A Critical Analysis about the Underestimated Role of the Electrolyte in Batteries Based on Organic Materials

Gerlach, Patrick; Balducci, Andrea

doi:10.1002/celc.202000166

Cited by 18 publications

(13 citation statements)

References 70 publications

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“…However, solvents with larger δ h values, such as isopropyl alcohol, 1,2-propanediol, ethanol, and dimethyl sulfoxide (DMSO), do not dissolve PTMA, but not all of these solvents are suitable battery electrolytes. Other considerations include the electrolyte’s dielectric constant (ε) and electrochemical stability. ,− For example, DMSO is predicted to be a nondissolving solvent and has been studied as an electrolyte solvent in Li–O 2 batteries. , However, our attempts with DMSO have yielded no PTMA electroactivity, possibly due to a reaction of the oxoammonium cation with the DMSO . We also tested glycerol carbonate/dimethyl carbonate (DMC) electrolyte (DMC must be added to reduce the viscosity); however, the resulting electrochemical performance was still poor.…”

Section: Results and Discussionmentioning

confidence: 99%

“…The most commonly investigated macromolecular radical is poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PTMA) owing to its simple synthesis, high theoretical capacity (111 mA·h·g –1 ), and fast charge–discharge kinetics. − ORBs use common lithium-ion battery electrolytes, such as linear and cyclic carbonates. However, a large number of studies have observed dissolution of the macromolecular radical into the electrolyte (see Table S1 for specific examples), resulting in pronounced capacity fade with cycling. ,− ,− Therefore, it is important to identify nondissolving electrolytes for practical ORB design. Unfortunately, the PTMA–solvent interactions have not been quantified, and the solubility parameter of PTMA is unknown.…”

Section: Introductionmentioning

confidence: 99%

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Nitroxide Radical Polymer–Solvent Interactions and Solubility Parameter Determination

et al. 2020

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Redox-active polymers such as macromolecular nitroxide radicals have been studied as electrode materials for organic batteries and electronics. Polymer−solvent interactions are essential to processing and device performance, but macromolecular nitroxide radical−solvent interactions are currently not well described. In this work, the Hildebrand and Hansen solubility parameters of poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PTMA), oxidized PTMA (PTMA + ), and PTMA's precursor (PTMPM) are determined using both experimental and group contribution methods for the first time. This work indicates that the hydrogen-bonding Hansen solubility parameter (δ h ) and the solubility sphere radii (R) provide the best prediction of the macromolecular radical's interaction with solvents. From these solubility parameters, the group contribution values for the nitroxide and oxoammonium cation were then calculated. It is shown that this information allows for the prediction of polymer−solvent interactions for other nitroxide-based macromolecular radicals. Finally, the discovered solubility parameters are used to predict PTMA electrode formulations for batteries that outperform controls.

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Section: Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Nitroxide Radical Polymer–Solvent Interactions and Solubility Parameter Determination

et al. 2020

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“…[1] In the light of promoting efficient, safe, and low-polluting electrochemical energy storage systems, [2] electroactive organic materials (EOMs) have sparked considerable attention in recent compounds, [53] and the most recently reported N-substituted salts of viologen derivatives. [52] Since 2008 (a year witnessed as the modern area revival of EOMs), dozens of review articles have been published from different perspectives (e.g., molecular design, [20,22,23,27,41,42,49,50,[54][55][56][57][58][59][60][61][62][63][64][65][66][67][68][69] sustainability, [70,71] opportunity, [3,[72][73][74] practicability, [75][76][77][78] and technology [79][80][81][82] ). It is worth noting that most reviews are focused on OPEMs with less consideration to ONEMs, except two reviews dedicated to ONEMs for Na/K-ion batteries, [37,83] yet presenting only a summary of advances and no critical discussion or suggested solutions for remai...…”

Section: Introductionmentioning

confidence: 99%

Organic Negative Electrode Materials for Metal‐Ion and Molecular‐Ion Batteries: Progress and Challenges from a Molecular Engineering Perspective

