Theoretical and experimental evidence for irreversible lithiation of the conformationally flexible polyimide: Impact on battery performance

Shestakov, Alexander F.; Romanyuk, Olga; Mumyatov, Alexander V.; Luchkin, Sergey Yu.; Slesarenko, A. A.; Yarmolenko, O. V.; Stevenson, Keith J.; Troshin, Pavel A.

doi:10.1016/j.jelechem.2019.01.063

Cited by 11 publications

(11 citation statements)

References 17 publications

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“…Increasing the flexibility of the polymer backbone in PTCDA- n But and PTCDA- n Hex also substantially increases the diffusion-limited processes in Li + cells, which strongly correlates with the substantial loss of retention at faster charge/discharge rates for these materials. Li + is likely to have a solvation shell that is difficult to shed, which could result in a more intact solvation shell upon insertion into the polymers. , Previous work suggests that highly flexible diimide polymers can fold around ions, effectively acting like a solvating polymer and leading to slow ion diffusion. This likely accounts for the poor performance of PTCDA- n But and PTCDA- n Hex in Li half-cells.…”

Section: Resultsmentioning

confidence: 99%

“…Organic electrode materials have generated increased interest due to their low cost, tunable and flexible structures, and high theoretical specific capacities. − ,,, In addition, organic materials are compatible with a wide range of charge-compensating ions. These qualities make organic electroactive materials versatile candidates for diverse applications, including high-power energy storage and electrocatalysis. ,− However, the structural tunability of organic electrode materials necessitates a better understanding of how polymer crystallinity, porosity, dimensionality, and flexibility affect the redox properties. ,,− …”

Section: Introductionmentioning

confidence: 99%

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Flexible Backbone Effects on the Redox Properties of Perylenediimide-Based Polymers

Kim

Milner

2023

ACS Appl. Mater. Interfaces

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Organic electrode materials are appealing candidates for a wide range of applications, including heterogeneous electrocatalysis and electrochemical energy storage. However, a narrow understanding of the structure−property relationships in these materials hinders the full realization of their potential. Herein, we investigate a family of insoluble perylenediimide (PDI) polymers to interrogate how backbone flexibility affects their thermodynamic and kinetic redox properties. We verify that the polymers generally access the highest percentage of redox-active groups with K + ions (vs Na + and Li + ) due to its small solvation shell/energy and favorable soft−soft interactions with reduced PDI species. Through cyclic voltammetry, we show that increasing the polymer flexibility does not minimize barriers to ion-insertion processes but rather increases the level of diffusion-limited processes. Further, we propose that the condensation of imides to iminoimides can truncate the imide polymer chain growth for certain diamine monomers, leading to greater polymer solubilization and reduced cycling stability. Together, our results provide insight into how polymer flexibility, ion−electrode interactions, and polymerization side reactions dictate the redox properties of PDI polymers, paving the way for the development of next-generation organic electrode materials.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Flexible Backbone Effects on the Redox Properties of Perylenediimide-Based Polymers

Kim

Milner

2023

ACS Appl. Mater. Interfaces

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“…Li + is likely to have a solvation shell that is difficult to shed, which could result in a more intact solvation shell when inserting into the polymers. 65,66 Previous work suggests that highly flexible diimide polymers can fold around ions, 31 effectively acting like a solvating polymer and leading to slow ion diffusion. This likely accounts for the poor performance of PTCDA-nBut and PTCDA-nHex in Li half cells.…”

Section: Resultsmentioning

confidence: 99%

“…These qualities make organic electroactive materials versatile candidates for diverse applications, including high-power energy storage and electrocatalysis. 4,[23][24][25][26][27][28][29][30][31] However, the structural tunability of organic electrode materials necessitates a better understanding of how polymer crystallinity, porosity, dimensionality, and flexibility affect redox properties. 8,16,[31][32][33][34][35][36][37][38][39] Among organic electrode materials, diimides have been widely investigated due to their (electro)chemical stability.…”

Section: Introductionmentioning

confidence: 99%

“…4,[23][24][25][26][27][28][29][30][31] However, the structural tunability of organic electrode materials necessitates a better understanding of how polymer crystallinity, porosity, dimensionality, and flexibility affect redox properties. 8,16,[31][32][33][34][35][36][37][38][39] Among organic electrode materials, diimides have been widely investigated due to their (electro)chemical stability. In particular, soft perylene diimide (PDI) polymers are very redox-stable, especially when paired with soft cations like K + .…”

Section: Introductionmentioning

confidence: 99%

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Flexible Backbone Effects on the Redox Properties of Perylene Diimide-Based Polymers

Kim

Milner

2023

Preprint

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Organic electrode materials are appealing candidates for a wide range of applications, including heterogeneous electroca-talysis and electrochemical energy storage. However, the narrow understanding of structure-property relationships in these materials hinders the full realization of their potential. Herein, we investigate a family of insoluble, perylene diimide (PDI) polymers to interrogate how backbone flexibility affects their thermodynamic and kinetic redox properties. We verify that the polymers generally access the highest percentage of redox-active groups with K+ (versus Na+ and Li+) due to its small solvation shell/energy and favorable soft-soft interactions with reduced PDI species. Through cyclic voltammetry, we show that increasing polymer flexibility does not minimize barriers to ion-insertion processes but ra-ther increases diffusion-limited processes. Further, we propose that the condensation of imides to iminoimides can trun-cate imide polymer chain growth for certain diamine monomers, leading to greater polymer solubilization and reduced cycling stability. Together, our results provide insight into how polymer flexibility, ion-electrode interactions, and polymerization side reactions dictate the redox properties of PDI polymers, paving the way for the development of next-generation organic electrode materials.

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Gelled tetraglyme-based electrolyte for organic electrode materials

Baymuratova

Khatmullina²,

Tulibaeva³

et al. 2022

Russ Chem Bull

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Theoretical and experimental evidence for irreversible lithiation of the conformationally flexible polyimide: Impact on battery performance

Cited by 11 publications

References 17 publications

Flexible Backbone Effects on the Redox Properties of Perylenediimide-Based Polymers

Flexible Backbone Effects on the Redox Properties of Perylenediimide-Based Polymers

Flexible Backbone Effects on the Redox Properties of Perylene Diimide-Based Polymers

Gelled tetraglyme-based electrolyte for organic electrode materials

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