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京都大学 / 新制・課程博士 / 博士(工学) / 甲第25287号 / 工博第5246号 / 新制||工||1999(附属図書館) / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 杉村 博之, 教授 邑瀬 邦明, 准教授 小林 圭 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

With the ever-advancing technology, there is an incessant need for reliable electrochemical energy storage (EES) components that can provide desired energy and power. At the forefront of EES systems are electrochemical capacitors (ECs), also known as supercapacitors that typically have higher power and superior cycle longevity but lower energy densities than their battery counterparts. One of the routes to achieve higher energy density for ECs is using the hybrid EC configuration, which typically utilizes a redox electrode coupled with a counter double-layer type electrode. In this dissertation, both scale-up (coin-cell type) as well as scale-down (on-chip miniaturized) hybrid ECs were designed, constructed and evaluated. The first part of the dissertation comprised material identification, syntheses, and electrochemical analyses. Lithium titanate-anatase titanium oxide (Li4Ti5O12-TiO2) composites were synthesized via electrostatic spray deposition (ESD) and characterized in both half-cell and full-cell assembly against lithium and nanostructured carbon based counter electrodes, respectively. The second redox type material studied for hybrid electrochemical capacitors was ESD derived manganese oxide (MnOx). The MnOx electrodes exhibited a high gravimetric capacitance of 225F g-1 in aqueous media. Further improvement in the rate handling of the MnOx electrodes was achieved by using CNT additives. The MnOx-CNT composites were tested in full-cell assembly against activated carbon counter electrodes and tested for different anode and cathode mass ratios in order to achieve the best energy-power tradeoff, which was the second major goal of the dissertation. The optimized hybrid capacitor was able to deliver a high specific energy density of 30.3 Wh kg-1 and a maximal power density of 4kW kg-1. The last part of the dissertation focused on a scale-down miniaturized hybrid microsupercapacitor; an interdigitated electrode design was adopted in order to shorten the ion-transport pathway, and MnOx and reduced graphene oxide (rGO) were chosen as the redox and double layer components, respectively. The hybrid microsupercapacitor was able to deliver a high stack energy density of 1.02 mWh cm-3 and a maximal stack power density of 3.44 W cm-3, both of which are comparable with thin-film batteries and commercial supercapacitor in terms of volumetric energy and power densities.

The dissertation thesis deals with investigation of electrode materials for Lithium-ion batteries. The main aim of investigation was focused to materials for negative electrode of Litihum-ion batteries. These negative electrode materials operate on intercalation principle. Object of interest are carbonaceous materials, especially their graphite forms. Graphite plays host role in lithium ion – graphite interactions that provides LiC6 compound. As a result of that investigation can be considered improving of graphite materials from stability, irreversible capacity and other parameters points of view. This kind of investigation takes an important part in field of elementary investigation work engaged to the next generation of Lithium-ion batteries. The work also describes the fire safety issue of Lithium-ion batteries along with compatibility of negative electrode materials and aprotic electrolytes.

Litiumjon-batterier har blivit väldigt populära för tillämpning i fordon. Den här teknologin har fler olika kemier att erbjuda som kontinuerligt förbättras. Litium-titanat-oxid-batterier använder (LTO) LTO som anod och erbjuder långt cyklingsliv samt minskar risk för SEI-bildning och litiumplätering.  Det här examensarbetet siktade på att undersöka om LTO-batterier kan användas som startbatterier i kommersiella fordon. Metodologin inkluderade två motorstart försök med en kommersiell 12s1p LTO-modul, laddnings/urladdningtester med en kommersiell LTO-cell med nominell spänning 2.3V samt överurladdningstester med byggda pouchceller. Materialet för pouchceller extraherades från en kommersiell LTO-cell och sedan studerades med SEM-EDX före och efter överurladdningstesterna. Resultatet visade att LTO-batterier kan användas som startbatterier i en diesel V8 motor även vid 39%SoC. Dessutom visade simuleringar att LTO-batterier kan användas inom Kinetic Energy Recovery System (KERS) tillämpning och behålla 60% SoC efter 500 laddning/urladdnings cykler. Resultaten från både KERS och motorstarterna visade att LTO är en lovande kandidat för ersättning av blybatterier. Laddnings/urladdnings tester visade att en kommersiell 12s1p LTO modul kan maximalt uppnå 73%SoC när den laddas med fordon-liknande strömmar. Däremot var SoC oberoende av laddningsström. Överurladdningstester med pouchceller visade att det är relativt ofarligt att urladda LTO 0.4V under spänningsgränsen utan stora ökningar i impedans eller stor kapacitetsförlust. Största förluster kopplades till åldring av NMC-baserade positiva elektroden. / Lithium ion batteries have become quite popular in vehicle applications in the past few decades. This technology offers multiple chemistries to choose from, that are continuously studied and improved. Lithium-titanate-oxide (LTO) batteries use LTO material as an anode, providing long cycling life, as well as essentially eliminating risk for SEI formation and lithium plating.  This Master thesis project aimed to investigate how well LTO-based lithium-ion batteries can perform in Start Ignition Lighting (SLI) application in commercial vehicles. The methodology included two engine crank tests with a commercial 12s1p LTO module, charge/discharge tests on a commercial LTO cell with nominal voltage 2.3V, as well as overdischarge cycling tests on assembled pouch cells. The materials for the pouch cells were extracted from a commercial LTO cell and later analysed with SEM-EDX before and after overdischarge tests. The results demonstrated that LTO-based Li-ion batteries can be successfully start a diesel V8 engine even at 39% SoC. Furthermore, when simulating an urban vehicle with an implemented Kinetic Energy Recovery System (KERS) application, a commercial cell LTO cell achieved and retained around 60\%SoC throughout 500 charge/discharge cycles. Combined results from KERS and engine start tests imply that LTO is a strong candidate for replacing lead-acid in these applications. Charge/discharge tests showed that commercial 12s1p LTO cell can maximum reach around 73%SoC when charged in a vehicle-like way. However, this maximum SoC limit was more or less independent of applied charging current. Furthermore, electrochemical overdischarge tests on the pouch cells demonstrated that it is relatively safe to overdischarge the cell 0.4V below the specified safety limit without significant rise in impedance or capacity fade. Major performance losses were attributed to the aging of the NMC-based positive electrode.