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Applications in soft, flexible optical, and optoelectronic applications demand polymer thin film coatings that can accommodate substantial physical deformations. The preparation of high refractive index polymers (HRIPs) through the quaternization of poly(4‐vinylpyridine) (P4VP) thin films with (di)halomethanes is presented. P4VP thin films are prepared by initiated chemical vapor deposition (iCVD) and then quaternized through exposure to saturated vapors of iodomethane (CH3I), dibromomethane (CH2Br2), and diiodomethane (CH2I2), resulting in refractive indices (RI) as high as 1.67, 1.71, and 2.07, respectively (at 632.8 nm). Fourier‐transform infrared (FTIR) spectroscopy and X‐ray photoelectron spectroscopy (XPS) confirmed the quaternization of pyridine pendant groups on the polymer chain to n‐methylpyridinium with primarily an iodide or bromide counterion, though a minor fraction of polyiodides are also detected. Additionally, these films demonstrate superior thermal stability, retaining their refractive index and thickness after thermal excursions to 200 °C. The halogenated P4VP films exhibit superior mechanical flexibility relative to conventional inorganic coatings (Al2O3 and Ta2O5) and do not fracture at uniaxial tensile strains as high as 10%. This new material chemistry and fabrication approach method may enable advanced optical designs and functionality in a wide range of substrates and device architectures. [ABSTRACT FROM AUTHOR]

Flexible optics and optoelectronic devices require stretchable and compliant antireflection coatings (ARC). Conventional optical coatings, typically inorganic thin films, are brittle and crack under strain, while porous or patterned surfaces often lack environmental endurance and/or involve complex processing. Polymeric optical thin films prepared by initiated chemical vapor deposition (iCVD) comprise a promising alternative class of materials. With iCVD, multilayered, uniform thin film coatings can be synthesized conformally on the surface of a temperature-sensitive substrate near room temperature with precise compositional and thickness control. In this study, a model two-layer coating design consisting of poly(1H,1H,6H,6H-perfluorohexyl diacrylate) (pPFHDA) with a refractive index at 633 nm of n633 = 1.426 was deposited atop poly(4-vinylpyridine) (p4VP, n633 = 1.587). Broadband antireflection over the visible wavelength range (400–750 nm) was conferred to a transparent, flexible thermoplastic polyurethane (TPU) substrate (n633 ∼ 1.51), reducing the front-surface reflectance from ∼4% to ∼2%. The superior mechanical compliance of polymer ARCs over conventional inorganic coatings (MgF2, SiO2, and Al2O3) on the TPU substrate was thoroughly investigated by monitoring the evolution of film morphology and tensile fracture with applied equibiaxial strain. The polymer ARC withstood at least ε = 1.64% equibiaxial strain without fracture, while all inorganic coatings cracked. Through a repeated application of strain over hundreds of cycles, the antireflection by the polymer film was shown to possess excellent stability and fatigue resilience. Finally, simulations of established iCVD polymer chemistries possessing larger index contrast revealed that reflectance can be further reduced to <1% or better. [ABSTRACT FROM AUTHOR]

This paper presents the fabrication and demonstration of an ultrathin microelectromechanical chemical sensing device. Microcantilevers are etched from 100-nm-thick silicon nitride, and a 75-nm-thick reactive copolymer film for sensing is deposited by initiated chemical vapor deposition. Cross-linking densities of the polymer films are controlled during the deposition process; it is shown that greater cross-linking densities yield greater cantilever deflections upon the polymer's reaction with the analyte. Considering that chemical reactions are necessary for stress formation, the sensing is selective. Cantilever deflections of greater than 3 [micro]m are easily attained, which allow a simple switch to be designed with resistance-based outputs. When exposed to a hexylamine vapor-phase concentration of 0.87 mol%, the resistance of the switch drops by over six orders of magnitude with a response time of less than 90 s. [2008-0132] Index Terms--Chemical-vapor deposition (CVD), microsensors, thin films, three-dimensional nanomanufacturing.

