Molecular Dynamics Study of a Dual‐Cation Ionomer Electrolyte

Chen, Xingyu; Chen, Fangfang; Jónsson, Erlendur; Forsyth, Maria

doi:10.1002/cphc.201600821

Cited by 10 publications

(5 citation statements)

References 36 publications

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“…We hypothesized that the strong interactions between lithium ions and ether oxygen atoms may cause an unexpected recoupling of the lithium diffusion dynamics with the polymer segmental motion, and this conclusion was supported by molecular dynamics (MD) simulations of similar ionomers . MD simulations of Li and Na ionic polymers with different compositions of co-cations were able to elucidate possible decoupling mechanisms and optimum compositions and sizes of the organic cation. , As shown in Figure , when the ratio of the Li ion to the ammonium co-cation is increased to 1:1 (vs 1:5), a hopping mechanism involving rearrangement of the Li coordination environment is possible along an interconnected cluster. This is believed to be the origin of the decoupling of the alkali metal cation from the bulk polymer dynamics.…”

Section: Anionic Single-ion Conductorsmentioning

confidence: 91%

“…24 MD simulations of Li and Na ionic polymers with different compositions of co-cations were able to elucidate possible decoupling mechanisms and optimum compositions and sizes of the organic cation. 25,26 As shown in Figure 3, when the ratio of the Li ion to the ammonium co-cation is increased to 1:1 (vs 1:5), a hopping mechanism involving rearrangement of the Li coordination environment is possible along an interconnected cluster. This is believed to be the origin of the decoupling of the alkali metal cation from the bulk polymer dynamics.…”

Section: "Mixed" Co-cation Approach To Decouple Li/na-ion Transport F...mentioning

confidence: 99%

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Innovative Electrolytes Based on Ionic Liquids and Polymers for Next-Generation Solid-State Batteries

et al. 2019

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Electrolytes based on organic solvents used in current Li-ion batteries are not compatible with the next-generation energy storage technologies including those based on Li metal. Thus, there has been an increase in research activities investigating solid-state electrolytes, ionic liquids (ILs), polymers, and combinations of these. This Account will discuss some of the work from our teams in these areas. Similarly, other metal-based technologies including Na, Mg, Zn, and Al, for example, are being considered as alternatives to Libased energy storage. However, the materials research required to effectively enable these alkali metal based energy storage applications is still in its relative infancy. Once again, electrolytes play a significant role in enabling these devices, and research has for the most part progressed along similar lines to that in advanced lithium technologies. Some of our recent contributions in these areas will also be discussed, along with our perspective on future directions in this field. For example, one approach has been to develop single-ion conductors, where the anion is tethered to the polymer backbone, and the dominant charge conductor is the lithium or sodium countercation. Typically, these present with low conductivity, whereas by using a copolymer approach or incorporating bulky quaternary ammonium co-cations, the effective charge separation is increased thus leading to higher conductivities and greater mobility of the alkali metal cation. This has been demonstrated both experimentally and via computer simulations. Further enhancements in ion transport may be possible in the future by designing and tethering more weakly associating anions to the polymer backbone. The second approach considers ion gels or composite polymer electrolytes where a polymerized ionic liquid is the matrix that provides both mechanical robustness and ion conducting pathways. The block copolymer approach is also demonstrated, in this case, to simultaneously provide mechanical properties and high ionic conductivity when used in combination with ionic-liquid electrolytes. The ultimate electrolyte material that will enable all high-performance solid-state batteries will have ion transport decoupled from the mechanical properties. While inorganic conductors can achieve this, their rigid, brittle nature creates difficulties. On the other hand, ionic polymers and their composites provide a rich area of chemistry to design and tune high ionic conductivity together with ideal mechanical properties.

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Section: Anionic Single-ion Conductorsmentioning

confidence: 91%

Section: "Mixed" Co-cation Approach To Decouple Li/na-ion Transport F...mentioning

confidence: 99%

Innovative Electrolytes Based on Ionic Liquids and Polymers for Next-Generation Solid-State Batteries

et al. 2019

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“…Although the low ionic conductivity hinders the application of anionic polymer electrolytes, its single ion conducting nature still makes this class of materials a favorite research area. One way to tune their ionic conductivities can be achieved through replacing a fraction of the alkali metal ions with a co‐cation, e.g., a bulky quaternary ammonium ionic liquid cation, or adding a neutral plasticizer molecule, as demonstrated both experimentally and computationally . MD simulations revealed that the size and amount of the co‐cation have a different effect on ionic interactions and transport within the solid electrolyte.…”

