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  • 1
    In: Electrochimica Acta, Elsevier BV, Vol. 275 ( 2018-06), p. 225-235
    Type of Medium: Online Resource
    ISSN: 0013-4686
    Language: English
    Publisher: Elsevier BV
    Publication Date: 2018
    detail.hit.zdb_id: 1483548-4
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  • 2
    In: ChemElectroChem, Wiley, Vol. 7, No. 3 ( 2020-02-03), p. 672-683
    Abstract: Fundamental charge‐transfer dynamics for technologically relevant carbons, such as disordered “hard” carbons, can be studied by designing planar mimics. We fabricate thin films of “pyrolytic carbon” (pyC) by decomposition of benzene at 1000 °C and examine the physical and electrochemical properties of the native pyC film, as well as variants after heteroatom doping, plasma oxidation, and metal nanoparticle modification. The pyC films are optically reflective at the macroscale, relatively planar (1–3 nm RMS roughness by atomic force microscopy) and disordered (via Raman scattering). Thiophenyl‐doped pyC films (0.6–1.7 atom % sulfur) suitably mimic the disorder, chemical state (X‐ray photoelectron spectroscopy), and work function (Kelvin probe) of a workhorse carbon black, Vulcan XC‐72. Using ferri/ferrocyanide as a redox probe, we find that oxygen functionalities enhance the heterogeneous electron‐transfer rate constant up to 3×, while high levels of sulfur dopants decrease the rate 2×. We also explore thiophenyl‐directed adsorption of Au nanoparticles and show that hydrogen evolution at 0.1 mA cm −2 occurs ∼95 mV more positive at 〈 1 % Au@pyC∼S than at pyC∼S.
    Type of Medium: Online Resource
    ISSN: 2196-0216 , 2196-0216
    URL: Issue
    Language: English
    Publisher: Wiley
    Publication Date: 2020
    detail.hit.zdb_id: 2724978-5
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  • 3
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2018-02, No. 3 ( 2018-07-23), p. 133-133
    Abstract: Manganese oxides (MnO x ) are a well-established class of active materials for electrochemical energy-storage technologies ranging from primary alkaline cells to rechargeable Li-ion batteries. More recently, the use of manganese oxides has extended to aqueous-electrolyte electrochemical capacitors (ECs) in which nanostructured forms of MnO x exhibit pseudocapacitive charge-storage behavior that can be tapped for pulse-power applications. The ability of MnO x to alternately express battery-like and capacitor-like functionality offers intriguing prospects to design electrode materials and corresponding devices that deliver both high energy content and rapid charge/discharge response. We are exploring such opportunities with electrode architectures comprising nanoscale MnO x coatings affixed to porous carbon frameworks [1,2,3]. The battery- and capacitor-like character of these materials can be tuned by varying such factors as the oxide crystal structure (layered birnessite-MnO x vs. cubic spinel LiMn 2 O 4 ) and the composition of the contacting electrolyte (mixtures of Na + , Li + , and/or Zn 2+ ) [4]. To deconvolve the complex electrochemical response of such systems, we apply a suite of electroanalytical methods that are based on voltammetry and impedance. The 3D projection of Bode-plot parameters has proven particularly useful in mapping frequency-dependent capacitance contributions onto the potential scale, revealing mechanisms that deliver/store charge at high rates. In parallel with investigations of macroscale electrode architectures, we also examine simplified 2D MnO x //carbon interfaces where surface-sensitive characterization methods (X-ray photoelectron spectroscopy, scanning-probe microscopy) provide insights on the impact of the carbon substrate on charge-transfer kinetics, charge-storage mechanisms, and stability. E. Fischer, K.A. Pettigrew, D.R. Rolison, R.M. Stroud, and J.W. Long, Nano Letters 2007 , 7 , 281–286. W. Long, M.B. Sassin, A.E. Fischer, and D.R. Rolison, J. Phys. Chem. C 2009 , 113 , 17595–17598. B. Sassin, S.G. Greenbaum, P.E. Stallworth, A.N. Mansour, B.P. Hahn, K.A. Pettigrew, D.R. Rolison, and J.W. Long, J. Mater. Chem. A 2013 , 1 , 2431–2440. S. Ko, M.B. Sassin, J.F. Parker, D.R. Rolison, and J.W. Long, Sustainable Energy Fuels , 2018 , 2 , 626–636.