Conventional lithium ion battery separators are microporous polyolefin membranes that play a passive role in the electrochemical cell. Next generation separators should offer significant performance enhancements, while being fabricated through facile, low cost approaches with the ability to readily tune physicochemical properties. This study presents a single-step manufacturing technique based on UV-initiated polymerization-induced phase separation (PIPS), wherein microporous separators are fabricated from multifunctional monomers and ethylene carbonate (EC), which functions as both the pore-forming agent (porogen) and electrolyte component in the electrochemical cell. By controlling the ratio of the 1,4-butanediol diacrylate (BDDA) monomer to ethylene carbonate, monolithic microporous membranes are readily prepared with 25 μm thickness and pore sizes and porosities ranging from 6.8 to 22 nm and 15.4% to 38.5%, respectively. With 38.5% apparent porosity and an average pore size of 22 nm, the poly(1,4-butanediol diacrylate) (pBDDA) separator takes up 127% liquid electrolyte, resulting in an ionic conductivity of 1.98 mS cm−1, which is greater than in conventional Celgard 2500. Lithium ion battery half cells consisting of LiNi0.5Mn0.3Co0.2O2 cathodes and pBDDA separators were shown to undergo reversible charge/discharge cycling with an average discharge capacity of 142 mA h g−1 and a capacity retention of 98.4% over 100 cycles – comparable to cells using state-of-the-art separators. Moreover, similar discharge capacities were achieved in rate performance tests due to the high ionic conductivity and electrolyte uptake of the film. The pBDDA separators were shown to be thermally stable to 374 °C, lack low temperature thermal transitions that can compromise cell safety, and exhibit no thermal shrinkage up to 150 °C. [ABSTRACT FROM AUTHOR]

Organic cathode materials have attracted significant research attention recently, yet their low electronic conductivity limits their application as solid-state cathodes in lithium batteries. This work describes the development of a novel organic cathode chemistry with significant intrinsic electronic conductivity for solid-state thin film batteries. A polymeric charge transfer complex (CTC) cathode, poly(4-vinylpyridine)-iodine monochloride (P4VP·ICl), was prepared by initiated chemical vapor deposition (iCVD). Critical chemical, physical, and electrochemical properties of the CTC complex were characterized. The complex was found to have an electronic conductivity of 4 x 10-7 S cm-1 and total conductivity of 2 x 10-6 S cm-1 at room temperature, which allows the construction of a 2.7 μm thick dense cathode. By fabricating a P4VP⋅ICl/LIPON.Li thin film battery, the discharge capacity of P4VP·ICl was demonstrated to be >320 mA h cm-3 on both rigid and flexible substrates. The flexible P4VP·ICl/LIPON/Li battery was prepared by simply replacing the rigid substrate with a flexible polyimide substrate and the as-prepared battery can be bent 180° while maintaining electrochemical performance. [ABSTRACT FROM AUTHOR]

Flexible, compliant permeation barrier layers are critically needed in the optics/optoelectronics industry to protect deformable, polymer‐based optical elements, such as those found in variable focus lenses. To address these needs, a transparent and deformable polymeric permeation barrier coating consisting of poly(1H,1H,6H,6H‐perfluorohexyl diacrylate) (pPFHDA) is prepared by initiated chemical vapor deposition. pPFHDA is a highly crosslinked fluoropolymer, which is deposited onto temperature‐sensitive elastomeric membranes at ambient temperature with high uniformity and conformality. This is believed to be the first demonstration of vapor deposition of the PFHDA monomer. Coatings with thicknesses nominally ranging from 200 to 750 nm are prepared and shown to be impermeable to high‐index optical fluid (polyphenyl thioether) over 2 months at 70 °C, which translates to more than 4 year lifespan at room temperature, even after being subjected to 0.26% biaxial strain. Moreover, due to its amorphous nature, the pPFHDA is transparent from wavelengths of 300–1690 nm and also thermally stable to temperatures of 300 °C. These properties should make pPFHDA coating a particularly compelling candidate for flexible optical/optoelectronic devices requiring transparent and compliant barrier layers. [ABSTRACT FROM AUTHOR]

