Design and properties of functional zwitterions derived from ionic liquids

Ohno, Hiroyuki; Yoshizawa‐Fujita, Masahiro; Kohno, Yuki

doi:10.1039/c7cp08592c

Cited by 80 publications

(75 citation statements)

References 85 publications

(132 reference statements)

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“…In Figure 5(a), we display the ideal NE conductivity for Motifs B and C as a function of r , wherein it is seen that the NE conductivity for the B polymer is greater than that of the C polymer. This result is qualitatively consistent with the Ohno experiment discussed in the introduction . Based on the results discussed in the context of Figure , we can understand the architectural influence on ionic conductivities to arise mainly from the much higher mobilities displayed by TFSI − in Motif B relative to the counterpart mobility of Li + in Motif C. We recall that such differences were shown to arise as a consequence of the relative TFSI − ‐ZI + and Li + ‐ZI − interactions.…”

Section: Resultsmentioning

confidence: 99%

“…Their ionic properties and hydrophilicity have made them targets for use in organic electronics, catalysis, battery electrolytes, surfactants, drug‐delivery, and antifouling coatings, among other applications . ZI‐incorporated polymers (polyZIs) have also been investigated as novel materials for chromatography, drug‐delivery, self‐assembled microstructures, and battery electrolytes …”

Section: Introductionmentioning

confidence: 99%

“…To render a comparison to the experimental results of Ohno discussed in the introduction, we compute the ideal, Nernst–Einstein (NE), conductivities. The NE conductivity is calculated using

σ_{NE} = \frac{1}{{Vk}_{B} T} \sum_{i}^{I} N_{i} q_{i}^{2} D_{i},

with a number of ion types I , system volume V , Boltzmann constant k B = 1.38 × 10 −23 J/K, temperature T , number of ions of type i N i , charges q i , and diffusivities D i .…”

Section: Introductionmentioning

confidence: 99%

“…[1][2][3][4] ZI-incorporated polymers (polyZIs) have also been investigated as novel materials for chromatography, drug-delivery, self-assembled microstructures, and battery electrolytes. [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] ZI-containing ionogels have shown promise in eliminating the trade-off between mechanical strength and conductivity through noncovalent crosslinking and ion-dissociation. 7,[22][23][24][25] The addition of ZIs to electrolyte formulations also purportedly improves cycling performance and energy density by increasing Coulombic efficiencies for lithium plating/stripping reactions.…”

mentioning

confidence: 99%

“…[18][19][20]32,35 In this context, we note a study reported by Ohno and coworkers, which highlighted a surprising impact of polymer architecture on ionic conductivity. 16 Specifically, they reported ionic conductivity for salt-polyZI blends of lithium bistrifluoromethylsulfonylimide (Li + -TFSI − ) with polyZIs composed of imidazolium cationic and triflate-like anionic moieties, arranged in a pendant configuration from the backbone as follows: anion-cation (Motif B) and cation-anion (Motif C). The ionic conductivity of Motif C (Fig.…”

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confidence: 99%

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Ion transport mechanisms in salt‐doped polymerized zwitterionic electrolytes

Keith

Ganesan

2020

Journal of Polymer Science

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Polyzwitterions (polyZIs), macromolecules with repeating ampholytic monomers, are a novel class of materials with attractive properties for battery electrolytes. In this study, we probe the ion transport characteristics and underlying mechanisms in two salt‐doped (Li+‐TFSI−) polyZIs of similar composition with contrasting zwitterion (ZI) ionic organization: pendant monomers organized via backbone‐anion‐cation (B‐ZI−‐ZI+, Motif B) and backbone‐cation‐anion (B‐ZI+‐ZI−, Motif C). Within both Motifs B and C, the counterion of the pendant‐end ZI moiety shows higher mobility. Similarly, when comparing Li+ or TFSI− across motifs, it is seen that the respective pendant‐end counterion possesses higher mobility than its backbone‐adjacent counterpart. Furthermore, when comparing counterions to same‐position ZI moieties, TFSI− is seen to possess higher mobility than Li+ in each case, a result rationalized by invoking the lower interaction strength between the TFSI− and ZI+. Analysis of ion‐transport mechanisms demonstrate that the mobility of countercharges to the pendant‐end ZI moiety correlates with the ion‐association relaxation timescale, similar to ideas noted in polymerized ionic liquids in past studies. However, the mobility of countercharges to the backbone‐adjacent ZI moiety is shown to be correlated with a cage relaxation time, which incorporates the combined effects of frustrated motion due to the presence of the polymer backbone and pendant‐end ZI moiety and the higher mobility in a population of lightly ZI‐coordinated ions. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020, 58, 578–588

