Biobased self-healing thin film coatings based on poly(itaconic acid esters).

Paper used for packaging applications is often coated with thin polymer coatings to improve the properties, like printability and barrier properties, respectively. Today, these coatings are still often based on petroleum-based polymers. In this study, the fabrication of biobased thin film coatings is described. Poly(itaconic acid ester)s, which are prepared by emulsion poly-meri-zation, are used as water-based coatings for paper. The thermal properties of the polymers are tuned by the side chain of the monomers (diethyl itaconate vs. dibutyl itaconate). Different formulations based on the polymer emulsion and additives, like rheology modifiers, are prepared and their film formation is studied. The usage of Rheobyk-7420 CA as rheology modifier results in excellent film formation. These polymer coatings feature an additional function - they are capable of self-healing. The healing ability is studied in scratch healing tests, in which almost complete recovery can be observed after healing at 100 °C. Moreover, the restoration of optical properties / aesthetics is studied. In gloss measurements before and after damage as well as after a healing time the complete recovery of the gloss can be observed. Furthermore, the barrier properties against fat are studied.

Investigation of the cooperative-effects of Lewis- and Brønstedt acids in homogeneously catalyzed OME fuel synthesis by inline-NMR monitoring.

Via inline-nuclear magnetic resonance measurements, the homogeneously catalyzed poly(oxymethylene dimethyl ether) fuel synthesis using trioxane and dimethoxy methane is investigated. Besides the Brønsted acid (BA) catalyst triflic acid (TfOH) different metal halides are studied as Lewis-acidic (LA) catalysts. Among the used LAs, MgCl2, the weakest based on electronegativity, reveals the highest catalytical activity. Additionally, the influence of the concentration of BA and LA is investigated. An increase in BA concentration leads to an exponential increase of the reaction rate, while increasing the concentration of the LA leads to a volcano plot with its optimum at a LA : BA ratio of 1 : 3. The influence of the LA on the electron density of the intermediate formaldehyde is concluded as the main factor for this behavior.

An Iridium Complex as Bidentate Halogen Bond-Based Anion Receptor Featuring an IncreasedOptical Response.

We present a luminescent Ir(III) complex featuring a bidentate halogen bond donor site capable of strong anion binding. The tailor-made Ir(III)(L)2 moiety offers a significantly higher emission quantum yield (8.4 %) compared to previous Ir(III)-based chemo-sensors (2.5 %). The successful binding of chloride, bromide and acetate is demonstrated using emission titrations. These experiments reveal association constants of up to 1.6×105 M-1. Furthermore, a new approach to evaluate the association constant by utilizing the shift of the emission was used for the first time. The experimentally observed characteristics are supported by quantum chemical simulations.

Development of a multi-step screening procedure for redox active molecules in organic radical polymer anodes and as redox flow anolytes.

Benzo[d]-X-zolyl-pyridinyl (XO, S, NH) radicals represent a promising class of redox-active molecules for organic batteries. We present a multistep screening procedure to identify the most promising radical candidates. Experimental investigations and highly correlated wave function-based calculations are performed to determine benchmark redox potentials. Based on these, the accuracies of different methods (semi-empirical, density functional theory, wave function-based), solvent models, dispersion corrections, and basis sets are evaluated. The developed screening procedure consists of three steps: First, a conformer search is performed with CREST. The molecules are selected based on the redox potentials calculated using GFN2-xTB. Second, HOMO energies calculated with reparametrized B3LYP-D3(BJ) and the def2-SVP basis set are used as selection criteria. The final molecules are selected based on the redox potentials calculated from Gibbs energies using BP86-D3(BJ)/def2-TZVP. With this multistep screening approach, promising molecules can be suggested for synthesis, and structure-property relationships can be derived.

Development of Novel Redox-Active Organic Materials Based on Benzimidazole, Benzoxazole, and Benzothiazole: A Combined Theoretical and Experimental Screening Approach.

Sustainability is one of the hot topics of today's research, in particular when it comes to energy-storage systems such as batteries. Redox-active molecules implemented in organic batteries represent a promising alternative to lithium-ion batteries, which partially rely on non-sustainable heavy metal salts. As an alternative, we propose benzothiazole, -oxazole and -imidazole derivatives as redox-active moieties for polymers in organic (radical) batteries. The target molecules were identified by a combination of theoretical and experimental approaches for the investigation of new organic active materials. Herein, we present the synthesis, electrochemical characterization and theoretical investigation of the proposed molecules, which can later be introduced into a polymer backbone and used in organic polymer batteries.