Next-generation, energy-dense, rechargeable lithium batteries require Li metal anodes that provide ten times the specific capacity of state-of-the-art graphite anodes. But, there are many challenges to the successful utilization of Li anodes, including high chemical reactivity and the propensity to deposit into non-dense, high surface area morphologies, which can result in dendritic growth and significant, associated safety hazards, such as short-circuiting and potential combustion of the liquid electrolyte. Solid-state thin film electrolytes have been used to address both of these challenges. In this review, we will provide an overview of thin film battery designs, highlighting the role of thin film electrolytes, lithium phosphorous oxynitride (LiPON) in particular, in enabling highly reversible, efficient cycling of Li metal anodes. We then discuss progress in thin film electrolyte compositions and vacuum deposition processing that has occurred in roughly the past 20 years. It will be shown how these novel electrolyte compositions and processing capabilities have been used to integrate thin film electrolytes with bulk Li metal anodes required for large format energy storage cells, such as those used in consumer electronics and electric vehicles. We end the review with a brief outlook on the outstanding questions and potential future research directions. [ABSTRACT FROM AUTHOR]

A critical challenge associated with the efficient fabrication of solid-state, three-dimensional microbatteries is the synthesis of conformal, solid-state thin film electrolytes. This study presents the synthesis of lithium ion conducting thin film polyelectrolytes based on poly(methacrylic acid-co-ethylene glycol diacrylate) using initiated chemical vapor deposition. These films are transformed to lithium-bearing polyelectrolytes through an H+/Li+ ion exchange reaction in a 1M LiOCH3 solution in methanol. Infrared spectroscopy of the vibrational stretching modes associated with the carbonyl bond in methacrylic acid confirmed that the ion exchange was successful, and quantification by x-ray photoelectron spectroscopy showed that ion exchange was nearly 100% complete. Incorporation of the crosslinking comonomer ethylene glycol diacrylate (EGDA) was necessary for physical stability of the film during the ion exchange process, and four polyelectrolyte compositions with varying crosslinking densities (ethylene glycol diacrylate content) were prepared to understand its role on ionic conductivity. The highest ionic conductivity was achieved in the polymer film with the lowest crosslinking density (9 mol. % EGDA); its conductivity was determined to be 6 × 10−9 S cm−1 at 20 °C and 1 × 10−5 S cm−1 at 100 °C. The activation energy for ionic conductivity was 0.88 eV. Using atomic force microscopy, the surfaces of thin film polyelectrolytes were shown to be continuous, smooth, and pinhole-free, suggesting that these films are suitable for integration into 3D microbatteries. [ABSTRACT FROM AUTHOR]

Abstract: Chemical vapor deposition (CVD) is an attractive technique for the fabrication of high‐quality polymer thin films. The scheme used to initiate polymer chain growth is fundamental to controlling polymer thin film chemistry. A new initiation scheme for polymer CVD utilizing cationic initiation with a strong Lewis acid, TiCl4, in combination with a hydrogen donor, H2O, is presented. This coinitiation scheme results in polystyrene deposition rates of 139 nm min−1, relative to just 34 nm min−1 when TiCl4 is used alone. Characterization by Fourier transform infrared spectroscopy shows that the polymer structures of polystyrene films prepared by conventional solution‐based techniques and cationic CVD are similar. Synthesis of cross‐linked polymer thin films is also demonstrated by depositing poly(divinylbenzene) and showing its insolubility in a range of solvents. The practical utility of these poly(divinylbenzene) films as corrosion resistant coatings is demonstrated. In 1 n HCl, 200 nm thick films on stainless steel increase the polarization resistance by a factor of 44 relative to bare, untreated stainless steel. [ABSTRACT FROM AUTHOR]

