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Engineering Solid Electrolytes for Lithium-Ion Battery Applications

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Engineering Solid Electrolytes for Lithium-Ion Battery Applications UCLA UCLA Electronic Theses and Dissertations Title Engineering Solid Electrolytes for Lithium-Ion Battery Applications Permalink https://escholarship.org/uc/item/5st377v1 Author Seegmiller, Trevor David Publication Date 2015 Peer reviewed|Thesis/dissertation eScholarship.org Powered by the California Digital Library University of California UNIVERSITY OF CALIFORNIA Los Angeles Engineering Solid Electrolytes for Lithium-Ion Battery Applications A thesis submitted in partial satisfaction of the requirements for the degree of Master of Science in Chemical Engineering by Trevor David Seegmiller 2015 ABSTRACT OF THE THESIS Engineering Solid Electrolytes for Lithium-Ion Battery Applications by Trevor David Seegmiller Master of Science in Chemical Engineering University of California, Los Angeles, 2015 Professor Jane P. Chang, Chair An investigation of lithium aluminum silicate (LASO) synthesized by atomic layer deposition (ALD) was investigated on various substrates and electrodes. Individual constituent and compound oxide depositions were characterized using in-situ FTIR to determine surface ligands after individual metal precursor and water pulses. Individual deposition rate of LiOH and Al2O3 are 1.2 Å/cycle and 1.4 Å/cycle respectively, while SiO2 depositions by ALD could not be achieved at low temperatures. LASO depositions have been demonstrated to be 25 Å/global cycle consisting of ten Al2O3 ALD cycles, six LiOH ALD cycles, and four SiO2 ALD cycles. Ionic conductivity values calculated for ALD lithium aluminum silicate (LASO) were in the range of 2.2×10-9 to 4.7×10-8 S/cm. The composites of ALD LASO and iCVD polymer solid electrolyte thin film on indium titanium oxide were also investigated and the corresponding ionic conduction was 1.8×10-8 S/cm at 110oC. In-situ electrochemical TEM showed lithium intercalation and deintercalation in silicon-germanium alloys coated with a 33nm LASO thin film. Galvanostatic charge-discharge cycling of LASO-coated carbon anodes showed 99.6% Coulombic efficiency, higher than 96.2% ii obtained with uncoated anodes. A solid state full cell comprised of LiCoO2 cathode, LASO solid electrolyte, and aluminum anode demonstrated ion transport between 0.9 V and 2.2 V cycling. iii The thesis of Trevor David Seegmiller is approved: Yi Tang Bruce Dunn Jane P. Chang, Committee Chair University of California, Los Angeles 2015 iv TABLE OF CONTENTS CHAPTER 1 INTRODUCTION AND BACKGROUND ..........................................................1 1.1 Motivation ...................................................................................................................... 2 1.2 History and Challenges of Lithium Ion Cells .................................................................. 4 1.3 3D Battery Architecture ................................................................................................ 11 1.4 Electrolytes for Lithium Ion Battery ............................................................................. 19 1.5 Thin Film Deposition Techniques for Solid Electrolytes ............................................... 32 1.6 Summary ...................................................................................................................... 36 CHAPTER 2 METHOD OF APPROACH ............................................................................... 37 CHAPTER 3 EXPERIMENTAL METHOD ........................................................................... 38 3.1 LASO Atomic Layer Deposition Chamber and In-situ FTIR Chamber.......................... 38 3.2 iCVD Process ............................................................................................................... 42 3.3 Substrates and Nanowires as Electrodes ....................................................................... 45 3.4 Thin Film Characterization Techniques ........................................................................ 46 3.5 Electrochemical Characterization Techniques ............................................................... 59 CHAPTER 4 RESULTS .......................................................................................................... 68 4.1 In-situ FTIR of LASO and Its Constituent Oxides ........................................................ 68 4.2 ALD of LASO .............................................................................................................. 77 4.3 In-situ TEM Electrochemical Characterization of LASO on Si/Ge Nanowires .............. 80 4.4 Hybrid ALD-iCVD Solid Electrolyte Films .................................................................. 87 4.5 LASO in Half-Cell Applications ................................................................................... 