How Regiochemistry Influences Aggregation Behavior and Charge Transport in Conjugated Organosulfur Polymer Cathodes for Lithium–Sulfur Batteries

Schütze, Yannik; Gayen, Diptesh; Pałczynski, Karol; Silva, Ranielle de Oliveira; Lü, Yan; Tovar, Michael; Partovi–Azar, Pouya; Bande, Annika; Dzubiella, Joachim

doi:10.1021/acsnano.3c01523

Cited by 13 publications

(11 citation statements)

References 111 publications

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“…PTBT as an organosulphur cathode on its aggregation behaviour and charge transport (Figure 4b) [26]. The morphology of a polymer can significantly affect its conductive behaviour.…”

Section: Schütze Et Al Investigated the Effect Of The Regiochemistry ...mentioning

confidence: 99%

Electropolymerisation Technologies for Next-Generation Lithium–Sulphur Batteries

Kim,

Lee

2023

Polymers

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Lithium–sulphur batteries (LiSBs) have garnered significant attention as the next-generation energy storage device because of their high theoretical energy density, low cost, and environmental friendliness. However, the undesirable “shuttle effect” by lithium polysulphides (LPSs) severely inhibits their practical application. To alleviate the shuttle effect, conductive polymers have been used to fabricate LiSBs owing to their improved electrically conducting pathways, flexible mechanical properties, and high affinity to LPSs, which allow the shuttle effect to be controlled. In this study, the applications of various conductive polymers prepared via the simple yet sophisticated electropolymerisation (EP) technology are systematically investigated based on the main components of LiSBs (cathodes, anodes, separators, and electrolytes). Finally, the potential application of EP technology in next-generation batteries is comprehensively discussed.

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“…PTBT as an organosulphur cathode on its aggregation behaviour and charge transport (Figure 4b) [26]. The morphology of a polymer can significantly affect its conductive behaviour.…”

Section: Schütze Et Al Investigated the Effect Of The Regiochemistry ...mentioning

confidence: 99%

Electropolymerisation Technologies for Next-Generation Lithium–Sulphur Batteries

Kim,

Lee

2023

Polymers

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“…Also, there is no commonly accepted equilibration method due to the rather different microstructures of SCPs, e.g., from semicrystalline polymers to amorphous glasses, and the wide range of glass-transition temperature T g (or melting points) for different SCPs . With respect to the third step, many alternatives are available including semiempirical, , tight binding, , and DFT methods, , which reduce the comparability between different works. The aforementioned inhomogeneities and implemental difficulties resulted in studying a limited number of models, i.e., only a few high-quality polymer models per investigation have been possible. , Thus, having fewer models studied and incomparable models generated in different studies has obstructed the development of structure–electronic property relationships required for formulating SCP design rules.…”

Section: Introductionmentioning

confidence: 99%

From Chemical Drawing to Electronic Properties of Semiconducting Polymers in Bulk: A Tool for Chemical Discovery

Burke,

Makki,

Troisi

2024

J. Chem. Theory Comput.

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A quantum chemistry (QC)/molecular dynamics (MD) scheme is developed to calculate electronic properties of semiconducting polymers in three steps: (i) constructing the polymer force field through a unified workflow, (ii) equilibrating polymer models, and (iii) calculating electronic structure properties (e.g., density of states and localization length) from the equilibrated models by QC approaches. Notably, as the second step of this scheme is generally the most time-consuming one, we introduce an alternative method to compute thermally averaged electronic properties in bulk, based on the simulation of a polymer chain in the solution of its repeat units, which is shown to reproduce the microstructure of polymer chains and their electrostatic effect (successfully tested for five benchmark polymers) 10 times faster than state-of-the-art methods. In fact, this scheme offers a consistent and speedy way of estimating electronic properties of polymers from their chemical drawings, thus ensuring the availability of a homogeneous set of simulations to derive structure−property relationships and material design principles. As an example, we show how the electrostatic effect of the polymer chain environment can disturb the localized electronic states at the band tails and how this effect is more significant in the case of diketopyrrolopyrrole polymers as compared to indacenodithiophene and dithiopheneindenofluorene ones.

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“…The thiophene ring in TBT acts as the conjugated backbone, while benzenethiol is the organosulfur-based side chain. In recent work, some of us have shown that out of different regioregularities of thiophene groups, a head-to-tail/head-to-tail regularity leads to a crystalline phase, while a head-to-head/tail-to-tail regularity shows no long-range order …”

Section: Introductionmentioning

confidence: 99%

Solvation Structure of Conjugated Organosulfur Polymers for Lithium–Sulfur Battery Cathodes

Gayen

Schütze

Groh

et al. 2023

ACS Appl. Polym. Mater.

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Lithium–sulfur (Li/S) batteries constitute a promising, next-generation energy storage technology due to their high theoretical energy density and low cost. To increase sustainability, processability, and battery performance, conducting organic polymers have become a focus of research for the development of better cathode materials. Here, we investigate the solvation structure of a single conjugated poly(4-(thiophen-3-yl)benzenethiol) (PTBT) polymer as a high-potential macromolecular candidate for synthesizing optimized cathodes in Li/S batteries. Using molecular dynamics (MD) simulation with newly optimized force-field parameters, we examine the effects of polymer length and various molar fractions of the popular dimethoxyethane (DME) and dioxolane (DOL) solvents on the structure of the PTBT polymer at a temperature of 300 K. We characterize basic polymeric properties as well as the composition-dependent solvent adsorption structure and thermodynamics and uncover significant tunability by the solvent. Importantly, we find an interesting cosolvency effect, namely that a solvent mixture composed of 25% DME and 75% DOL leads to maximum swelling behavior, which should be important for optimizing cathode fractality and permeability in applications. Our study thus reveals intriguing polymer–solvent correlations and serves as an important prerequisite for future MD studies of realistic polymeric cathode structures and processes, e.g., toward charge transport in vulcanized (S-linked) network topologies.

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How Regiochemistry Influences Aggregation Behavior and Charge Transport in Conjugated Organosulfur Polymer Cathodes for Lithium–Sulfur Batteries

Cited by 13 publications

References 111 publications

Electropolymerisation Technologies for Next-Generation Lithium–Sulphur Batteries

Electropolymerisation Technologies for Next-Generation Lithium–Sulphur Batteries

From Chemical Drawing to Electronic Properties of Semiconducting Polymers in Bulk: A Tool for Chemical Discovery

Solvation Structure of Conjugated Organosulfur Polymers for Lithium–Sulfur Battery Cathodes

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