Influencing ionic conductivity and mechanical properties of ionic liquid polymer electrolytes by designing the chemical monomer structure.

Polymeric single chloride-ion conductor networks based on acrylic imidazolium chloride ionic liquid monomers AACXImCYCl as reported previously are prepared. The chemical structure of the polymers is varied with respect to the acrylic substituents (alkyl spacer and alkyl substituent in the imidazolium ring). The networks are examined in detail with respect to the influence of the chemical structure on the resulting properties including thermal behavior, rheological behavior, swelling behavior, and ionic conductivity. The ionic conductivities increase (by two orders of magnitude from 10-6 to 10-4 S·cm-1 with increasing temperature), while the complex viscosities of the polymer networks decrease simultaneously. After swelling in water for 1 week the ionic conductivity reaches values of 10-2 S·cm-1. A clear influence of the spacer and the crosslinker content on the glass transition temperature was shown for the first time in these investigations. With increasing crosslinker content, the Tg values and the viscosities of the networks increase. With increasing spacer length, the Tg values decrease, but the viscosities increase with increasing temperature. The results reveal that the materials represent promising electrolytes for batteries, as proven by successful charging/discharging of a p(TEMPO-MA)/zinc battery over 350 cycles.

Molecular in situ monitoring of the pH-triggered response in adaptive polymers by two-dimensional Raman micro-correlation-spectroscopy.

Stimuli-responsive polymers can switch specific physical properties in response to a change of the environmental conditions. This behavior offers unique advantages in applications where adaptive materials are needed. To tune the properties of stimuli-responsive polymers, a detailed understanding of the relationship between the applied stimulus and changes in molecular structure as well as the relationship between the latter and macroscopic properties is required, which until now has required laborious methods. Here, we present a straightforward way to investigate the progressing trigger, the change of the chemical composition of the polymer and the macroscopic properties simultaneously. Thereby, the response behavior of the reversible polymer is studied in situ with molecular sensitivity and spatial as well as temporal resolution utilizing Raman micro-spectroscopy. Combined with two-dimensional correlation analysis (2DCOS), this method reveals the stimuli-response on a molecular level and determines the sequence of changes and the diffusion rate inside the polymer. Due to the label-free and non-invasive approach, it is furthermore possible to combine this method with the investigation of macroscopic properties revealing the response of the polymer to the external stimulus on both the molecular and the macroscopic level.

Organic Redox Targeting Flow Battery Utilizing a Hydrophilic Polymer and Its In-Operando Characterization via State-of-Charge Monitoring of The Redox Mediator.

The hydrophilic poly(2,2,6,6-tetramethylpiperdinyloxy-4-yl-methacrylamide) (PTMAm) was utilized as redox target material in an aqueous organic redox targeting flow battery (RTFB). This polymer is processed into granules, which contain a conductive agent and an alginate binder. By this, a hydrophilic, yet water-insoluble redox target can be obtained. The target was combined with the redox mediator molecule N,N,N-trimethyl-2-oxo-2-[(2,2,6,6-tetramethylpiperidin-4-yloxyl)amino]ethan-1-ammonium chloride (TEMPOAmide), that has been reported earlier as flow battery active material. This target/mediator combination has been characterized electrochemically and flow battery testing has been done. Furthermore, in-operando characterization of the redox target via electrolyte state-of-charge (SOC) monitoring has been performed for the first time. The approach provides estimates for the redox target's SOC changes during cycling. In addition, a figure of merit - the "redox targetivity" - is proposed, which provides insights into the efficiency of the targeting reaction and supports the future optimization of materials, cell designs, and operational parameters for RTFBs.

Oxymethylene Ether (OME) Fuel Catalyst Screening Using In Situ NMR Spectroscopy.