92 4.6 LASO in Full-Cell 2D Applications .............................................................................. 94 CHAPTER 5 SUMMARY....................................................................................................... 96 APPENDIX .............................................................................................................................. 98 BIBLIOGRAPHY ................................................................................................................... 139 v TABLE OF FIGURES Figure 1.1: Comparison of volumetric and gravimetric energy density of different battery chemistries. Lithium-ion and lithium-polymer ion batteries have high energy and power density compared to lead-acid and nickel-metal hydride chemistries (Tarascon 2001). ........4 Figure 1.2: Schematic of discharging lithium-ion cell, where lithium metal intercalated into the anode material and travels through the electrolyte to be intercalated into the cathode material. ..............................................................................................................................7 Figure 1.3: General electrode configuration (left) and 3D array electrode configuration (right).. 12 Figure 1.4: Thin film Li-ion solid state batteries provide favorable properties in energy density and capacity (Kim 2015) ................................................................................................... 15 Figure 1.5: Schematic of vapor-liquid-solid mechanism for silicon nanowire growth using gold nanodots as a catalyst and silane precursor for silicon metal. ............................................. 16 Figure 1.6: Monomer chemical structures for PV3D3 (left) and PV4D4 (right) in solid polymer electrolyte applications (Reeja-Jayan 2015). ...................................................................... 27 Figure 1.7: Phase equilibrium diagram for Li2O-Al2O3-SiO2 system. Modified from (Roy 1949). .......................................................................................................................................... 30 Figure 1.8: Schematic representation of the atomic layer deposition (ALD) process using self- limiting surface chemistry. A metal-organic precursor flows into the chamber and reacts on the surface-terminated hydroxide group. After which, an oxidant reacts with the surface metal-organic species to form a metal oxide layer (George 2010). ..................................... 34 Figure 3.1: (a) Schematic of the hot-wall atomic layer deposition chamber for synthesizing LASO thin films. (b) Schematic of the in-situ FTIR chamber for observing surface reactions in the ALD process. ........................................................................................................... 39 Figure 3.2: Schematic of a iCVD chamber where precursor flows into the chamber and decomposes on a wire array above the substrate to begin the polymerization process on the surface (Chen 2015). ......................................................................................................... 43 Figure 3.3: Schematic of spectroscopic ellipsometry measurement principles showing the direction changes in polarized light after striking a sample (Ohkoshi 2005). ...................... 46 Figure 3.4: An example of an optical model to measure thickness of thin film oxides using spectroscopic ellipsometry (Li 2011). ................................................................................ 47 vi Figure 3.5: Experimental spectroscopic ellipsometry data obtained from 30 cycles of ALD Al2O3 deposited on Si (110) substrate. Sample thickness was 43 Å. ............................................ 49 Figure 3.6: In-situ difference FTIR spectra obtained during the first LTB and H2O exposures during ALD deposition cycles. The absorption regions of interest include the surface hydroxyl region (O-H stretching at 3800-3550 cm-1), surface lithium butoxide species -1 -1 (*LiOC(CH3)3)(C-H region at 3000-2800 cm and C-O stretching in 1215-970 cm ). ...... 52 Figure 3.7: Survey Spectra of LASO deposited by ALD with the highlighted binding energies for oxygen (~530 eV), carbon (~285 eV), silicon (~100 eV), aluminum (73 eV), and lithium (~55 eV) by dashed lines at the appropriate peaks. This survey scan was completed on a 63 nm LASO sample deposited on Si (100). ........................................................................... 54 Figure 3.8: A scanning electron microscope (SEM) image of a single carbon pillar electrode coated with a 23nm LiAlSiO coating imaged under an excitation voltage of 10 kV. .......... 55 Figure 3.9: A high resolution transmission electron microscope (HRTEM) image of a Ge0.4Si0.6 alloy nanowire of diameter ~80 nm with a conformal LASO coating of 33 nm. The operating voltage of the electron microscope was
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