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2018
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  • 4
    Online Resource
    Online Resource
    The Electrochemical Society ; 2019
    In:  ECS Meeting Abstracts Vol. MA2019-02, No. 6 ( 2019-09-01), p. 511-511
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2019-02, No. 6 ( 2019-09-01), p. 511-511
    Abstract: Hard (non-graphitizable) carbon has emerged as a prospective charge-storage material for negative electrodes in sodium-ion batteries, yet reported electrochemical performance across this broad category of carbons varies widely. Such discrepancies arise in part due to the multiple distinct sodiation reactions that are possible with disordered carbon electrodes, whereby sodium ions can be stored in defect sites, graphitic layers, and/or micropores depending on the pore–solid architecture, surface chemistry, and solid-state structure of a particular carbon. To address both fundamental questions and practical application in Na-ion batteries, we are investigating carbon nanofoam papers (CNFPs), synthesized by infiltrating the voids of carbon-fiber paper with resorcinol–formaldehyde (R–F) formulations to form porous polymer nanofoam that is subsequently converted to the conductive carbon analog via pyrolysis at 1000°C [1]. When tested as free-standing electrode architectures in Na-ion cells, CNFPs deliver specific capacity 〉 300 mAh g –1 at a 1C rate and 〉 250 mAh g –1 at 10C, with a first-cycle Coulombic efficiency near 85% under galvanostatic operation. The galvanostatic intermittent titration technique (GITT) confirms that Na-ion diffusion is facile in the defect-mediated charge-storage regime. We attribute these favorable properties to the high defect concentration in the disordered R–F-derived carbon domains, the 3D-interconnected porosity within the carbon nanofoam, and the absence of otherwise-necessary binder and conductive additives that are commonly used in conventional powder-composite electrodes. Our results demonstrate the utility of CNFPs as device-ready, self-supported electrodes and advance the design of related carbon materials for next-generation Na-ion batteries. [1] J.C. Lytle, J.M. Wallace, M.B. Sassin, A.J. Barrow, J.W. Long, J.L. Dysart, C.H. Renninger, M.P. Saunders, N.L. Brandell, and D.R. Rolison, Energy Environ. Sci. , 4 (2011) 1913–1925.
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2019
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  • 5
    Online Resource
    Online Resource
    The Electrochemical Society ; 2020
    In:  ECS Meeting Abstracts Vol. MA2020-02, No. 3 ( 2020-11-23), p. 560-560
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2020-02, No. 3 ( 2020-11-23), p. 560-560
    Abstract: We recently demonstrated that advanced multifunctional 3D MnO x @carbon nanofoam (MnO x @CNF) electrodes cycled in mixed-salt aqueous electrolytes [1] extend the performance advantages of rechargeable “zinc-ion” batteries, an emerging energy-storage technology with inherent cost and safety benefits. [2] , [3] The combination of the multifunctional birnessite-MnO x @CNF and mild-pH Zn 2+ -containing electrolyte results in a complex charge-storage mechanism in which a H + inserts into the birnessite-MnO x during discharge, resulting in an increase in the local pH that triggers precipitation of Zn 4 (OH) 6 SO 4 ·5H 2 O, while Na-ions support pseudocapacitance reactions. [4] This dual charge-storage mechanism yields high capacity at low rates (308 mA h g -1 at 1C, MnO x theoretical capacity) and pulse power at high rates (100 mA h g -1 at 20C) via pseudocapacitance; these mechanisms are reversible over hundreds of cycles, attributed in part to the through-connected pore structure of the CNF. In order to explore the efficacy of other MnO x polymorphs in such 3D multifunctional electrode designs, we developed an “in-place” conversion to generate nanocrystalline ZnMn 2 O 4 spinel from the birnessite-MnO x coating on the