Online NMR measurements are introduced in the current study as a new analytical setup for investigation of the oxymethylene dimethyl ether (OME) synthesis. For the validation of the setup, the newly established method is compared with state-of-the-art gas chromatographic analysis. Afterwards, the influence of different parameters, such as temperature, catalyst concentration and catalyst type on the OME fuel formation based on trioxane and dimethoxymethane is investigated. As catalysts, AmberlystTM 15 (A15) and trifluoromethanesulfonic acid (TfOH) are utilized. A kinetic model is applied to describe the reaction in more detail. Based on these results, the activation energy (A15: 48.0 kJ mol-1 and TfOH: 72.3 kJ mol-1 ) and the order in catalyst (A15: 1.1 and TfOH: 1.3) are calculated and discussed.

Hydrophilic Crosslinked TEMPO-Methacrylate Copolymers - a Straight Forward Approach towards Aqueous Semi-Organic Batteries.

Crosslinked hydrophilic poly(2,2,6,6-tetramethylpiperidinyl-N-oxyl-co-[2-(methacryloyloxy)-ethyl]trimethyl ammonium chloride) [poly(TEMPO-co-METAC)] polymers with different monomer ratios are synthesized and characterized regarding a utilization as electrode material in organic batteries. These polymers can be synthesized rapidly utilizing commercial starting materials and reveal an increased hydrophilicity compared to the state-of-the-art poly(2,2,6,6-tetramethylpiperidinyl-N-oxyl-4-methacrylate) (PTMA). By increasing the hydrophilicity of the polymer, a preparation of cathode composites is enabled, which can be used for aqueous semi-organic batteries. Detailed battery testing confirms that the additional METAC groups do not impair the battery behavior while enabling straight-forward zinc-TEMPO batteries.

Synthesis and Characterization of Metallopolymer Networks Featuring Triple Shape-Memory Ability Based on Different Reversible Metal Complexes.

This study presents the synthesis and characterization of metallopolymer networks with a triple shape-memory ability. A covalently crosslinked polymer network featuring two different additional ligands in its side chains is synthesized via free radical polymerization (FRP). The subsequent addition of different metal salts leads to the selective formation of complexes with two different association constants (Ka), proven via isothermal titration calorimetry (ITC). Those two supramolecular crosslinks feature different activation temperatures and can act as two individual switching units enabling the fixation and recovery of two temporary shapes. The presented samples were investigated in a detailed fashion via differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and FT-Raman spectroscopy. Furthermore, thermo-mechanical analyses (TMA) revealed excellent dual and triple shape-memory abilities of the presented metallopolymer networks.

State of Charge and State of Health Assessment of Viologens in Aqueous-Organic Redox-Flow Electrolytes Using In Situ IR Spectroscopy and Multivariate Curve Resolution.

Aqueous-organic redox flow batteries (RFBs) have gained considerable interest in recent years, given their potential for an economically viable energy storage at large scale. This, however, strongly depends on both the robustness of the underlying electrolyte chemistry against molecular decomposition reactions as well as the device's operation. With regard to this, the presented study focuses on the use of in situ IR spectroscopy in combination with a multivariate curve resolution approach to gain insight into both the molecular structures of the active materials present within the electrolyte as well as crucial electrolyte state parameters, represented by the electrolyte's state of charge (SOC) and state of health (SOH). To demonstrate the general applicability of the approach, methyl viologen (MV) and bis(3-trimethylammonium)propyl viologen (BTMAPV) are chosen, as viologens are frequently used as negolytes in aqueous-organic RFBs. The study's findings highlight the impact of in situ spectroscopy and spectral deconvolution tools on the precision of the obtainable SOC and SOH values. Furthermore, the study indicates the occurrence of multiple viologen dimers, which possibly influence the electrolyte lifetime and charging characteristics.

All-Organic Redox Targeting with a Single Redox Moiety: Combining Organic Radical Batteries and Organic Redox Flow Batteries.