The stability of NASICON-type conducting glass–ceramic electrolyte, Li 1+x+y Al x Ti 2−x Si y P 3−y O 12 (Ohara LICGC) has been characterized after prolonged exposure to deionized water and HCl(aq) solutions supported with LiCl. X-ray diffraction shows that the bulk crystallographic structure of the LICGC membranes remains unchanged when exposed to these solutions. Electrochemical impedance spectroscopy (EIS) shows that the conductivity of LICGC membranes immersed in deionized water remains stable over a one month period, while there is a significant increase in resistance when exposed to the acidic solutions. When exposed to pH 4 and 2 solutions for just 24 h, the resistances of the LICGC membrane increase by a factor of 8.5 and 23.5, respectively. EIS coupled with morphological characterization by scanning electron microscopy, shows that this resistance growth is due to the development of a surface layer on the LICGC membrane. However, this substantial increase in resistance can be mitigated by adding LiCl to the HCl solutions. For a pH 4 solution supported with 6.75 M LiCl, the impedance spectrum and surface morphology are qualitatively comparable to pristine, dry LICGC material, suggesting that surface layer formation was suppressed. This was also confirmed via cyclic voltammetry measurements in four-electrode electrochemical cells. [ABSTRACT FROM AUTHOR]

Non-Newtonian, shear-thickening lithium-ion battery electrolytes show promise for improved safety in high impact events by exhibiting a reversible transition to a solid-like phase under high shear. This aids in the prevention of shorting and subsequent combustion of volatile electrolyte under such conditions. In this work, we investigate the electrodynamics of shear-thickening electrolytes using conductivity under shear measurements, as well as finite-element modeling. We observe an order of magnitude drop in ionic conductivity under shear-thickening conditions.We suggest aworking model to explain substantial drops in conductivity observed in shear-thickening electrolytes under shear. The results here can be generally applied to any electrolyte that exhibits non- Newtonian hydrodynamic properties. [ABSTRACT FROM AUTHOR]

Solid polymer electrolytes, such as polyethylene oxide (PEO) based systems, have the potential to replace liquid electrolytes in secondary lithium batteries with flexible, safe, and mechanically robust designs. Previously reported PEO nanocomposite electrolytes routinely use metal oxide nanoparticles that are often 5–10 nm in diameter or larger. The mechanism of those oxide particle-based polymer nanocomposite electrolytes is under debate and the ion transport performance of these systems is still to be improved. Herein we report a 6-fold ion conductivity enhancement in PEO/lithium bis(trifluoromethanesulfonyl) imide (LiTFSI)-based solid electrolytes upon the addition of fullerene derivatives. The observed conductivity improvement correlates with nanometer-scale fullerene crystallite formation, reduced crystallinities of both the (PEO)6:LiTFSI phase and pure PEO, as well as a significantly larger PEO free volume. This improved performance is further interpreted by enhanced decoupling between ion transport and polymer segmental motion, as well as optimized permittivity and conductivity in bulk and grain boundaries. This study suggests that nanoparticle induced morphological changes, in a system with fullerene nanoparticles and no Lewis acidic sites, play critical roles in their ion conductivity enhancement. The marriage of fullerene derivatives and solid polymer electrolytes opens up significant opportunities in designing next-generation solid polymer electrolytes with improved performance. [ABSTRACT FROM AUTHOR]