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…To render a comparison to the experimental results of Ohno discussed in the introduction, we compute the ideal, Nernst–Einstein (NE), conductivities. The NE conductivity is calculated using

σ_{NE} = \frac{1}{{Vk}_{B} T} \sum_{i}^{I} N_{i} q_{i}^{2} D_{i},

with a number of ion types I , system volume V , Boltzmann constant k B = 1.38 × 10 −23 J/K, temperature T , number of ions of type i N i , charges q i , and diffusivities D i .…”

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Ion transport mechanisms in salt‐doped polymerized zwitterionic electrolytes

Keith

Ganesan

2020

Journal of Polymer Science

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Advances in Functional Organosulfur‐Based Mediators for Regulating Performance of Lithium Metal Batteries

Fan,

Zhang,

Fan

et al. 2024

Advanced Materials

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Rechargeable lithium metal batteries (LMBs) are promising next‐generation energy storage systems due to their high theoretical energy density. However, their practical applications are hindered by lithium dendrite growth and various intricate issues associated with the cathodes. These challenges can be mitigated by using organosulfur‐based mediators (OSMs), which offer the advantages of abundance, tailorable structures, and unique functional adaptability. These features enable the rational design of targeted functionalities, enhance the interfacial stability of the lithium anode and cathode, and accelerate the redox kinetics of electrodes via alternative reaction pathways, thereby effectively improving the performance of LMBs. Unlike the extensively explored field of organosulfur cathode materials, OSMs have garnered little attention. This review systematically summarizes recent advancements in OSMs for various LMB systems, including lithium–sulfur, lithium–selenium, lithium–oxygen, lithium‐intercalation cathode batteries, and other LMB systems. It briefly elucidates the operating principles of these LMB systems, the regulatory mechanisms of the corresponding OSMs, and the fundamentals of OSMs activity. Ultimately, strategic optimizations are proposed for designing novel OSMs, advanced mechanism investigation, expanded applications, and the development of safe battery systems, thereby providing directions to narrow the gap between rational modulation of organosulfur compounds and their practical implementation in batteries.

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Designing Zwitterionic Gel Polymer Electrolytes with Dual‐Ion Solvation Regulation Enabling Stable Sodium Ion Capacitor

Liu

Cheng

Mao

et al. 2023

Advanced Energy Materials

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Sodium ion capacitors (SICs) show high energy/power densities owing to the special dual‐ion energy storage mechanism with cation intercalation and anion adsorption. However, the strong ion‐solvent interactions make it difficult for interfacial ion desolvation, which not only limits the ion transport kinetics, but also results in the solvent co‐intercalation into electrode materials. Here, an advanced zwitterionic gel polymer electrolyte (GPE) is developed to weaken the ion‐solvent interactions. The 3‐(1‐vinyl‐3‐imidazolio) propanesulfonate (VIPS) zwitterions help to lower the desolvation barriers, enabling fast ion transfer kinetics for constructing stable quasi‐solid‐state SICs. Furthermore, the decomposition of VIPS contributes to the formation of S‐ and N‐based inorganic interphase on the surface of hard carbon anode, which reduces the Na+ ion diffusion barriers and improves electrochemical compatibility. The designed Zwitterionic GPE can stabilize 4.0 V hard carbon//activated carbon SICs with 95.3% capacity retention after 9000 cycles, showing a high energy density of 140.2 Wh kg−1. This study highlights the regulation of ion‐solvent chemistry and provides a guiding principle in electrolyte design for advanced hybrid ion capacitors.

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Design and properties of functional zwitterions derived from ionic liquids

Cited by 80 publications

References 85 publications

Ion transport mechanisms in salt‐doped polymerized zwitterionic electrolytes

Ion transport mechanisms in salt‐doped polymerized zwitterionic electrolytes

Advances in Functional Organosulfur‐Based Mediators for Regulating Performance of Lithium Metal Batteries

Designing Zwitterionic Gel Polymer Electrolytes with Dual‐Ion Solvation Regulation Enabling Stable Sodium Ion Capacitor

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