The volumetric capacities and the lifetime of organic redox flow batteries (RFBs) are strongly dependent on the concentrations of the redox-active molecules in the electrolyte. Single-molecule redox targeting represents an efficient approach toward realizing viable organic RFBs with low to moderate electrolyte concentrations. For the first time, an all-organic Nernstian potential-driven redox targeting system is investigated that directly combines a single-electrode material from organic radical batteries (ORBs) with a single redox couple of an aqueous, organic RFB, which are based on the same redox moiety. Namely, poly(TEMPO-methacrylate) (PTMA) is utilized as the redox target ("solid booster") and N,N,N-2,2,6,6-heptamethylpiperidinyloxy-4-ammonium chloride (TMATEMPO) is applied as the sole redox mediator to demonstrate the redox targeting mechanisms between the storage materials of both battery types. The formal potentials of both molecules are investigated, and the targeting mechanism is verified by cyclic voltammetry and state-of-charge measurements. Finally, battery cycling experiments demonstrate that 78-90% of the theoretical capacity of the ORB electrode material can be addressed when this material is present as the redox target in the electrolyte tank of an operating, aqueous organic RFB.

Trust is good, control is better: a review on monitoring and characterization techniques for flow battery electrolytes.

Flow batteries (FBs) currently are one of the most promising large-scale energy storage technologies for energy grids with a large share of renewable electricity generation. Among the main technological challenges for the economic operation of a large-scale battery technology is its calendar lifetime, which ideally has to cover a few decades without significant loss of performance. This requirement can only be met if the key parameters representing the performance losses of the system are continuously monitored and optimized during the operation. Nearly all performance parameters of a FB are related to the two electrolytes as the electrochemical storage media and we therefore focus on them in this review. We first survey the literature on the available characterization methods for the key FB electrolyte parameters. Based on these, we comprehensively review the currently available approaches for assessing the most important electrolyte state variables: the state-of-charge (SOC) and the state-of-health (SOH). We furthermore discuss how monitoring and operation strategies are commonly implemented as online tools to optimize the electrolyte performance and recover lost battery capacity as well as how their automation is realized via battery management systems (BMSs). Our key findings on the current state of this research field are finally highlighted and the potential for further progress is identified.

Red-light sensitized hole-conducting polymer for energy conversion.

We report a novel hole conductive polymer with photoactive Os(ii) complexes in the side chains. This PPV derivative can be activated upon absorption of red visible light and delivers notable photocurrents when used as photocathode material. Thus, the polymer presents as a stepping stone towards developing soft matter alternatives to NiO photocathodes, which function under visible light irradiation. To show the concept we combine electrical impedance spectroscopy with steady state spectroscopy. As light-driven hole injection from Os complex to the PPV polymer is thermodynamically feasible both based on reductive quenching of photoexcited PPV and based on oxidative quenching of the photoexcited Os chromophores we investigate the impact of illumination wavelengths on the photocathode behavior and photochemical stability of the material. While both blue and red light excitation, i.e., excitation of the chromophoric units PPV and excitation of the metal-to-ligand charge transfer transitions in the side-chain pendant Os chromophores yield cathodic photocurrents, the photochemical stability is drastically enhanced upon red-light excitation. Hence, the results of the investigations discussed show the validity of the concept developing red-light sensitized hole-conducting polymers for energy conversion.

In-depth characterization of self-healing polymers based on π-π interactions.

The self-healing behavior of two supramolecular polymers based on π-π-interactions featuring different polymer backbones is presented. For this purpose, these polymers were synthesized utilizing a polycondensation of a perylene tetracarboxylic dianhydride with polyether-based diamines and the resulting materials were investigated using various analytical techniques. Thus, the molecular structure of the polymers could be correlated with the ability for self-healing. Moreover, the mechanical behavior was studied using rheology. The activation of the supramolecular interactions results in a breaking of these noncovalent bonds, which was investigated using IR spectroscopy, leading to a sufficient increase in mobility and, finally, a healing of the mechanical damage. This scratch-healing behavior was also quantified in detail using an indenter.

Halogen bonding in polymer science: towards new smart materials.

The halogen bond is a special non-covalent interaction, which can represent a powerful tool in supramolecular chemistry. Although the halogen bond offers several advantages compared to the related hydrogen bond, it is currently still underrepresented in polymer science. The structural related hydrogen bonding assumes a leading position in polymer materials containing supramolecular interactions, clearly indicating the high potential of using halogen bonding for the design of polymeric materials. The current developments regarding halogen bonding containing polymers include self-assembly, photo-responsive materials, self-healing materials and others. These aspects are highlighted in the present perspective. Furthermore, a perspective on the future of this rising young research field is provided.