• Polymerization-induced phase separation was used to prepare microporous separators. • Co-polymerization led to high conversion, strength, and ionic conductivity. • Cross-linked acrylate chemistry yielded thermal and thermomechanical stability. • Lack of thermal shrinkage/melting avoids thermal runaway, improves battery safety. • High-porosity separator facilitated high capacity in lithium ion battery coin cells. Next generation, multifunctional separators can enhance energy storage, power, and safety performance of lithium ion batteries but must be simple to fabricate and incorporate with existing roll-to-roll manufacturing. This study presents a strategy to facilely prepare these separators using UV-initiated polymerization-induced phase separation (PIPS), wherein microporous polymer separators are fabricated directly from constituent monomers and ethylene carbonate (EC) porogen. This enables a wide compositional design space as co-monomers with specific chemical functionality can be readily incorporated into the PIPS precursor mixture. Herein, 1,4-butanediol diacrylate (BDDA) was copolymerized with poly(ethylene glycol) diacrylate (PEGDA) to increase the acrylate conversion in the photopolymerization and improve mechanical properties. By tuning the ratio of PEGDA and EC, separators with high porosity (41.3%) and effective ionic conductivity (2.09 mS cm−1) were prepared. Inclusion of PEGDA was essential to increasing the elastic modulus to > 345 MPa, which is required for cell assembly by roll-to-roll manufacturing. All separators prepared were shown to enable reversible cycling of lithium metal/LiNi 0.5 Mn 0.3 Co 0.2 O 2 half-cells for 100 cycles. Unlike conventional polyolefin separators, which were shown to melt at 160 °C and shrink by up to 29.8% at elevated temperatures, the PIPS separators possess exceptional, safety-enhancing thermomechanical properties, undergoing no phase transitions or thermal shrinkage. [Display omitted]. [ABSTRACT FROM AUTHOR]

We report the first direct measurement of the extent of the spontaneous non-electrochemically driven reaction between a lithium ion battery electrode surface (Si) and a liquid electrolyte (1.2 M LiPF6–3 : 7 wt% ethylene carbonate : dimethyl carbonate). This layer is estimated to be 35 Å thick with a SLD of ∼ 4 × 10−6Å−2 and likely originates from the consumption of the silicon surface. [ABSTRACT FROM AUTHOR]

The synthesis, processing, and performance of a low-cost monolithic battery electrode, produced entirely of natural and renewable resources, are reported. This anode material exhibits tunable electrochemical performance suitable for both high power and high energy applications. A synthesis method that directly results in electrically interconnected three-dimensional architectures is presented, where the carbon framework functions as current collector and lithium insertion material, eliminating the extra mass and expense of inactive materials in conventional designs. Fibrous carbon electrode materials are produced from solvent extracted lignin using scalable melt processing technology and thermal conversion methods. The resulting free-standing electrodes exhibit comparable electrochemical performance to commercial carbon-based anodes at a fraction of the materials and processing costs. Compositional and electrochemical characterization shows that carbonized lignin has a disordered nano-crystalline microstructure. The carbonized mats cycle reversibly in conventional aprotic organic electrolytes with Coulombic efficiencies over 99.9%. Moreover, lignin carbon fibers carbonized at 2000 °C can cycle reversibly in 1 m LiPF6 in propylene carbonate. [ABSTRACT FROM AUTHOR]

Abstract: Effective conductivity and mechanical properties of composite polymer electrolytes, in which the reinforcement phase is a sintered packed bed of Li-ion conductive ceramics particles, were estimated using finite element analyses. The computations targeted estimation of the effect of sintering degree, i.e. size of the inter-particle connective necks, on the overall properties of the composite. Methods for microstructure generation and computational procedures were presented. The mechanical ability of the membrane to block lithium dendrites was assessed based on a stability criterion, which depends on the computed effective stiffness. It was found that the minimum size of the inter-particle connections necessary to provide mechanical stability without losing the enhancement in conductivity was 0.05 times the mean particle radius. [Copyright &y& Elsevier]

The atmospheric pressure chemical vapor deposition (APCVD) of SiO2–TiO2 thin films on glass by employing a [[(tBuO)3SiO]2–Ti(OiPr)2] single-source precursor, which can be prepared from commercially available materials, results in antireflective thin films with high silica SiO2 : TiO2 ratio (i.e. SiO2 ＞ 1) on float glass under industrially relevant manufacturing conditions. [ABSTRACT FROM AUTHOR]

