| 1. |
- Ghorbani Shiraz, Hamid, 1989-
(författare)
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Electrochemical reduction of protons and organic molecules in hydrogen technologies : Liquid Organic Hydrogen carrier and Hydrogen Evolution
- 2022
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- In accordance with preventable actions to mitigate the effect of climate change in the modern societal applications, renewable energy is an unavoidable and decisive factor in the energy industry. The energy sources that offer non-depleted and environment-friendly pathways for the energy sector are in focus. Amongst, hydrogen has been defined as one of the best candidates to meet the criteria such as high energy-content and zero-emission of CO2, and of course, renewability. In this work, we focused on the areas of hydrogen generation and hydrogen storage.In the first part, we employed an inorganic electrocatalyst (nanosheets) to drive the hydrogen evolution reaction (HER), where we proved that the overpotential of few millivolts (0.016 V) is enough to run the HER reaction. We studied the effect of interlayer gap (for the nanosheets) on the catalytic performance. The chemical intercalation showed a huge effect for the suppression of the HER, which could be applicable for the devices like batteries the formation of any gaseous species has detrimental effect on the performance. It should not be left unmentioned that the measurements were carried out in a platinum group metal free (PGM-free) system, where graphite felt were used as a counter electrode, to avoid any platinum contamination. Next, we investigated the effect of oxygen poisoning on both pristine electrocatalyst and intercalated one. The XPS and UPS measurements confirmed the formation of oxygen-containing groups on the electrocatalysts. Electrochemical measurements showed the increase of the overpotential toward HER as the electrocatalysts are exposed to air for longer time. However, study of the hydrogen oxidation reaction (HOR) showed that there is an optimum concentration of oxygenic functional groups that can lead to a high current density of HOR process. The study of exchange current density showed that, after 10 days of exposure of electrocatalyst to atmospheric air, pristine sample possesses the best performance toward HER and intercalated one shows the highest performance for the HOR. In the other section, hydrogen storage for the organic redox-active molecule (dissolved in organic solvent) was studied. One of the main problems in hydrogen economy concept, is the storage of the hydrogen for transportation. The new concept of Liquid Organic Hydrogen Carrier (LOHC) offers a low-cost and safe approach to this challenge. Herein, we demonstrated an electrochemical pathway to hydrogenate the organic system via conversion of proton of a proton donor into a covalent-bonded hydrogen, through a proton coupled electron transfer (PCET) reaction of 2nH+ + 2ne¯ + Rox nH2Rred. Here, we studied the 9-fluorenone/fluorenol (Fnone/Fnol) as a model PCET reaction. The electrochemical activation of starting component of (Fnone), through two successive electron transfers was investigated with in-situ and operando spectroscopies purely, and in presence of different proton donors of different reactivity. We succeed to both quantify and qualify the investigated the reaction. The hydrogen release step was demonstrated chemically with the aid of catalyst. To conclude, we employed a PGM-free system to demonstrate and characterize a high performing electrocatalyst for hydrogen evolution. Surprisingly, HOR was revealed to perform well using the oxygen poisoned electrocatalyst for HER. In the other section of this work, an electrochemical assisted synthesis of LOHC, in the lab-scale, was proved. A PCET pathway was conceptualized with mechanistic insight. Our work opens new avenue for the technology of hydrogenation of LOHC as we showed for the first time that this could be realized by electrochemistry without the need of hydrogen gas as a prerequisite. We believe that in the future both works could contribute slightly to the concept of the hydrogen economy.
