Understanding the charge storage mechanism of conductive polymers as hybrid battery-capacitor materials in ionic liquids by <i>in situ</i> atomic force microscopy and electrochemical quartz crystal microbalance studies

Schoetz, Theresa; Kurniawan, Mario; Stich, Michael; Peipmann, Ralf; Efimov, Igor; Ispas, Adriana; Bund, Andreas; León, Carlos Ponce de; Ueda, Mikito

doi:10.1039/c8ta06757k

Cited by 35 publications

(15 citation statements)

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“…The change of the material state in the redox reactions often induces a mechanical breathing strain and a dynamic change of the mechanical properties of the polymers, although there is little consensus in existing studies on how the mechanical behavior quantitatively evolves over electrochromic processes. Previous measurements of the mechanical properties of poly(3,4-ethylenedioxythiophene) (PEDOT) using acoustic impedance showed that the shear modulus was sensitive to the doping level [28][29][30] , temperature 28,29 , electrolyte 28,29 , crosslinker 31,32 , and even film thickness 33 . Ispas et al 28 .…”

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confidence: 99%

Mechanical breathing in organic electrochromics

et al. 2020

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The repetitive size change of the electrode over cycles, termed as mechanical breathing, is a crucial issue limiting the quality and lifetime of organic electrochromic devices. The mechanical deformation originates from the electron transport and ion intercalation in the redox active material. The dynamics of the state of charge induces drastic changes of the microstructure and properties of the host, and ultimately leads to structural disintegration at the interfaces. We quantify the breathing strain and the evolution of the mechanical properties of poly(3,4-propylenedioxythiophene) thin films in-situ using customized environmental nanoindentation. Upon oxidation, the film expands nearly 30% in volume, and the elastic modulus and hardness decrease by a factor of two. We perform theoretical modeling to understand thin film delamination from an indium tin oxide (ITO) current collector under cyclic load. We show that toughening the interface with roughened or silica-nanoparticle coated ITO surface significantly improves the cyclic performance.

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confidence: 99%

Mechanical breathing in organic electrochromics

et al. 2020

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“…The charge storage of conducting polymers occurs not only on the surface (or near surface) but also throughout the entire bulk of materials, displaying both pseudocapacitive and battery-type behaviors. [129,130] Research on conducting polymers toward Si electrodes has extensively focused on the synergistic effect of Faradaic charge transfer in conducting polymers and double layer capacitance based on large surface area of Si nanostructures. Following a CVD route, Aradilla et al synthesized Si nanowires based on VLS mechanism via gold catalysis, and then coated with PEDOT by electrochemical polymerization.…”

Section: Conducting Polymers For Si Electrodesmentioning

confidence: 99%

“…A recent in situ atomic force microscopy study revealed the hybrid battery-pseudocapacitive behavior of conducting polymers in ionic liquids, where the conducting polymers demonstrate pseudocapacitive behavior at a high charging condition, and a battery-type behavior at a low charging condition. [129] Furthermore, studies on thin-film electrochemistry of conducting polymers show that as the film thickness increases, the pseudoca-pacitive characteristic changes to battery-type due to the mass transport restriction within the polymer film. [130] Conducting polymers such as polypyrrole (PPy), polyaniline (PANI), polyacetylene (PA), and poly(3,4-ethy lenedioxythiophene) (PEDOT) have been widely investigated as electrode materials of supercapacitors.…”

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confidence: 99%

Advances in Si and SiC Materials for High‐Performance Supercapacitors toward Integrated Energy Storage Systems

