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An Environmental and Economic Analysis of The Near Future of Lithium Ion Batteries

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Lithium ion batteries are quintessential components of modern life. They are used to power smart devices — phones, tablets, laptops, and are rapidly becoming major elements in the automotive industry. Demand projections for lithium are skyrocketing with production struggling to

Lithium ion batteries are quintessential components of modern life. They are used to power smart devices — phones, tablets, laptops, and are rapidly becoming major elements in the automotive industry. Demand projections for lithium are skyrocketing with production struggling to keep up pace. This drive is due mostly to the rapid adoption of electric vehicles; sales of electric vehicles in 2020 are more than double what they were only a year prior. With such staggering growth it is important to understand how lithium is sourced and what that means for the environment. Will production even be capable of meeting the demand as more industries make use of this valuable element? How will the environmental impact of lithium affect growth? This thesis attempts to answer these questions as the world looks to a decade of rapid growth for lithium ion batteries.

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2021-05

Experimental and Theoretical Investigation of Tetrel Clathrates for Li-ion Batteries: Electrochemistry, Structure and Applications

Description

Current Li-ion battery technologies are limited by the low capacities of theelectrode materials and require developments to meet stringent performance demands for
future energy storage devices. Electrode materials that alloy with Li, such as Si, are one
of the most

Current Li-ion battery technologies are limited by the low capacities of theelectrode materials and require developments to meet stringent performance demands for
future energy storage devices. Electrode materials that alloy with Li, such as Si, are one
of the most promising alternatives for Li-ion battery anodes due to their high capacities.
Tetrel (Si, Ge, Sn) clathrates are a class of host-guest crystalline structures in which
Tetrel elements form a cage framework and encapsulate metal guest atoms. These
structures can form with defects such as framework/guest atom substitutions and
vacancies which result in a wide design space for tuning materials properties. The goal of
this work is to establish structure property relationships within the context of Li-ion
battery anode applications. The type I Ba 8 Al y Ge 46-y clathrates are investigated for their
electrochemical reactions with Li and show high capacities indicative of alloying
reactions. DFT calculations show that Li insertion into the framework vacancies is
favorable, but the migration barriers are too high for room temperature diffusion. Then,
guest free type I clathrates are investigated for their Li and Na migration barriers. The
results show that Li migration in the clathrate frameworks have low energy barriers (0.1-
0.4 eV) which suggest the possibility for room temperature diffusion. Then, the guest
free, type II Si clathrate (Na 1 Si 136 ) is synthesized and reversible Li insertion into the type
II Si clathrate structure is demonstrated. Based on the reasonable capacity (230 mAh/g),
low reaction voltage (0.30 V) and low volume expansion (0.21 %), the Si clathrate could
be a promising insertion anode for Li-ion batteries. Next, synchrotron X-ray
measurements and pair distribution function (PDF) analysis are used to investigate the
lithiation pathways of Ba 8 Ge 43 , Ba 8 Al 16 Ge 30 , Ba 8 Ga 15 Sn 31 and Na 0.3 Si 136 . The results
show that the Ba-clathrates undergo amorphous phase transformations which is distinct
from their elemental analogues (Ge, Sn) which feature crystalline lithiation pathways.
Based on the high capacities and solid-solution reaction mechanism, guest-filled
clathrates could be promising precursors to form alloying anodes with novel
electrochemical properties. Finally, several high temperature (300-550 °C)
electrochemical synthesis methods for Na-Si and Na-Ge clathrates are demonstrated in a
cell using a Na β’’-alumina solid electrolyte.

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2021

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Advanced Synthesis Methods for Lithium Conducting Garnets

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Lithium conducting garnets in the family of Li7La3Zr2O12 (LLZO) are promising lithium conductors for solid-state batteries, due to their high ionic conductivity, thermal stability, and electrochemical stability with metallic lithium. Despite these advantages, LLZO requires a large energy input to