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| 2. |
- Lienemann, Samuel Lukas, 1988-
(författare)
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Materials and Devices for Stretchable Electronic Nerve Interfaces
- 2022
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Within our body, there is a large network of nerves that facilitates communication between the brain and the body’s organs. This network is called our peripheral nervous system, consisting of soft and stretchable nerve bundles that gradually increase in their functional specificity as they split and branch out the closer they get to their target organ. Communication within the nerve is based on action potentials, fast fluctuations in electric trans-membrane potential along the neurons within the nerve. These action potentials can be recorded and artificially triggered by interfacing electronically with peripheral nerves. In doing so, modern medicine is able to elucidate the mechanisms behind disorders related to the nervous system and even applies novel electronic therapies to treat them. Over the last decade, the field of biomedical engineering has therefore seen a surge of interest in electronic devices that interface with the peripheral nervous system, such as cuff electrodes. The device function is based on electrodes that are implanted in close proximity of the nerves they intend to record or stimulate. A cuff electrode, specifically, is wrapped around a peripheral nerve and applies stimulation pulses at electrodes located on the inside of the cuff to evoke action potentials within the nerve. Our body is not welcoming to foreign objects though. Any implant within our body triggers a foreign body reaction with an intensity dependent on the biocompatibility of the implant. Recent studies have found that one of the major factors governing the foreign body reaction is the mechanical mismatch of the implant to the interfacing tissue, with softer, more mechanically similar implants, exhibiting reduced foreign body response. This has prompted an ongoing push for thin and soft peripheral nerve interfaces. However, to truly match the mechanical properties of peripheral nerves, peripheral nerve interfaces need not only to be soft and flexible, they need to become as elastic and stretchable as the nerve themselves. A common strategy to achieve stretchable conductors is by incorporating highly conductive filler materials in an elastomeric matrix. The resulting composite remains conductive even when stretched due to the ability of the filler material to dislocate with the elastomeric matrix while retaining its interconnectivity and thus conductivity. Electronic composites based on gold nanowires and silicones are promising candidates for stretchable peripheral nerve interfaces, due to their material-based biocompatibility, good stretchability, and versatile patterning possibilities.Based on this, the thesis at hand investigated stretchable electronic composite materials and devices to interface with the peripheral nervous system. Publication I and II develop gold-nanowire/polydimethylsiloxane-based cuff electrodes, which are functional even at 50% strain, as peripheral nerve interfaces in vivo. These publications highlight the beneficial conformability of stretchable devices, with a stretchable bi-polar cuff for low-voltage stimulation of the rat sciatic nerve in publication I and a stretchable multi-electrode cuff for selective stimulation of the pig sciatic nerve in publication II. Publication III investigates stretchable gold-nanowire composites based on a variety of elastomers, therein, elucidating the influence of the varying elastomer properties on the electromechanical performance of gold-nanowire composites. Lastly, publication IV establishes a stretchable ion delivery device with potential use for the peripheral nervous system. The device is based on an ionically conductive membrane as the conductive filler, and the device can be reversibly stretched to 100% strain. Overall, this thesis presents stretchable materials and devices that advance the possibilities for peripheral nerve interfaces.
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| 3. |
- Say, Mehmet Girayhan, 1992-
(författare)
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Hybrid Materials for Wearable Electronics and Electrochemical Systems
- 2022
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Flexible electronic systems such as wearable devices, sensors and electronic skin require power sources and sensing units that are mechanically robust, operational at low bending radius, and environmentally friendly. Recently, there has been an enormous interest in active materials such as thin film semiconductors, conductive polymers, and ion-electron conductors. These materials can be deposited with both printing and microfabrication techniques onto the flexible substrates such as plastics and paper. In addition, paper-based composites with nanofibrillated cellulose are favorable due to their mechanical strength, porosity, and solution-processability. Printing of such systems enables mass-production of large area electrochemical devices i.e., batteries, supercapacitors and fuel cells. Moreover, designing ultrathin devices for such concepts are promising for implantable and skin-like conformable electronics.The aim of this thesis is the development of flexible electronic devices where, both organic and inorganic materials are explored, and examples of smart packaging and wearable electronics are demonstrated. Within the thesis, two different fabrication approaches are presented to achieve flexible electronics: (1) fabrication of porous paper electrodes for printable, wearable supercapacitor applications, where our efforts towards sustainable solutions for energy storage and (2) development of ultraflexible devices for electronic skin and implantable electronics to attain miniaturized, ultrathin device concepts. Overall, high performance electronic devices and demonstrators shown here have a significant impact on portable hybrid systems and flexible electronics applications.
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| 4. |
- Ghorbani Shiraz, Hamid, 1989-, et al.
(författare)
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3R-TaS2 as an Intercalation-Dependent Electrified Interface for Hydrogen Reduction and Oxidation Reactions
- 2022
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 126:40, s. 17056-17065
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Tidskriftsartikel (refereegranskat)abstract
- Hydrogen technology, as a future breakthrough for the energy industry, has been defined as an environmentally friendly, renewable, and high-power energy carrier. The green production of hydrogen, which mainly relies on electrocatalysts, is limited by the high cost and/ or the performance of the catalytic system. Recently, studies have been conducted in search of bifunctional electrocatalysts accelerating both the hydrogen evolution reaction (HER) and the hydrogen oxidation reaction (HOR). Herein, we report the investigation of the high efficiency bifunctional electrocatalyst TaS2 for both the HER and the HOR along with the asymmetric effect of inhibition by organic intercalation. The linear organic agent, to boost the electron donor property and to ease the process of intercalation, provides a higher interlayer gap in the tandem structure of utilized nanosheets. XRD and XPS data reveal an increase in the interlayer distance of 22%. The HER and the HOR were characterized in a Pt group metal-free electrochemical system. The pristine sample shows a low overpotential of -0.016 Vat the onset. The intercalated sample demonstrates a large shift in its performance for the HER. It is revealed that the intercalation is a potential key strategy for tuning the performance of this family of catalysts. The inhibition of the HER by intercalation is considered as the increase in the operational window of a water-based electrolyte on a negative electrode, which is relevant to technologies of electrochemical energy storage.