CNF. Crystallization is achieved by heating at relatively mild temperatures (300°C), such that the nanoscale morphology of the original MnO x coating and through-connected pore structure of the underlying CNF are maintained. We used a suite of ex-situ characterization methods (SEM/EDS, XRD, XPS) to elucidate the charge-storage reaction of ZnMn 2 O 4 @CNF in 1 M ZnSO 4 and found that it is even more complex than the charge-storage mechanism of birnessite-MnO x @CNF. Discharge of ZnMn 2 O 4 @CNF proceeds via two steps, the first occurring by Zn 2+ insertion into the spinel and the second by H + insertion accompanied by Zn 4 (OH) 6 SO 4 ·5H 2 O precipitation; the reaction reverses upon recharge. We will discuss the implications of these mechanisms for such performance characteristics as rate capability and cycle life in their ultimate application as positive electrodes in next-generation zinc-ion batteries. [1] . J.S. Ko, M.B. Sassin, J.F. Parker, D.R. Rolison, and J.W. Long: Combining battery-like and pseudocapacitive charge storage in 3D MnO x @carbon electrode architectures for zinc-ion cells. Sustainable Energy Fuels 2 , 626–636 (2018). [2] . B. Tang, L. Shan, S. Liang, and J. Zhou: Issues and opportunities facing aqueous zinc-ion batteries. Energy Environ. Sci . 12 , 3288–3304 (2019). [3] . L. E. Blanc , D. Kundu , and L. F. Nazar : Scientific Challenges for the Implementation of Zn-Ion Batteries. Joule 4 , 771–799 (2020). [4] . J.S. Ko, M.D. Donakowski, M.B. Sassin, J.F. Parker, D.R. Rolison, and J.W. Long: Deciphering charge-storage mechanisms in 3D MnO x @carbon electrode nanoarchitectures for rechargeable zinc-ion cells. MRS Communications 9 , 99–106 (2019).
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2020
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  • 6
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2019-01, No. 2 ( 2019-05-01), p. 383-383
    Abstract: Manganese oxides (MnO x ) are a well- established class of active materials for electrochemical energy- storage technologies ranging from primary alkaline to rechargeable Li- ion batteries and more recently, have shown great promise in electrochemical capacitors. The widespan applicability of MnO x in these different devices stems from the use of different electrode structures and electrolyte compositions. However, we have demonstrated that with the use of an advanced 3D electrode architecture in which the MnO x component exists as a conformal nanoscale coating on a carbon nanofoam paper with a through-connected pore structure, it is possible to deliver full theoretical capacity of LiMn 2 O 4 , a nominal battery material, at EC-like rates in an aqueous electrolyte. We are now extending the performance enhancements gained via the 3D electrode architecture demonstrated for Li-ion battery chemistries to aqueous-based Zn-ion batteries comprised of a MnO x @carbon nanofoam cathode and a Zn anode. We show that the MnO x @carbon nanofoam delivers full theoretical capacity (308 mA h g -1 ) at 1 C when cycled in an aqueous mixed salt electrolyte (e.g., 0.75 M Na 2 SO 4 + 0.25 M ZnSO 4 ) – delivering high capacity at high rate in a single electrode. To gain a better understanding of the charge-storage reactions occurring in this complex system, we perform a suite of characterization methods as a function of potential. Electrochemical impedance spectroscopy confirms that MnO x stores charge via pseudocapacitance, supported by the presence of Na ions in the electrolyte, at potentials not associated with Zn 2+ insertion/extraction. Ex-situ surface characterization of discharged MnO x @carbon nanofoam electrodes reveal the formation of Zn 4 (OH) 6 SO 4 ·5H 2 O crystallites on the exterior surface, but no evidence of those precipitates after recharge. The ability to deposit/dissolve the Zn 4 (OH) 6 SO 4 ·5H 2 O precipitates in conjunction with pseudocapacitive charge-storage supports long-term cycling ability, with minimal decrease in capacity over 1000 cycles.
