electrical energy.Publication A Neutral pH Aqueous Organic–Organometallic Redox Flow Battery with Extremely High Capacity Retention(American Chemical Society (ACS), 2017) Beh, Eugene; De Porcellinis, Diana; Gracia, Rebecca; Xia, Kay; Gordon, Roy; Aziz, MichaelWe demonstrate an aqueous organic and organometallic redox flow battery utilizing reactants composed of only earth-abundant elements and operating at neutral pH. The positive electrolyte contains bis((3-trimethylammonio)propyl)ferrocene dichloride, and the negative electrolyte contains bis(3trimethylammonio)propyl viologen tetrachloride; these are separated by an anion-conducting membrane passing chloride ions. Bis(trimethylammoniopropyl) functionalization leads to ∼2 M solubility for both reactants, suppresses higher-order chemical decomposition pathways, and reduces reactant crossover rates through the membrane. Unprecedented cycling stability was achieved with capacity retention of 99.9943%/cycle and 99.90%/ day at a 1.3 M reactant concentration, increasing to 99.9989%/ cycle and 99.967%/day at 0.75−1.00 M; these represent the highest capacity retention rates reported to date versus time and versus cycle number. We discuss opportunities for future performance improvement, including chemical modification of a ferrocene center and reducing the membrane resistance without unacceptable increases in reactant crossover. This approach may provide the decadal lifetimes that enable organic−organometallic redox flow batteries to be cost-effective for grid-scale electricity storage, thereby enabling massive penetration of intermittent renewable electricity.Publication A Water-Miscible Quinone Flow Battery with High Volumetric Capacity and Energy Density(American Chemical Society (ACS), 2019) Jin, Shijian; Jing, Yan; Kwabi, David; Ji, Yunlong; Tong, Liuchuan; De Porcellinis, Diana; Goulet, Marc-Antoni; Pollack, Daniel A.; Gordon, Roy; Aziz, MichaelA water-miscible anthraquinone with polyethylene glycol (PEG)-based solubilizing groups is introduced as the redox-active molecule in a negative electrolyte (negolyte) for aqueous redox flow batteries, exhibiting the highest volumetric capacity among aqueous organic negolytes. We synthesized and screened a series of PEG-substituted anthraquinones (PEGAQs) and carefully studied one of its isomers, namely 1,8-bis(2-(2-(2- hydroxyethoxy)ethoxy)ethoxy)anthracene-9,10-dione (AQ-1,8-3E-OH), which has high electrochemical reversibility and is completely miscible in water of any pH. A negolyte containing 1.5 M AQ-1,8-3E-OH, when paired with a ferrocyanide-based positive electrolyte across an inexpensive, non-fluorinated permselective polymer membrane at pH 7, exhibits an open-circuit potential of 1.0 V, a volumetric capacity of 80.4 Ah/L, and an energy density of 25.2 Wh/L.Publication Molecular Engineering of an Alkaline Naphthoquinone Flow Battery(American Chemical Society (ACS), 2019-07-11) Tong, Liuchuan; Goulet, Marc-Antoni; De Porcellinis, Diana; Kerr, Emily; Fell, Eric; Aspuru-Guzik, Alan; Gordon, Roy; Aziz, Michael; Tabor, DanielAqueous organic redox flow batteries (AORFBs) have recently gained significant attention as a potential candidate for grid-scale electrical energy storage. Successful implementation of this technology will require redox-active organic molecules with many desired properties. Here we introduce a naphthoquinone dimer, bislawsone, as the redox-active material in a negative potential electrolyte (negolyte) for an AORFB. This novel dimerization strategy substantially improves the performance of the electrolyte vs. that of the lawsone monomer in terms of solubility, stability, reversible capacity, permeability and cell voltage. An AORFB pairing bislawsone with a ferri/ferrocyanide positive electrolyte delivers an open-circuit voltage of 1.05 V and cycles at a current density of 300 mA/cm2 with a negolyte concentration of 2 M electrons in alkaline solution. We determined the degradation mechanism for the naphthoquinone-based electrolyte using chemical analysis, and predict theoretically electrolytes based on naphthoquinones that will be even more stable.