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| 5. |
- Kumar, Divyaratan, et al.
(författare)
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Self-Discharge in Batteries Based on Lignin and Water-in-Polymer Salt Electrolyte
- 2022
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Ingår i: Advanced Energy and Sustainability Research. - : Wiley. - 2699-9412. ; 3:10
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Tidskriftsartikel (refereegranskat)abstract
- Lignin, the most abundant biopolymer on earth, has been explored as an electroactive material in battery applications. One essential feature for such lignin-based batteries to reach successful usage and implementation, e.g., large-scale stationary grid applications, is to have slow self-discharge characteristics on top of the essential safety and life-cycle properties. Water-in-polymer salt electrolytes (WIPSEs) have been demonstrated as an attractive route to solve this issue; however, little has been done to understand the fundamentals of actual self-discharge mechanisms. Herein, the impact of some critical chemical and physical parameters (pH, dissolved oxygen, viscosity, and cutoff potential) on self-discharge of batteries based on WIPSE and lignin has been investigated. The pH range is crucial as there is an interplay between long-term stability and high energy density. Indeed, lignin derivatives typically store relatively more charge in acidic media but later promote corrosion affecting device stability. A robust and high-performing organic battery, incorporating potassium polyacrylate as WIPSE, is demonstrated, which expresses good self-discharge behavior for a broad range of pH and with little impact on the atmosphere used for manufacturing. It is believed that the investigation will provide critical insights to the research community to promote the advancement of printed large-scale energy storage devices.
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| 6. |
- Ahmed, Fareed, et al.
(författare)
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Manufacturing Poly(3,4-Ethylenedioxythiophene) Electrocatalytic Sheets for Large-Scale H2O2 Production
- 2022
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Ingår i: Advanced Sustainable Systems. - : John Wiley and Sons Inc. - 2366-7486. ; 6:1
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Tidskriftsartikel (refereegranskat)abstract
- Producing thick films of conducting polymers by a low-cost manufacturing technique would enable new applications. However, removing huge solvent volume from diluted suspension or dispersion (1–3 wt%) in which conducting polymers are typically obtained is a true manufacturing challenge. In this work, a procedure is proposed to quickly remove water from the conducting polymer poly(3,4-ethylenedioxythiophene:poly(4-styrene sulfonate) (PEDOT:PSS) suspension. The PEDOT:PSS suspension is first flocculated with 1 m H2SO4 transforming PEDOT nanoparticles (≈50–500 nm) into soft microparticles. A filtration process inspired by pulp dewatering in a paper machine on a wire mesh with apertures dimension between 60 µm and 0.5 mm leads to thick free-standing films (≈0.5 mm). Wire mesh clogging that hinders dewatering (known as dead-end filtration) is overcome by adding to the flocculated PEDOT:PSS dispersion carbon fibers that aggregate and form efficient water channels. Moreover, this enables fast formation of thick layers under simple atmospheric pressure filtration, thus making the process truly scalable. Thick freestanding PEDOT films thus obtained are used as electrocatalysts for efficient reduction of oxygen to hydrogen peroxide, a promising green chemical and fuel. The inhomogeneity of the films does not affect their electrochemical function. © 2021 The Authors.
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| 7. |
- Berggren, Magnus, Professor, 1968-, et al.