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2019
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  • 7
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2019-01, No. 33 ( 2019-05-01), p. 1769-1769
    Abstract: The design platform around which our team creates high-performance electrodes for electrochemical energy devices that use aqueous electrolytes entails the use of porous, aperiodic architectures. The electrode structures, which are based on such form factors as papers and foams, are mostly nothing. Fabrication is based on bench top and scalable protocols with the final 3D form comprising a solid, bonded network co-continuous in three dimensions (3D) with micro- and nanoscale void. Three recent examples include: (1) Demonstrating the activity and stability of conformal RuO 2 “nanoskins” on technologically relevant, silica fiber paper for water oxidation in acid electrolyte. By wrapping the fibers with 〈 100 nm–thick shells of conductive pyrolytic carbon before nanoskin deposition, the RuO 2 @C@SiO 2 electrode evolves O 2 with an overpotential of 330 mV at 40–60 mA mg RuO₂ –1 and retains the high specific activity of RuO 2 nanoskins while using a catalyst density 300−580× less than that of bulk RuO 2 [1] . (2) Fabricating dendrite-prone zinc into monolithic anodes with porous, aperiodic architectured form-factors (“sponges”) that innately suppress zinc migration and dendrite development in alkaline electrolyte. With unprecedented cyclability at high depths-of-discharge (theoretical DOD Zn ), increased specific capacity relative to conventional powder-bed Zn electrodes, and tens of thousands of cycles at low-DOD Zn pulse-power profiles in prototype Ni–Zn cells [2], this breakthrough enables the entire family of alkaline Zn batteries (Ni–Zn, Ag–Zn, MnO 2 –Zn, and Zn–air) to be reconfigured in extensively rechargeable forms, with energy and power characteristics that are competitive with Li-ion batteries. Our second-generation emulsion protocol improves the volumetric density of the sponge thereby concomitantly improving the energy density and power density of the cell while adding mechanical ruggedness to the anode [3]. (3) Evaluating oxygen-evolution and -reduction electrocatalysts as a function of their pore–solid architecture in which the free volume can be adjusted from 〉 85% (aerogel) to 40–70% (ambigel) to ~30% (xerogel). Cryptomelane MnO 2 aerogel and xerogel yield identical electrocatalytic activity when cast as thin films onto rotating-disk electrodes, yet when formulated with conductive carbon and polymer binder into a microheterogeneous air cathode that balances the zinc sponge in a zinc–air button cell, the aerogel-catalyzed cell exhibits an overpotential for oxygen reduction lowered by ∼50 mV compared to the xerogel-based analog and improves discharge voltage by 100 mV at moderate-to-challenging current densities (5–125 mA cm –2 ) [4]. [1] P.A. DeSario, C.N. Chervin, E.S. Nelson, M.B. Sassin, and D.R. Rolison, Competitive oxygen evolution in acid electrolyte catalyzed at technologically relevant electrodes painted with nanoscale RuO 2 . ACS Appl. Mater. Interfaces , 9 , 2387–2395 (2017). [2] J.F. Parker, C.N. Chervin, I.R. Pala, M. Machler, M.F. Burz, J.W. Long, and D.R. Rolison, Rechargeable nickel–3D zinc batteries: An energy-dense, safer alternative to lithium-ion. Science , 356 , 415–418 (2017). [3] J.S. Ko, A.B. Geltmacher, B.J. Hopkins, D.R. Rolison, J.W. Long, and J.F. Parker, ACS Appl. Energy Mater. (doi: 10.1021/acsaem.8b01946). [4] J.S. Ko, J.F. Parker, M.N. Vila, M.A. Wolak, M.B. Sassin, D.R. Rolison, and J.W. Long, Electrocatalyzed oxygen reduction at manganese oxide nanoarchitectures: From electroanalytical characterization to device-relevant performance in composite electrodes. J. Electrochem. Soc ., 165 , H777–H783 (2018).