Lakraychi

Dolhem

Vlad

et al. 2021

Advanced Energy Materials

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Thanks to their versatility and flexibility, EOMs have shown broad applicability as bulky solid [3] or dissolved [4,5] active material, in aqueous [6][7][8] or non-aqueous electrolyte, [9][10][11] for portable and stationary batteries, respectively. In practice, OEMs are explored as main active materials in LIBs, [12] beyond Li systems (e.g., hydrogen, [13,14] Na-ion, [15][16][17][18][19] K-ion, [20][21][22][23][24] and multivalent batteries like magnesium, [25,26] zinc, [27] or aluminum [28,29] ) and also redox flow batteries; [30] or as supporting active materials such as redox mediators for Li-O 2 batteries, [31] Li-source sacrificial materials for Li-ion capacitor [32] and redox electrolytes for high-energy supercapacitors. [33] In contrast to the state-of-the-art inorganic materials, whose reactivity is based on redox of transition metal center and consequently Li + de/insertion, [34,35] the redox reaction of EOMs is based on the charge state change of the redox moiety, [12] for which the charge compensation during redox can be either made by cations, referring to n-type systems, or by anions, belonging then to p-type system, according to the proposed Hünig's classification. [36,37] The richness of organic chemistry coupled with molecular modifications have provided thus far a plethora of molecules and architectures operating within a large potential window with high specific capacities, extended cycling stability and high cycling rate. This has enabled building a broad database of electroactive compounds for both positive and negative electrode applications. Organic positive electrode materials (OPEMs) certainly benefit from larger attention since there are more possibilities to explore, for example, conducting polymers, [38,39] nitroxides, and other stable organic radicals, [40][41][42][43] sulfur compounds, [11] as well as conjugated amines, [44][45][46] conjugated sulfonamides, [47] nitro-aromatics, [48] and carbonyls. [49,50] The latter being certainly the most explored category owing to major advances attained so far but also to opportunities for further improvements to attain simultaneously high energy and power densities combined with good cycling stability. [12] On the opposite side, the chemical library is less rich for organic negative electrode materials (ONEMs), primarily due to much focus on positive electrode chemistries, for which many issues and strategies are to be addressed and explored, respectively. Today, the ONEMs database counts fewer redox families as OPEMs one, with also less specific chemistries within each class. To cite some: the most studied conjugated dicarboxylates, [51] Hückel-stabilized Schiff base, [52] nitrogen-redox azo

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“…As a facile approach for the control of solubility of organic redox-active materials, a deeper look at the active material–electrolyte interactions would open the possibility to choose the ideal electrolyte without the need for further chemical modifications, maybe even without cross-linking. , In the literature, some studies are available which shed light on the interactions of the solvent molecules in the electrolytes, but they do not discuss in detail why a certain redox polymer or organic material is soluble in an electrolyte. − Recently, a study suggested that the electrolytes can help to access a possible second oxidation of single molecules with heterocyclic ring systems by adjusting the donor number and the salt concentration of the electrolyte, which emphasizes the power of the electrolyte-active material interplay …”

Section: Introductionmentioning

confidence: 99%

Insights into the Solubility of Poly(vinylphenothiazine) in Carbonate-Based Battery Electrolytes

Perner

Diddens

Otteny

et al. 2021

ACS Appl. Mater. Interfaces

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Organic materials are promising candidates for next-generation battery systems. However, many organic battery materials suffer from high solubility in common battery electrolytes. Such solubility can be overcome by introducing tailored high-molecular-weight polymer structures, for example, by crosslinking, requiring enhanced synthetic efforts. We herein propose a different strategy by optimizing the battery electrolyte to obtain insolubility of non-cross-linked poly(3-vinyl-N-methylphenothiazine) (PVMPT). Successive investigation and theoretical insights into carbonate-based electrolytes and their interplay with PVMPT led to a strong decrease in the solubility of the redox polymer in ethylene carbonate/ethyl methyl carbonate (3:7) with 1 M LiPF 6 . This allowed accessing its full theoretical specific capacity by changing the charge/discharge mechanism compared to previous reports. Through electrochemical, spectroscopic, and theoretical investigations, we show that changing the constituents of the electrolyte significantly influences the interactions between the electrolyte molecules and the redox polymer PVMPT. Our study demonstrates that choosing the ideal electrolyte composition without chemical modification of the active material is a successful strategy to enhance the performance of organic polymer-based batteries.

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A Critical Analysis about the Underestimated Role of the Electrolyte in Batteries Based on Organic Materials

Cited by 18 publications

References 70 publications

Nitroxide Radical Polymer–Solvent Interactions and Solubility Parameter Determination

Nitroxide Radical Polymer–Solvent Interactions and Solubility Parameter Determination

Organic Negative Electrode Materials for Metal‐Ion and Molecular‐Ion Batteries: Progress and Challenges from a Molecular Engineering Perspective

Insights into the Solubility of Poly(vinylphenothiazine) in Carbonate-Based Battery Electrolytes

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