(författare)
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In Vivo Organic Bioelectronics for Neuromodulation
- 2022
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Ingår i: Chemical Reviews. - : American Chemical Society (ACS). - 0009-2665 .- 1520-6890. ; 122:4, s. 4826-4846
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Forskningsöversikt (refereegranskat)abstract
- The nervous system poses a grand challenge for integration with modern electronics and the subsequent advances in neurobiology, neuroprosthetics, and therapy which would become possible upon such integration. Due to its extreme complexity, multifaceted signaling pathways, and similar to 1 kHz operating frequency, modern complementary metal oxide semiconductor (CMOS) based electronics appear to be the only technology platform at hand for such integration. However, conventional CMOS-based electronics rely exclusively on electronic signaling and therefore require an additional technology platform to translate electronic signals into the language of neurobiology. Organic electronics are just such a technology platform, capable of converting electronic addressing into a variety of signals matching the endogenous signaling of the nervous system while simultaneously possessing favorable material similarities with nervous tissue. In this review, we introduce a variety of organic material platforms and signaling modalities specifically designed for this role as "translator" , focusing especially on recent implementation in in vivo neuromodulation. We hope that this review serves both as an informational resource and as an encouragement and challenge to the field.
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| 8. |
- Gerasimov, Jennifer Yevgenia, 1985-, et al.
(författare)
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Rational Materials Design for In Operando Electropolymerization of Evolvable Organic Electrochemical Transistors
- 2022
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Ingår i: Advanced Functional Materials. - : John Wiley and Sons Inc. - 1616-301X .- 1616-3028. ; 32
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Tidskriftsartikel (refereegranskat)abstract
- Organic electrochemical transistors formed by in operando electropolymerization of the semiconducting channel are increasingly becoming recognized as a simple and effective implementation of synapses in neuromorphic hardware. However, very few studies have reported the requirements that must be met to ensure that the polymer spreads along the substrate to form a functional conducting channel. The nature of the interface between the substrate and various monomer precursors of conducting polymers through molecular dynamics simulations is investigated, showing that monomer adsorption to the substrate produces an increase in the effective monomer concentration at the surface. By evaluating combinatorial couples of monomers baring various sidechains with differently functionalized substrates, it is shown that the interactions between the substrate and the monomer precursor control the lateral growth of a polymer film along an inert substrate. This effect has implications for fabricating synaptic systems on inexpensive, flexible substrates. © 2022 The Authors.
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| 9. |
- Keene, Scott T., et al.
(författare)
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Exploiting mixed conducting polymers in organic and bioelectronic devices
- 2022
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 24:32, s. 19144-19163
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Forskningsöversikt (refereegranskat)abstract
- Efficient transport of both ionic and electronic charges in conjugated polymers (CPs) has enabled a wide range of novel electrochemical devices spanning applications from energy storage to bioelectronic devices. In this Perspective, we provide an overview of the fundamental physical processes which underlie the operation of mixed conducting polymer (MCP) devices. While charge injection and transport have been studied extensively in both ionic and electronic conductors, translating these principles to mixed conducting systems proves challenging due to the complex relationships among the individual materials properties. We break down the process of electrochemical (de)doping, the basic feature exploited in mixed conducting devices, into its key steps, highlighting recent advances in the study of these physical processes in the context of MCPs. Furthermore, we identify remaining challenges in further extending fundamental understanding of MCP-based device operation. Ultimately, a deeper understanding of the elementary processes governing operation in MCPs will drive the advancement in both materials design and device performance.
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| 10. |
- Lander, Sanna, 1990-, et al.
(författare)
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Sulfonated Cellulose Membranes Improve the Stability of Aqueous Organic Redox Flow Batteries
- 2022
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Ingår i: Advanced Energy and Sustainability Research. - : Wiley. - 2699-9412. ; 3:9
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Tidskriftsartikel (refereegranskat)abstract
- The drawbacks of current state-of-the-art selective membranes, such as poor barrier properties, high cost, and poor recyclability, limit the large-scale deployment of electrochemical energy devices such as redox flow batteries (RFBs) and fuel cells. In recent years, cellulosic nanomaterials have been proposed as a low-cost and green raw material for such membranes, but their performance in RFBs and fuel cells is typically poorer than that of the sulfonated fluoropolymer ionomer membranes such as Nafion. Herein, sulfonated cellulose nanofibrils densely cross-linked to form a compact sulfonated cellulose membrane with limited swelling and good stability in water are used. The membranes possess low porosity and excellent ionic transport properties. A model aqueous organic redox flow battery (AORFB) with alizarin red S as negolyte and tiron as posolyte is assembled with the sulfonated cellulose membrane. The performance of the nanocellulose-based battery is superior in terms of cyclability in comparison to that displayed by the battery assembled with commercially available Nafion 115 due to the mitigation of crossover of the redox-active components. This finding paves the way to new green organic materials for fully sustainable AORFB solutions.
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