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Additive Manufacturing of Batteries and IR-Active Microparticles : = Polyborane-Based Electrolytes for Solid State Batteries and Additively Manufactured, TiN-Coated Microbridges.

Record Type:	Language materials, manuscript : Monograph/item
Title/Author:	Additive Manufacturing of Batteries and IR-Active Microparticles :/
Reminder of title:	Polyborane-Based Electrolytes for Solid State Batteries and Additively Manufactured, TiN-Coated Microbridges.
Author:	Villafuerte, Fernando Joaquin.
Description:	1 online resource (108 pages)
Notes:	Source: Dissertations Abstracts International, Volume: 85-06, Section: B.
Contained By:	Dissertations Abstracts International85-06B.
Subject:	Materials science. -
Online resource:	click for full text (PQDT)
ISBN:	9798380871440

Additive Manufacturing of Batteries and IR-Active Microparticles : = Polyborane-Based Electrolytes for Solid State Batteries and Additively Manufactured, TiN-Coated Microbridges.
Villafuerte, Fernando Joaquin.

Additive Manufacturing of Batteries and IR-Active Microparticles :Polyborane-Based Electrolytes for Solid State Batteries and Additively Manufactured, TiN-Coated Microbridges. - 1 online resource (108 pages)

Source: Dissertations Abstracts International, Volume: 85-06, Section: B.

Thesis (Ph.D.)--California Institute of Technology, 2024.

Includes bibliographical references

Advances in additive manufacturing (AM) processes are continuously opening up the material design space, providing scientists with opportunities to explore the relationship between structure, processing, and materials properties in new contexts. The first project presented in this thesis presents the design and refinement of a novel, polyborane-based solid electrolyte, whose design and investigation were motivated by the advent of additively manufactured, 3D electrodes, which could play a pivotal role in enabling next-generation batteries that can store more energy without sacrificing power. The first iteration of this electrolyte was synthesized by hydroborating polybutadiene with 9-borabicyclo(3.3.1)nonane (9-BBN). The resultant poly(9-BBN) was then reacted with precise amounts of n-butyllithium (n-BuLi), an organolithium reagent, to create the final polymer electrolyte. The polymer electrolyte films were assembled into a custom apparatus for impedance measurements, and though found to be ionically conductive, these measurements were not consistent, even within films made from the same batch of polymer in solution.This necessitated the modification of the electrolyte into a UV-cured version, which was achieved by hydroboration of polybutadiene using 9-BBN. The resulting poly(9-BBN)-co-polybutadiene is treated with lithium tert-butoxide (LiOtBu) and crosslinked to produce a precursor resin, which is then drop cast onto PTFE spacers, UV-cured for 5 minutes, dried, and assembled into coin cells for electrochemical impedance spectroscopy (EIS) and into pans for differential scanning calorimetry (DSC). The ionic conductivity (\uD835\uDF0E)of the PBEs as measured by EIS as a function of molar salt ratio, r = molLi/molB, does not track with their measured glass transition temperatures, Tg or the activation energies, Ea, extracted from fitting the Vogel-Tammann-Fulcher (VTF) equation to the conductivity data. Beyond r = 0.33, values for Tg and Ea demonstrate insensitivity to increasing concentration, while \uD835\uDF0E continues to change with concentration and reaches a maximum at r = 0.75. Moreover, measurement of ionic conductivity of control PBE films without boron on the polybutadiene backbone confirms that the presence of Lewis-acidic boron groups is necessary for ionic solvation and conduction. Further analysis that compared the PBEs to a well-studied PEO-based electrolyte in the literature through the calculation of a reduced conductivity, \uD835\uDF0Er, to control for polymer viscosity and segmental motion revealed that PBEs obtain optimal conductivity at higher salt concentrations than PEO, and that their ionic conductivities are far below that of PEO. We posit that we are observing a mechanism of ionic conduction in a glassy regime partially decoupled from the relaxation of the polymer host. We attribute these effects to the strong interaction between the Lewis-acidic boron centers and the strongly Lewis-basic tert-butoxide anions, which limits ionic conductivity by suppressing motion of the anions and presenting a large activation barrier for motion of Li+, which is optimized at high concentrations where the distance between the boron-anion centers is sufficiently small to increase the probability of a hopping event from one center to another.Nanorods fashioned from noble metals are ideal for maximizing extinction of electromagnetic radiation, which is necessary for plasmonically active materials in numerous applications, from contrast agents for biological imaging to effective obscurants. Key challenges that prevent nanorods from being employed for these technological applications include the prohibitively expensive cost of Au and Ag, their lack of requisite thermal and chemical stability, and the limitations in resolution and attainable feature sizes produced by existing wet chemistry techniques. The second project in this thesis focuses on the development of an AM process to create arrays of TiN-coated microbridges with lengths of 4.749 microns, cross-sections with dimensions of 0.692 by 2.256 microns, and effective aspect ratios of 3.368, that are capable of attenuating light reflected from a TiN-coated sapphire substrate by more than 80% in the mid-infrared (mid-IR), as measured by Fourier Transform Infrared (FTIR) spectroscopy. FTIR spectroscopy measurements further reveal attenuation of light transmitted through the same TiN-coated structures by up to 35% in the near- to mid-IR. These results indicate a promising pathway for AM of plasmonically active microparticles with broad reflectance and transmittance attenuation of light in the near- and mid-IR.

Electronic reproduction.
Ann Arbor, Mich. :
ProQuest,
2024

Mode of access: World Wide Web

ISBN: 9798380871440Subjects--Topical Terms:

557839
Materials science.
Subjects--Index Terms:

Additive manufacturingIndex Terms--Genre/Form:

554714
Electronic books.

Additive Manufacturing of Batteries and IR-Active Microparticles : = Polyborane-Based Electrolytes for Solid State Batteries and Additively Manufactured, TiN-Coated Microbridges.
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