Incipient microphase separation in short chain perfluoropolyether-block-poly(ethylene oxide) copolymers

Chintapalli, Mahati; Timachova, Ksenia; Olson, Kevin R.; Banaszak, M.; Thelen, Jacob L.; Mecham, Sue J.; DeSimone, Joseph M.; Balsara, Nitash P.

doi:10.1039/c7sm00738h

Cited by 8 publications

(11 citation statements)

References 47 publications

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“…A similar trend with temperature has also been observed by Balsara and group for PFPE E10 -Diol systems. [54] In summary, the above WAXS characterizations suggest that there is a similar chain packing density for all polymers at 30 °C. The polymers M0I1, M1I3, M3I1 show no preferred orientations, polymer M1I1, and polymer M1I0 show prominent preferred orientations.…”

Section: Polymer Nanostructurementioning

confidence: 64%

Effects of Polymer Coating Mechanics at Solid‐Electrolyte Interphase for Stabilizing Lithium Metal Anodes

Huang

Choudhury

Paul

et al. 2021

Advanced Energy Materials

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Lithium metal batteries are next‐generation energy storage devices that rely on the stable electrodeposition of lithium metal during the charging process. The major challenge associated with this battery chemistry is related to the uneven deposition that leads to dendritic growth and poor coulombic efficiency (CE). A promising strategy for addressing this challenge is utilizing a polymer coating on the anodic surface. While several works in the past have evaluated polymer coatings, the requirements for polymer design are still unclear. In this work, the effect of polymer dynamics on lithium metal deposition is specifically investigated. Electrolyte (solvent) blocking perfluoropolyether polymer networks with evenly spaced H‐bonding sites of various strengths are designed, resulting in significant differences in the molecular ordering, as analyzed by X‐ray scattering measurements. The differences in the H‐bonding strength directly impact the mechanical properties of these materials, thus providing a controlled set of samples with a range of polymer dynamics for electrodeposition studies. Finally, a systematic evaluation of the lithium metal electrodeposition quality with these polymers as anodic coating shows that polymers with flowability or faster polymer dynamics exhibit higher CE. These experimental findings provide rational design principles for soft polymer coatings on lithium metal anodes.

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Section: Polymer Nanostructurementioning

confidence: 64%

Effects of Polymer Coating Mechanics at Solid‐Electrolyte Interphase for Stabilizing Lithium Metal Anodes

Huang

Choudhury

Paul

et al. 2021

Advanced Energy Materials

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“…In linear chains, the sum over all matrix elements in s 0,+ is connected to whole chain scattering~g 1 . This formula has been found many times in the literature [3,21]. For clarity, I calculated the scattering functions for the three materials and their mixtures.…”

Section: Examplesmentioning

confidence: 82%

“…So, if the phase boundary is crossed, the approach is invalid and does not predict the scattering function anymore. Good comparisons between calculations and experiments can be found in [21].…”

Section: Examplesmentioning

confidence: 87%

Scattering of multicomponent polymer blends

Frielinghaus

2021

Colloid Polym Sci

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The random phase approximation for polymer blends was developed by H. Benoît and described small angle scattering functions as well as mean field phase boundaries. It is a pure mean field theory that loses validity close to the real phase boundaries due to strong fluctuations. However, it gives a very clear roadmap about phase diagrams and scattering functions. A simplification of the random phase approximation is discussed that comes into effect when several polymers are mixed that involve a rather low number of chemically different repeat units. Then, the correlation functions of the same repeat unit pairs can be added up in a specific way such that the overall complexity for the calculations is reduced. The scattering functions and mean field phase boundaries are discussed within this concept. Graphical abstract

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“…Carbonate PFPAEs were extensively used by the DeSimone research group (Scheme , reaction 1). − ,− Indeed, this specific end-group enabled them to use it as a polymer electrolyte in a mixture with the salt LiTFSI for lithium batteries. ,,, These compounds exhibited low T g and good thermal stability up to 200 °C. The transference number t + , which is defined as the ratio of the electric current derived from the cation to the total electric current, was near unity.…”

Section: Condensation Reactionsmentioning

confidence: 99%

“…These polymers with hydroxyl and carbonate as end groups were studied by wide-angle X-ray scattering (WAXS). They exhibited a significant scattering intensity certainly caused by a microphase separation between the fluorinated phase and the hydrogenated one . Nonetheless, the insulation created by the insertion of ethylene oxide units (Fluorolink or Fomblin ZDOLTX) between the electron-withdrawing effect of the fluoropolymer (Fomblin ZDOL) and the alcohol group provides similar reactivity to hydrogenated alcohols.…”

Section: Nucleophilic Reactionsmentioning

confidence: 99%

Diversity of Synthetic Approaches to Functionalized Perfluoropolyalkylether Polymers

et al. 2021

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Perfluoropolyalkylethers (PFPAEs) are a class of fluorinated polymers having −OCF2–, −OCF2CF2–, and −OCF2CF(CF3)– as common chain units. The ether linkages distinguish them from other famous fluorinated polymers such as poly(tetrafluoroethylene). Their higher mobility highlighted by below zero glass transition temperatures permit them to be noncrystalline, which makes them easy to use for many applications. They possess interesting tribological properties, combined with an excellent thermal and chemical stability, make them very useful as lubricants. However, after chemical modifications, they also demonstrated to be very useful in numerous applications as surfactants, electrolytes, high performance coatings, vitrimers, or microfluidic devices, to give a few examples. This Perspective aims to summarize all the chemical modifications reported on these PFPAEs to provide a new insight into their potential utility in emerging fields. Indeed, the end group can modulate the properties of PFPAE-based materials such as lubricity, superhydrophobicity, biofouling, antibacterial activity, amphiphilicity, and the ability to react further with comonomers under photochemical and thermal processes. It can also modulate their intrinsic properties such as viscosity and solubility in common organic solvents. The chemical modifications are sorted in five main parts: the condensation reactions, the nucleophilic reactions, the click chemistry reactions, the radical reactions, and finally reactions going through other mechanisms or requiring a multistep process. They can be employed as such or for further polymerization processes depending on the targeted application. Examples of applications are thoroughly described to demonstrate their current usefulness and to help provide direction for their future use.

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Incipient microphase separation in short chain perfluoropolyether-block-poly(ethylene oxide) copolymers

Cited by 8 publications

References 47 publications

Effects of Polymer Coating Mechanics at Solid‐Electrolyte Interphase for Stabilizing Lithium Metal Anodes

Effects of Polymer Coating Mechanics at Solid‐Electrolyte Interphase for Stabilizing Lithium Metal Anodes

Scattering of multicomponent polymer blends

Diversity of Synthetic Approaches to Functionalized Perfluoropolyalkylether Polymers

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