Nguyen

Aberoumand

Dao

2021

Small

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recently attracted considerable research attention thanks to its low mass density (2.33 g cm −3 ), nontoxicity, and biocompatibility. [6,7] Besides, the intrinsic semiconductor and tunable on-chip characteristics enable Si to be a central platform of several applications, including optoelectronics, [8,9] microelectronics, [10] smart sensors, [11,12] solar cells, [13][14][15] and drug-delivery systems. [16] From an energy perspective, seamless integration of energy storage systems onto these Si-based functional devices is highly desirable toward portable and wearable applications, or when the power supply is intermittent. Therefore, significant research has focused on Sibased energy storage, including Si-based batteries (mainly Li-ion batteries) and Sibased supercapacitors.In Li-ion batteries, Si has been intensively studied as a promising anode candidate due to the low working potential of 0.4 V (vs Li + /Li) and high theoretical capacity (3579 mAh g −1 ), compared to the conventional graphite anode. [17] However, as an alloy-type material, Si anode notoriously suffers from huge volume expansion/shrinkage during lithiation/delithiation (over 300%), leading to severe delamination and pulverization of electrodes, together with unstable and nonuniform solid electrolyte interphase layers. [18] These characteristics considerably affect the cyclic stability of Si-anode Li-ion batteries. Several strategies have been implemented to address the aforementioned challenges, including composite and coating materials design, [19][20][21][22][23][24] binder design, [25][26][27][28] and electrolyte modification. [29][30][31][32] These approaches nevertheless are mainly based on wet-chemistry methods with complicated synthesis techniques, which are not suitable for an integrated system. A very thin layer of Si has been proven to accommodate the mechanical stress during alloying/ dealloying. [33][34][35] Inspired by this concept, several studies have focused on thin film Si-anode batteries based on integrated circuit (IC)-compatible routes, and their potentials to be integrated with other functional Si-based devices. [36][37][38][39] However, the intricate charge storage mechanism of Si-based batteries inevitably limits their applications. In particular, batteries suffer from low power performance. Although parallel and/or series connections of batteries can guarantee high power, the device volume will be increased, which is not desirable for an integrated system. Furthermore, owing to their inferior stability and lifetime, batteries unavoidably require frequent replacements, meaning that they cannot be applied in devices such as bioimplant chips, biosensors, and harsh-environment sensors. [40,41] Silicon (Si), as the second most abundant element on Earth, has been a central platform of modern electronics owing to its low mass density and unique semiconductor properties. From an energy perspective, all-in-one integration of power supply systems onto Si-based functional devices is highly desirable, which inspires significant study ...

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“…Since their discovery in 1977 and subsequent Nobel Prize in 2000, conducting polymers (CPs) have been a breakthrough in material science with a wide range of applications in electronics (e.g., ChemFET, flexible circuits, OLED), [1][2][3] solar cell technology, [4][5][6][7][8] batteries (e.g., supercapacitors) [9][10][11][12][13] and biomedical engineering (e.g., electrode coating for recording and stimulation, drug delivery, scaffolds for tissue engineering). [14][15][16][17][18][19][20] These materials are highly versatile thanks to their chemical structure consisting of repeating alternating chains of single and double (π-π) carbon bonds, allowing electrons to move freely alongside the polymeric chains.…”

Section: Introductionmentioning

confidence: 99%

Leveraging Conducting Polymers and Hydrogels for Direct Current Stimulation

Ordonez¹,

Shaner²,

Matter³

et al. 2022

Preprint

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<p>The tunable electrical properties of conducting polymers (CPs), biocompatibility, fabrication versatility, and cost-efficiency make them an ideal coating material for stimulation electrodes in biomedical applications. Several biological processes like wound healing, neuronal regrowth, and cancer metastasis, which rely on constant electric fields, demand electrodes capable of delivering direct current stimulation (DCs) for long times without developing toxic electrochemical reactions. Recently, CPs such as poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT/PSS) have demonstrated outstanding capability for delivering DCs without damaging cells in culture while not requiring intermediate buffers, contrary to the current research setups relying on noble-metals and buffering bridges. However, a clear understanding of how electrode design and CP synthesis influence DCs properties of these materials is still needed. This study demonstrates that various PEDOT-based CP coatings and hydrogels on rough electrodes can deliver DCs without substantial changes to the electrode and noticeable development of chemical byproducts depending on the electrode area and polymer thickness. A comprehensive analysis of the tested coatings is provided according to the desired application and available resources alongside a proposed explanation for the observed electrochemical behavior. The CPs tested herein can pave the way toward the widespread implementation of DCs as a therapeutic stimulation paradigm.</p>

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Understanding the charge storage mechanism of conductive polymers as hybrid battery-capacitor materials in ionic liquids by in situ atomic force microscopy and electrochemical quartz crystal microbalance studies

Abstract: Morphological changes of a conductive polymer in an ionic liquid during charging and discharging.

Cited by 35 publications

References 37 publications

Mechanical breathing in organic electrochromics

Mechanical breathing in organic electrochromics

Advances in Si and SiC Materials for High‐Performance Supercapacitors toward Integrated Energy Storage Systems

Leveraging Conducting Polymers and Hydrogels for Direct Current Stimulation

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