Visualization of structural changes and degradation of porphyrin-based battery electrodes

Philipp, Tom; Neusser, Gregor; Abouzari‐Lotf, Ebrahim; Shakouri, Shirin; Wilke, Franziska; Fichtner, Maximilian; Rüben, Mario; Mundszinger, Manuel; Biskupek, Johannes; Kaiser, Ute; Scheitenberger, Philipp; Lindén, Mika; Kranz, Christine

doi:10.1016/j.jpowsour.2022.231002

Cited by 11 publications

(8 citation statements)

References 54 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The small gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the TPMs and the fact that the charges in the redox process will be stabilized in the mesomeric core enable high redox activities via fast electron uptake and release [7a] . Facile redox of TPMs is well known, and complexes with promising redox behavior in diverse storage systems of Li, [9] Na, [10] K, [11] Mg [12] and Al [13] were reported recently. To mitigate the undesired solubility of TPMs, researchers have either polymerized the active materials in advance [14] or enabled polymerization in‐situ during cycling [8a,11,15] .…”

Section: Introductionmentioning

confidence: 99%

High Active Material Loading in Organic Electrodes Enabled by an in‐situ Electropolymerized π‐Conjugated Tetrakis (4‐Aminophenyl) Porphyrin

Smok

Abouzari‐Lotf

Frentzen

et al. 2023

Batteries & Supercaps

Self Cite

View full text Add to dashboard Cite

Porphyrin complexes have been widely studied as promising electrode material in diverse energy storage systems and chemistries. However, like other organic electrodes, porphyrins often suffer from low conductivity and, consequently, require a significant amount (typically 40 %) of electrochemically inactive conductive carbon that occupies volume and mass without storing energy. In this study, we investigate [5,10,15,20 tetrakis(4‐aminophenyl)‐porphyrin] (TAPP) and its metal complexes as redox‐active cathode materials to address the aforementioned issues. The lithium‐ion cells prepared with a high content of CuTAPP active material (70 wt %) demonstrate a stable discharge capacity of ∼120 mAh/g when cycling with a constant current density of 1000 mA/g. The material also showed superior rate capability, e. g., ∼60 mAh/g at 8 A/g. The results of DFT calculations and experimental analysis indicate that the degree of planarity of the metalloporphyrins directly correlates to their cycling stability. Moreover, the contribution from the central metal redox during the cycling is found to be the reason for the significantly higher performance of the Cu‐complex compared to the metal‐free complex. The findings of this study show a general approach for facing common conductivity challenges of organic electrodes and open up a pathway for practical application of organics electrode materials in energy storage application.

show abstract

Section: Introductionmentioning

confidence: 99%

High Active Material Loading in Organic Electrodes Enabled by an in‐situ Electropolymerized π‐Conjugated Tetrakis (4‐Aminophenyl) Porphyrin

Smok

Abouzari‐Lotf

Frentzen

et al. 2023

Batteries & Supercaps

Self Cite

View full text Add to dashboard Cite

show abstract

“…XRS is a bulk analysis technique that can be used semiquantitatively to monitor the level of electrochemical conversion and has only recently found application in organic materials . Although electron microscopy is extensively used to study the mechanism and degradation of inorganic active materials, its use in the field of organic electrode materials is somehow limited to qualitative assessments of electrode morphology, dissolution phenomena, and detection of passive layers. ,, …”

Section: Investigation Of the Electrochemical Mechanismmentioning

confidence: 99%

“…128 Although electron microscopy is extensively used to study the mechanism and degradation of inorganic active materials, its use in the field of organic electrode materials is somehow limited to qualitative assessments of electrode morphology, dissolution phenomena, and detection of passive layers. 52,129,130 As described above, there are a plethora of analysis techniques devoted to the determination of the reaction mechanism in organic electrode materials. However, only limited emphasis was put on the nature of the metal cations involved in the electrochemical process.…”

Section: Mechanismmentioning

confidence: 99%

Organic Cathodes, a Path toward Future Sustainable Batteries: Mirage or Realistic Future?

Bitenc,

Pirnat,

Lužanin

et al. 2024

Chem. Mater.

View full text Add to dashboard Cite

Organic active materials are seen as next-generation battery materials that could circumvent the sustainability and cost limitations connected with the current Li-ion battery technology while at the same time enabling novel battery functionalities like a bioderived feedstock, biodegradability, and mechanical flexibility. Many promising research results have recently been published. However, the reproducibility and comparison of the literature results are somehow limited due to highly variable electrode formulations and electrochemical testing conditions. In this Perspective, we provide a critical view of the organic cathode active materials and suggest future guidelines for electrochemical characterization, capacity evaluation, and mechanistic investigation to facilitate reproducibility and benchmarking of literature results, leading to the accelerated development of organic electrode active materials for practical applications.

show abstract

“…The close intermolecular distances (∼3.5 Å), such as those found in Cu porphyrin π‐stacks, [36] facilitate large spatial overlap between the highest occupied and lowest unoccupied molecular orbitals (HOMOs and LUMOs, respectively) on neighbouring molecules, which strongly affect the electronic properties of the material. [44] The aggregation of such rigid π‐structures (sometimes called self‐assembly [45] or self‐conditioning [36] ) during the battery operation[ 26 , 42 , 46 ] provides a powerful strategy for suppressing their undesired solubility. These structures are also presumed to enhance the electronic conduction during the charge‐discharge process and to improve retention of the structural integrity upon high rate cycling.…”

Section: Introductionmentioning

confidence: 99%

Molecular Engineering of Metalloporphyrins for High‐Performance Energy Storage: Central Metal Matters

et al. 2023

Self Cite

View full text Add to dashboard Cite

Porphyrin derivatives represent an emerging class of redox‐active materials for sustainable electrochemical energy storage. However, their structure–performance relationship is poorly understood, which confines their rational design and thus limits access to their full potential. To gain such understanding, we here focus on the role of the metal ion within porphyrin molecules. The A2B2‐type porphyrin 5,15‐bis(ethynyl)‐10,20‐diphenylporphyrin and its first‐row transition metal complexes from Co to Zn are used as models to investigate the relationships between structure and electrochemical performance. It turned out that the choice of central metal atom has a profound influence on the practical voltage window and discharge capacity. The results of DFT calculations suggest that the choice of central metal atom triggers the degree of planarity of the porphyrin. Single crystal diffraction studies illustrate the consequences on the intramolecular rearrangement and packing of metalloporphyrins. Besides the direct effect of the metal choice on the undesired solubility, efficient packing and crystallinity are found to dictate the rate capability and the ion diffusion along with the porosity. Such findings open up a vast space of compositions and morphologies to accelerate the practical application of resource‐friendly cathode materials to satisfy the rapidly increasing need for efficient electrical energy storage.

show abstract

Visualization of structural changes and degradation of porphyrin-based battery electrodes

Cited by 11 publications

References 54 publications

High Active Material Loading in Organic Electrodes Enabled by an in‐situ Electropolymerized π‐Conjugated Tetrakis (4‐Aminophenyl) Porphyrin

High Active Material Loading in Organic Electrodes Enabled by an in‐situ Electropolymerized π‐Conjugated Tetrakis (4‐Aminophenyl) Porphyrin

Organic Cathodes, a Path toward Future Sustainable Batteries: Mirage or Realistic Future?

Molecular Engineering of Metalloporphyrins for High‐Performance Energy Storage: Central Metal Matters

Contact Info

Product

Resources

About