Novel, Stable Catholyte for Aqueous Organic Redox Flow Batteries: Symmetric Cell Study of Hydroquinones with High Accessible Capacity.

Owing to their broad range of redox potential, quinones/hydroquinones can be utilized for energy storage in redox flow batteries. In terms of stability, organic catholytes are more challenging than anolytes. The two-electron transfer feature adds value when building all-quinone flow battery systems. However, the dimerization of quinones/hydroquinones usually makes it difficult to achieve a full two-electron transfer in practical redox flow battery applications. In this work, we designed and synthesized four new hydroquinone derivatives bearing morpholinomethylene and/or methyl groups in different positions on the benzene ring to probe molecular stability upon battery cycling. The redox potential of the four molecules were investigated, followed by long-term stability tests using different supporting electrolytes and cell cycling methods in a symmetric flow cell. The derivative with two unoccupied ortho positions was found highly unstable, the cell of which exhibited a capacity decay rate of ~50% per day. Fully substituted hydroquinones turned out to be more stable. In particular, 2,6-dimethyl-3,5-bis(morpholinomethylene)benzene-1,4-diol (asym-O-5) displayed a capacity decay of only 0.45%/day with four-week potentiostatic cycling at 0.1 M in 1 M H3PO4. In addition, the three fully substituted hydroquinones displayed good accessible capacity of over 82%, much higher than those of conventional quinone derivatives.

Study of Anion Exchange Membrane Properties Incorporating N-spirocyclic Quaternary Ammonium Cations and Aqueous Organic Redox Flow Battery Performance.

Flexible cross-linked anion exchange membranes (AEMs) based on poly (p-phenylene oxide) grafted with N-spirocyclic quaternary ammonium cations were synthesized via UV-induced free-radical polymerization by using diallylpiperidinium chloride as an ionic monomer. Five membranes with ion exchange capacity (IEC) varying between 1.5 to 2.8 mmol Cl-·g-1 polymer were obtained and the correlation between IEC, water uptake, state of water in the membrane and ionic conductivity was studied. In the second part of this study, the influence of properties of four of these membranes on cell cycling stability and performance was investigated in an aqueous organic redox flow battery (AORFB) employing dimethyl viologen (MV) and N,N,N-2,2,6,6-heptamethylpiperidinyl oxy-4-ammonium chloride (TMA-TEMPO). The influence of membrane properties on cell cycling stability and performance was studied. At low-current density (20 mA·cm-2), the best capacity retention was obtained with lower IEC membranes for which the water uptake, freezable water and TMA-TEMPO and MV crossover are low. However, at a high current density (80 mA·cm-2), membrane resistance plays an important role and a membrane with moderate IEC, more precisely, moderate ion conductivity and water uptake was found to maintain the best overall cell performance. The results in this work contribute to the basic understanding of the relationship between membrane properties and cell performance, providing insights guiding the development of advanced membranes to improve the efficiency and power capability for AORFB systems.

Photocathodes beyond NiO: charge transfer dynamics in a π-conjugated polymer functionalized with Ru photosensitizers.

A conductive polymer (poly(p-phenylenevinylene), PPV) was covalently modified with RuII complexes to develop an all-polymer photocathode as a conceptual alternative to dye-sensitized NiO, which is the current state-of-the-art photocathode in solar fuels research. Photocathodes require efficient light-induced charge-transfer processes and we investigated these processes within our photocathodes using spectroscopic and spectro-electrochemical techniques. Ultrafast hole-injection dynamics in the polymer were investigated by transient absorption spectroscopy and charge transfer at the electrode-electrolyte interface was examined with chopped-light chronoamperometry. Light-induced hole injection from the photosensitizers into the PPV backbone was observed within 10 ps and the resulting charge-separated state (CSS) recombined within ~ 5 ns. This is comparable to CSS lifetimes of conventional NiO-photocathodes. Chopped-light chronoamperometry indicates enhanced charge-transfer at the electrode-electrolyte interface upon sensitization of the PPV with the RuII complexes and p-type behavior of the photocathode. The results presented here show that the polymer backbone behaves like classical molecularly sensitized NiO photocathodes and operates as a hole accepting semiconductor. This in turn demonstrates the feasibility of all-polymer photocathodes for application in solar energy conversion.