Abstract: Mechanical properties and conductivity were computed for several composite polymer electrolyte structures. A multi-phase effective medium approach was used to estimate effective conductivity. The Mori–Tanaka approach was applied for calculating the effective stiffness tensor of the composites. An analysis of effective mechanical properties was performed in order to identify the composite structures, which would be capable of blocking the dendrites forming in Li-ion battery when Li metal is used as anode. The stability parameter which combines both stiffness and compressibility of the electrolyte was used in the analysis. The calculations were done over the wide range of Young''s modulus of the polymer matrix showing the threshold concentration of the filler necessary for the mechanical stability. The results can be used to formulate design criteria for solid electrolytes that would exhibit appropriate stiffness and compressibility to suppress lithium dendrite growth while maintaining high effective conductivities. [Copyright &y& Elsevier]

We present a method to prepare shear thickening electrolytes consisting of silica nanoparticles in conventional liquid electrolytes with limited flocculation. These electrolytes rapidly and reversibly stiffen to solidlike behaviors in the presence of external shear or high impact, which is promising for improved lithium ion battery safety, especially in electric vehicles. However, in initial chemistries the silica nanoparticles aggregate and/or sediment in solution over time. Here, we demonstrate steric stabilization of silica colloids in conventional liquid electrolyte via surface-tethered PMMA brushes, synthesized via surface-initiated atom transfer radical polymerization. The PMMA increases the magnitude of the shear thickening response, compared to the uncoated particles, from 0.311 to 2.25 Pa s. Ultrasmall-angle neutron scattering revealed a reduction in aggregation of PMMA-coated silica nanoparticles compared to bare silica nanoparticles in solution under shear and at rest, suggesting good stabilization. Conductivity tests of shear thickening electrolytes (30 wt % solids in electrolyte) at rest were performed with interdigitated electrodes positioned near the meniscus of electrolytes over the course of 24 h to track supernatant formation. Conductivity of electrolytes with bare silica increased from 10.1 to 11.6 mS cm -1 over 24 h due to flocculation. In contrast, conductivity of electrolytes with PMMA-coated silica remained stable at 6.1 mS cm -1 over the same time period, suggesting good colloid stability.

Using neutron reflectometry, we have determined the thickness and scattering length density profile of the electrode-electrolyte interface for the high-voltage cathode LiMn(1.5)Ni(0.5)O4 in situ at open circuit voltage and fully delithiated. Upon exposure to a liquid electrolyte, a thin 3.3 nm Li-rich interface forms due to the ordering of the electrolyte on the cathode surface. This interface changes in composition, as evident by an increase in the scattering length density of the new layer, with charging as the condensed layer evolves from being lithium rich to one containing a much higher concentration of F from the LiPF6 salt. These results show the surface chemistry evolves as a function of the potential.

Initiated chemical vapor deposition (iCVD) of alternating copolymer thin films has been achieved for the first time. Copolymerization is desirable for maleic anhydride (Ma) since this monomer does not homopolymerize to an appreciable extent. At conditions where the observed deposition rates for styrene (S) and Ma homopolymers were only 0 and 5.5 nm/min, respectively, combining the two monomers resulted in a much higher deposition rate of 75.4 nm/min. iCVD processes utilize low energy (<30 W) to generate peroxy radicals from initiator molecules while avoiding degradation of functional groups in the monomers. Indeed, full retention of the anhydride functionality from the Ma monomer and avoidance of undesirable side reactions was observed in iCVD of poly(styrene-alt-maleic anhydride) (PSMa) copolymer films. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and 13C nuclear magnetic resonance (NMR) conclusively demonstrate that all of the copolymer films contain 50% styrene and 50% Ma (within experimental error), irrespective of gas feed ratios employed during the deposition. The 13C NMR signal in the 136-140 ppm region from the quaternary carbon in styrene and additional distortionless enhancement polarization transfer experiments confirmed that the copolymers are strictly alternating. Varying the gas feed ratio of Ma to styrene provided control over deposition rates and number-average molecular weights. Number-average molecular weights varied from 1380 to 4680 g/mol, and deposition rates varied from 6.3 to 75.4 nm/min.