Section: Simulation‐assisted Design Of New Solid‐state Electrolytesmentioning

confidence: 99%

“…On one hand, the increased ammonium improved the total ionic conductivity due to the plasticizing effect, and on the other hand it disrupted ion aggregation and thus reduced the ability for Li + hopping. Therefore, an intermediate ammonium concentration of 50 mol% was suggested to maximize Li + ion conduction . Furthermore, it was also found that the size of the ammonium cation affects alkali metal ion diffusion; the larger ammonium cations led to more disruption of ion aggregation, and therefore the smaller ammonium cation is a better option to achieve higher conductivity in these systems …”

Section: Simulation‐assisted Design Of New Solid‐state Electrolytesmentioning

confidence: 99%

Toward High‐Energy‐Density Lithium Metal Batteries: Opportunities and Challenges for Solid Organic Electrolytes

et al. 2020

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The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/adma.201905219.With increasing demands for safe, high capacity energy storage to support personal electronics, newer devices such as unmanned aerial vehicles, as well as the commercialization of electric vehicles, current energy storage technologies are facing increased challenges. Although alternative batteries have been intensively investigated, lithium (Li) batteries are still recognized as the preferred energy storage solution for the consumer electronics markets and next generation automobiles. However, the commercialized Li batteries still have disadvantages, such as low capacities, potential safety issues, and unfavorable cycling life. Therefore, the design and development of electromaterials toward high-energy-density, long-life-span Li batteries with improved safety is a focus for researchers in the field of energy materials. Herein, recent advances in the development of novel organic electrolytes are summarized toward solid-state Li batteries with higher energy density and improved safety. On the basis of new insights into ionic conduction and design principles of organic-based solid-state electrolytes, specific strategies toward developing these electrolytes for Li metal anodes, high-energy-density cathode materials (e.g., high voltage materials), as well as the optimization of cathode formulations are outlined. Finally, prospects for next generation solid-state electrolytes are also proposed.

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“…Noor et al selected poly(2-acrylamido-2-methyl-1-propane-sulfonate) (PAMPS) homopolymer [609] or PAMPS with polyvinyl sulfonate [610] as a polymer backbone. With the addition of a small amount of a tetraglyme plasticizer, the conductivity reached 10 −5 S cm −1 at 50 °C; however, tetraglyme displays no effect on the Li + dynamics in PAMPS-based ionomers, the reasons for which have been explained by molecular dynamics calculations [611,612,613]. Usually, these polymers are tested in Na/Na symmetric cells to verify their compatibility with sodium.…”

Section: Sodium-ion Batteriesmentioning

confidence: 99%

Building Better Batteries in the Solid State: A Review

et al. 2019

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Most of the current commercialized lithium batteries employ liquid electrolytes, despite their vulnerability to battery fire hazards, because they avoid the formation of dendrites on the anode side, which is commonly encountered in solid-state batteries. In a review two years ago, we focused on the challenges and issues facing lithium metal for solid-state rechargeable batteries, pointed to the progress made in addressing this drawback, and concluded that a situation could be envisioned where solid-state batteries would again win over liquid batteries for different applications in the near future. However, an additional drawback of solid-state batteries is the lower ionic conductivity of the electrolyte. Therefore, extensive research efforts have been invested in the last few years to overcome this problem, the reward of which has been significant progress. It is the purpose of this review to report these recent works and the state of the art on solid electrolytes. In addition to solid electrolytes stricto sensu, there are other electrolytes that are mainly solids, but with some added liquid. In some cases, the amount of liquid added is only on the microliter scale; the addition of liquid is aimed at only improving the contact between a solid-state electrolyte and an electrode, for instance. In some other cases, the amount of liquid is larger, as in the case of gel polymers. It is also an acceptable solution if the amount of liquid is small enough to maintain the safety of the cell; such cases are also considered in this review. Different chemistries are examined, including not only Li-air, Li–O2, and Li–S, but also sodium-ion batteries, which are also subject to intensive research. The challenges toward commercialization are also considered.

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Molecular Dynamics Study of a Dual‐Cation Ionomer Electrolyte

Cited by 10 publications

References 36 publications

Innovative Electrolytes Based on Ionic Liquids and Polymers for Next-Generation Solid-State Batteries

Innovative Electrolytes Based on Ionic Liquids and Polymers for Next-Generation Solid-State Batteries

Toward High‐Energy‐Density Lithium Metal Batteries: Opportunities and Challenges for Solid Organic Electrolytes

Building Better Batteries in the Solid State: A Review

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