Lithium conducting garnets in the family of Li7La3Zr2O12 (LLZO) are promising lithium conductors for solid-state batteries, due to their high ionic conductivity, thermal stability, and electrochemical stability with metallic lithium. Despite these advantages, LLZO requires a large energy input to synthesize and process. Generally, LLZO is synthesized using solid-state reaction (SSR) from oxide precursors, requiring high reaction temperatures (900-1000 °C) and producing powder with large particle sizes, necessitating high energy milling to improve sinterability. In this dissertation, two classes of advanced synthesis methods – sol-gel polymer-combustion and molten salt synthesis (MSS) – are employed to obtain LLZO submicron powders at lower temperatures. In the first case, nanopowders of LLZO are obtained in a few hours at 700 °C via a novel polymer combustion process, which can be sintered to dense electrolytes possessing ionic conductivity up to 0.67 mS cm-1 at room temperature. However, the limited throughput of this combustion process motivated the use of molten salt synthesis, wherein a salt mixture is used as a high temperature solvent, allowing faster interdiffusion of atomic species than solid-state reactions. A eutectic mixture of LiCl-KCl allows formation of submicrometer undoped, Al-doped, Ga-doped, and Ta-doped LLZO at 900 °C in 4 h, with total ionic conductivities between 0.23-0.46 mS cm-1. By using a highly basic molten salt medium, Ta-doped LLZO (LLZTO) can be obtained at temperatures as low as 550 °C, with an ionic conductivity of 0.61 mS cm-1. The formation temperature can be further reduced by using Ta-doped, La-excess pyrochlore-type lanthanum zirconate (La2Zr2O7, LZO) as a quasi-single-source precursor, which convert to LLZTO as low as 400 °C upon addition of a Li-source. Further, doped pyrochlores can be blended with a Li-source and directly sintered to a relative density up to 94.7% with high conductivity (0.53 mS cm-1). Finally, a propensity for compositional variation in LLZTO powders and sintered ceramics was observed and for the first time explored in detail. By comparing LLZTO obtained from combustion, MSS, and SSR, a correlation between increased elemental inhomogeneity and reduced ionic conductivity is observed. Implications for garnet-based solid-state batteries and strategies to mitigate elemental inhomogeneity are discussed.

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2021

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Secondary Ion Mass Spectrometry Analysis of Lithium-Content and Isotopic Compositions in Kerogen

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Lithium (Li) is a trace element in kerogen, but the content and isotopic distribution (δ7Li) in kerogen has not previously been quantified. Furthermore, kerogen has been overlooked as a potential source of Li to sedimentary porefluids and buried sediments. Thus,

Lithium (Li) is a trace element in kerogen, but the content and isotopic distribution (δ7Li) in kerogen has not previously been quantified. Furthermore, kerogen has been overlooked as a potential source of Li to sedimentary porefluids and buried sediments. Thus, knowing the content and isotopic composition of Li derived from kerogen may have implications for research focused on the Li-isotopes of buried sediments (e.g., evaluating paleoclimate variations using marine carbonates).The objective of this work is to better understand the role of kerogen in the Li geochemical cycle. The research approach consisted of 1) developing reference materials and methodologies to measure the Li-contents and δ7Li of kerogen in-situ by Secondary Ion Mass Spectrometry, 2) surveying the Li-contents and δ7Li of kerogen bearing rocks from different depositional and diagenetic environments and 3) quantifying the Li-content and δ7Li variations in kerogen empirically in a field study and 4) experimentally through hydrous pyrolysis.
A survey of δ7Li of coals from depositional basins across the USA showed that thermally immature coals have light δ7Li values (–20 to – 10‰) compared to typical terrestrial materials (> –10‰) and the δ7Li of coal increases with burial temperature suggesting that 6Li is preferentially released from kerogen to porefluids during hydrocarbon generation. A field study was conducted on two Cretaceous coal seams in Colorado (USA) intruded by dikes (mafic and felsic) creating a temperature gradient from the intrusives into the country rock. Results showed that δ7Li values of the unmetamorphosed vitrinite macerals were up to 37‰ lighter than vitrinite macerals and coke within the contact metamorphosed coal.
To understand the significance of Li derived from kerogen during burial diagenesis, hydrous pyrolysis experiments of three coals were conducted. Results showed that Li is released from kerogen during hydrocarbon generation and could increase sedimentary porefluid Li-contents up to ~100 mg/L. The δ7Li of coals becomes heavier with increased temperature except where authigenic silicates may compete for the released Li. These results indicate that kerogen is a significant source of isotopically light Li to diagenetic fluids and is an important contributor to the global geochemical cycle.

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2022