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2019
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  • 8
    In: Energy Storage Materials, Elsevier BV, Vol. 21 ( 2019-09), p. 481-486
    Type of Medium: Online Resource
    ISSN: 2405-8297
    Language: English
    Publisher: Elsevier BV
    Publication Date: 2019
    detail.hit.zdb_id: 2841602-8
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  • 9
    Online Resource
    Online Resource
    Royal Society of Chemistry (RSC) ; 2018
    In:  Sustainable Energy & Fuels Vol. 2, No. 3 ( 2018), p. 626-636
    In: Sustainable Energy & Fuels, Royal Society of Chemistry (RSC), Vol. 2, No. 3 ( 2018), p. 626-636
    Type of Medium: Online Resource
    ISSN: 2398-4902
    Language: English
    Publisher: Royal Society of Chemistry (RSC)
    Publication Date: 2018
    detail.hit.zdb_id: 2882651-6
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  • 10
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2019-02, No. 3 ( 2019-09-01), p. 145-145
    Abstract: The primary alkaline Zn/MnO 2 battery remains a ubiquitous energy-storage solution for many consumer uses, though its application space is narrowing due to limited rechargeability. The inherent cost and safety benefits of the Zn/MnO 2 pairing electrodes can be translated to a new class of rechargeable “zinc-ion” batteries that are enabled by specific nanostructured manganese oxides that undergo reversible redox reactions in mild-pH Zn 2+ -based electrolytes. We are exploring two such MnO x polymorphs—layered, birnessite-type and cubic-spinel ZnMn 2 O 4 —for zinc-ion storage, where the oxide is expressed as a nanoscale coating on carbon nanofoam (CNF) paper substrates. The optimized electron/ion transport characteristics of MnO x –CNF electrode architectures ensures high oxide-normalized capacity delivered at moderate-to-high rates and over hundreds of charge–discharge cycles. Pseudocapacitive reactions at the MnO x are also activated when Na + or Li + salts are added to the Zn 2+ -based aqueous electrolyte, enabling pulse-power functionality at time scales approaching those for electrochemical capacitors [1]. Redox reactions at MnOx zinc-ion electrolytes may follow multiple pathways that including direct Zn 2+ insertion/association and proton-insertion processes that shift local pH to induce the precipitation of Zn x (OH) y (SO 4 ) z at the MnO x surface. Ex situ characterization by diffraction, spectroscopy, and microscopy confirms that the latter process is dominant with birnessite-MnO x –CNF electrodes, with the reversibility of this complex precipitation/dissolution process promoted by the pore–solid architecture of the CNF [2]. To further unravel the mechanisms of Zn-ion storage, we examine 2D-planar MnOx–carbon electrodes that mimic the surfaces of their 3D counterparts, applying such in situ techniques as scanning-probe microscopy and quartz-crystal microbalance measurements. Insights from these investigations inform the design of advanced electrode architectures for high-performance, rechargeable zinc-ion batteries. [1] “Combining Battery-Like and Pseudocapacitive Charge Storage in 3D MnO x @Carbon Electrode Architectures in Zinc-Ion Cells.” J.S. Ko, M.B. Sassin, J.F. Parker, D.R. Rolison, and J.W. Long, Sustain. Energy Fuels , 2 (2018) 626–636. [2] J.S. Ko, M.D. Donakowski, M.B. Sassin, J.F. Parker, D.R. Rolison, and J.W. Long, MRS Comm ., 9 (2019) 99–106.
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2019
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