LEE- Metalurji ve Malzeme Mühendisliği-Doktora
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Yazar "Arslan, Cüneyt" ile LEE- Metalurji ve Malzeme Mühendisliği-Doktora'a göz atma
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ÖgeCold sintering process on molybdenum disilicide and graphite composite electrodes( 2020) Nayir, Selda ; Arslan, Cüneyt ; 635746 ; Metalurji ve Malzeme Mühendisliği Ana Bilim DalıSintering is a compaction process of particulate matters with a diffusional process that minimizes surface energy to densify particles against the competitive force of coarsening (Dejonghe and Rahaman 2003; German 1996; S.-J L Kang 2005). In a conventional aspect, effective consolidation is usually accomplished at 50-75% of melting temperatures of sintered materials and with an occasional aid of pressure. The primary driving force behind the consolidation process is a reduction of surface free energy. In order to improve the effect of sintering, some of the processing techniques, such as hot isostatic pressing, field-assisted sintering (FAST), utilize pressure up to 200 MPa (German 1996; S.-J L Kang 2005; Li, Liao, and Hermansson 1996; Stanciu, Kodash, and Groza 2001). Although, the application of pressure improves the performance of densification in the particle-particle level, densification is still highly dependent on high temperature, due to the slow solid-state diffusional process. Cold sintering process (CSP) is a densification process at a low-temperature provides an opportunity to sinter a wide range of ceramic materials at extremely low temperatures (<300˚C) with the aid of transient acidic or basic aqueous solutions. As it is reported on many occasions, the aid of liquid media, preferentially water, amplifies consolidation during the sintering process (H. Guo, Baker, et al. 2016b, 2016a; H. Guo, Guo, et al. 2016; J. Guo et al. 2016; Hirano and Somiya 1976). The other advantage of cold sintering is bringing together the materials that have different melting temperatures during the sintering process, which used to be a challenge. Since densifications happen at very low temperatures, co-sintering of the different types of materials is possible such as polymer and ceramic (PET and PC with Li2MoO4 to produce a capacitor) is co-sintered with this method as reported earlier (Baker et al. 2016; de Beauvoir et al. 2019; Guo et al. 2017; J. Guo et al. 2016). The successful implementation of CSP in different types of materials provided an opportunity to shift its focus to a covalently bonded structure, which is studied within this thesis context. The covalently bonded structures, Molybdenum disulfide, and graphite are cold sintered with the aid of water, and a slurry at very low temperatures. The slurry able to produce micron size MoS2 flakes that grow onto the surface of the pristine MoS2 flakes and enables the bonding of the mixed constituents. The approach provides the fabrication of highly dense and electrochemically active MoS2/Graphite (MG) composites at an extremely low processing temperature of ~140˚C. The process offers an opportunity to sinter covalently bonded materials effectively to produce either dense or near dense pellets or thick films. The composites that include up to 20 wt% graphite, as well as a solid electrolyte, could be easily integrated and densified using this method. The composites with varying weight proportions of Graphite and the solid electrolytes are cold sintered under 520 MPa pressure at 140°C for 60 min to achieve dense pellets. The densification of the pellets is tested with calculating their relative densities based on theoretical densities for MoS2, Graphite AHM, and Thiourea, which are 5.06, 2.26, 2.49, and 1.43 g/cm3, respectively. Production of electrode film is started after achieving ~88% relatively dense pellets, with following general production procedure of the pellet. The electrode film production differentiates from the pellets where at tape casting of the prepared slurry. The slurry, which includes the principle constituents (MoS2, Graphite) besides of binder materials, is used to produce a flexible tape that can endure the subsequent processes. The binder mixture was tape cast on a copper foil with 2.5 mg/cm2 active material loading and binders removed from the system with a heat treatment in a tube furnace at 180˚C. Afterward, a transient liquid (water), is included in the system with humidifying the films, and they were cold sintered with under a uniaxial pressure of 90 MPa at 120°C. The microstructural characterization of both pellet and film of MoS2 composites conducted with, X-ray diffraction (XRD), Scanning electron microscope (SEM), Energy Dispersive X-Ray Spectroscopy (EDS), Electron