Polymer electrolyte membranes with exceptional conductivity anisotropy via holographic polymerization

Smith, Derrick M.; Cheng, Shan; Wang, Wenda; Bunning, Timothy J.

doi:10.1016/j.jpowsour.2014.07.172

Cited by 17 publications

(9 citation statements)

References 35 publications

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“…Poly(ethylene oxide) (PEO), which has strong lithium ion solvating ability and high dielectric constant, has been extensively used for SPE systems. Mainly five types of PEO‐containing SPEs show promising properties, which include cross‐linked networks, nanoparticle‐containing hybrid SPEs, block/grafted copolymers, SPEs via polymerization‐induced phase separation, and SPEs via holographic polymerization . To date, cross‐linked SPEs based on polyethylene, polyurethane, polysiloxane, polyacrylate, and polyphosphazene, have been reported.…”

Section: Composition Thermal Behavior Storage Modulus and Ionic Comentioning

confidence: 99%

Hybrid Electrolytes with Controlled Network Structures for Lithium Metal Batteries

et al. 2015

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Solid polymer electrolytes (SPEs) with tunable network structures are prepared by a facile one-pot reaction of polyhedral oligomeric silsesquioxane and poly(ethylene glycol). These SPEs, with high conductivity and high modulus, exhibit superior resistance to lithium dendrite growth even at high current densities. Measurements of lithium metal batteries with a LiFePO4 cathode show excellent cycling stability and rate capability.

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Section: Composition Thermal Behavior Storage Modulus and Ionic Comentioning

confidence: 99%

Hybrid Electrolytes with Controlled Network Structures for Lithium Metal Batteries

et al. 2015

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“…The authors emphasized the enhancing influence of moisture absorption by the polymer gels on their conductivity. Also a holographic polymerization nanomanufacturing technique was used for fabrication of polymer electrolyte membranes and anisotropy of ca 5000 was obtained . The holographic polymer electrolyte membranes comprised alternating nanolayers.…”

Section: Applicationsmentioning

confidence: 99%

Photoinitiated polymerization in ionic liquids and its application

Andrzejewska

2016

Polymer International

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Ionic liquids (ILs) are low-melting organic salts often liquid at room temperature, whose unique properties are the reason of increasing interest for their applications as solvents, reaction media and functional additives. The exceptional properties of ILs have proved to be particularly useful in polymer science giving the potential to produce polymeric materials with improved properties or to immobilize ILs in polymer matrices while keeping their special characteristics. One of the possibilities is polymerization in ILs which can also affect positively polymerization reactions. An especially attractive technique is photopolymerization due to the ease of process control, short reaction time and ambient working temperature. This review gives a literature survey of developments in photopolymerization processes carried out in ILs as well as applications of these processes. It covers both the photopolymerization in ILs as well as photopolymerization of IL monomers. The first part presents a short overview of physicochemical and photochemical properties of ILs; it includes also photochemical reactions and photoinitiation of polymerization in ILs. The second part covers both the basic research (kinetics of photopolymerization including polymerization rate coefficients and polymerization of IL monomers) as well as applications of UV-induced polymerization in ILs.

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“…The conductivity anisotropy ratio of hPEM•R15, defined as

\frac{σ_{∥}}{σ_{⊥}}

, is ≈3.00 × 10 5 , which is the highest for ion transport membranes we are aware of in literature to date, compared with ≈2–1000 for typical anisotropic PEMs aligned using mechanical, electrical, and magnetic fields. [3d,16,17] This extraordinarily high conductivity anisotropy is due to the intrinsic 1D nature of the hPEM•R: layer structures that are formed in the system, and it is much more difficult for ions to transfer through the resin domains orthogonal to the layer as compared with traveling in‐plane to the layers. As the electrolyte content increases, the anisotropy ratio reduces to close to one, which can also be explained by the TEM images.…”

Section: Resultsmentioning

confidence: 99%

“…While the reaction and network formations in these systems are usually inherently complex due to the interplay between phase mixing, diffusion, and polymerization during HP, careful material choices, such as varying the monomer functionality, or switching from a radical to a step‐growth polymerization, have proven to be an effective way to tune the morphology and quality of the holograms. Previously, hPEMs were fabricated using Norland Optical Adhesive 65 as the monomer, and PEG/LiTFSI or ionic liquid as the conducting phase. However, these membranes show low conductivity and mechanical properties and are not viable for battery applications.…”

Section: Introductionmentioning

confidence: 99%

Nanostructured, Highly Anisotropic, and Mechanically Robust Polymer Electrolyte Membranes via Holographic Polymerization

Smith

Pan

Cheng

et al. 2017

Adv Materials Inter

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to replace flammable liquid electrolytes, much research focus has been devoted to solid polymer electrolytes (SPEs) with combined high modulus and ionic conductivity in order to inhibit or retard Li dendrite growth. [3] For example, polyethylene oxide (PEO) has been blended with lithium salt to form SPEs since it has a low T g , high dielectric constant, and complexes well with Li ions. [4] Most SPEs to date have a few orders of magnitude lower conductivity than liquid-based electrolytes; to account for this, many attempts have been made to increase the conductivity while maintaining mechanical properties; however, SPE-based polymer electrolyte membranes (PEMs) typically lack the adequate combination of ionic conductivity and mechanical properties desired for long term or fast cycling in lithium batteries. The main solution for this has been to decouple the bulk electrolyte membrane mechanical and ion transport properties. To this end, block copolymers [3c,5] offer an elegant solution. More recently, mechanical blockades, such as 2D graphene oxide [6] and 1D nanofillers, [7] crosslinked networks, [8] polymerization-induced phase separation, [9] and liquid crystal-containing ion gel [10] have been demonstrated as viable candidates for next generation PEM design. While initial results for all these methods have been promising, each of these candidates brings different obstacles, and much work remains in understanding the underlying mechanisms of dendrite growth and cell failure and optimizing the materials to meet the required combination of properties.This paper reports a series of nanostructured, holographically polymerized PEMs (hPEMs) comprised of poly(ethylene glycol)/bis(trifluoromethane)sulfonimide lithium (PEG/ LiTFSI) electrolyte and acrylate-thiol-ene crosslinked resin. In holographical polymerization (HP), [11] a photopolymerizable monomer(s) is mixed with a photoinert material to form a homogenous mixture. [12] This prepolymer mixture is exposed to an interference pattern, inducing polymerization in the areas of constructive interference, which then leads to a concentration gradient, driving more monomer into the polymerization zone, simultaneously expelling the photoinert material into the volumes of destructive interference. While the reaction and network formations in these systems are usually inherently

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Polymer electrolyte membranes with exceptional conductivity anisotropy via holographic polymerization

Cited by 17 publications

References 35 publications

Hybrid Electrolytes with Controlled Network Structures for Lithium Metal Batteries

Hybrid Electrolytes with Controlled Network Structures for Lithium Metal Batteries

Photoinitiated polymerization in ionic liquids and its application

Nanostructured, Highly Anisotropic, and Mechanically Robust Polymer Electrolyte Membranes via Holographic Polymerization

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