backscatter diffraction (EBSD), Thermal gravimetric analysis and mass spectroscopy (TGA-MS), and Raman spectroscopy. The XRD results revealed that cold sintered film and pellet showed consistent peaks of hexagonal structure that matched with reference ICDS card. In addition, pellets and film showed a strong (002) basal plane reflection, which is a strong indication of stacked planes along the loading direction. The results also showed a strong textural intensity along <001> direction in both produced pellets and films. Microscopy analysis with SEM showed that the sintered constituents were incorporated with the structure and small MoS2 flakes formed on the surface of the constituents and enabled their bonding. The chemistry information acquired with EDS also supports the incorporation with homogeneous dispersion of LAGP and graphite flakes in the structure. The EBSD analysis of both pellet and films were conducted to reveal the anisotropic feature of the samples. The pellets were scanned in both directions (c- and a-axis) while the film was only investigated on the surface, due to lack of thickness on the cross-section. The pole figure for {0001} planes of the pellets, which is measured perpendicular to the pressure loading, had shown a strong intensity along the <0001> direction, which is a strong basal orientation with ~24x randomly distributed intensity. The measurements parallel to applied pressure had a texture mainly orientated along the a-axis with ~15x randomly distributed intensity that shows an anisotropy between the two directions of cold sintered pellets. The findings are also in a consensus with the XRD results showing proof of stacked platelets along the c-axis that are arranged by applied uniaxial force. In order to evaluate the impact of Graphite in the system, electrical resistivities of the pellets were measured by a four-probe method. The resistivity measurements of samples in different graphite contents are conducted with respect to the temperature. The directional dependencies seen in the previous results were also investigated with this electrical testing with measuring samples in both directions, which are a, and c-axes. According to the results, the resistivities of a pure MoS2 pellet in a- and c-directions are 400 ohm.m and 120 ohm.m while MoS2-Graphite pellet (containing 20 wt.% Graphite) had 5 ohm.m and 1.5 ohm.m, respectively. It is believed that the preferential stacking of MoS2 planes along c-direction induced a higher resistivity along this direction. The results also suggest that the preferred orientation of the planes can create a barrier during current flow that increases the resistivity. The ratio of the resistivities between the two axes is found as~ 4.1, which is lower than the reported values (~1000) (El Beqqali et al. 1997; Hermann et al. 1973; Hippalgaonkar et al. 2017; Kam 1982; Souder and Brodie 1971). The testing of the electrodes in terms of electrochemical capabilities was conducted after preparing a half-cell in the argon-filled glove box. The results were displayed as Cyclic voltammetry (CV), and charge, and discharge profiles. The CV graphs of the MG electrode showed cathodic peaks at 0.28, 1.1, and 1.8V and anodic peaks at 0.29, and 2.5V, which are consistent with reported redox peaks of MoS2 electrodes. The cathodic peaks are signatures of Li+ insertion into MoS2 galleries and phase transformation of the structures. The first encountered anodic peak represents the lithium de-intercalation, graphite oxidation, and Mo oxidation to MoS2. The charge and discharge profiles have an agreement with CV curves, and the discharge curve depicts two visible plateaus at 1V vs. Li+/Li, the indicative formation of LixMoS2 and 0.5V vs. Li+/Li, the reduction of Mo4+ to Mo metal with Li2S formation. Cycling capability and capacity retention of the composites were significantly improved with the addition of solid electrolyte during the cold sintering process. The modified electrodes showed a first cycle capacity retention as 85.7%, and specific capacity as ~ 1000 mAh/g between 0 to 2.5 V vs. Li+/Li, after the 10th cycle. In summary, the thesis investigated the cold sintering of MoS2/Graphite composite structures, and results showed that consolidation of the composites was accomplished at low-temperatures with the aid of transient liquid-slurry, which includes AHM/Thiourea. The slurry provides a facile production of MoS2 flakes that can act as if cement between the pristine MoS2 and Graphite constituent and enables their bonding during the cold sintering process. It is believed that the uniaxial pressure, which is applied during the process, is amplified the anisotropy of the composite structure. The argument is supported by EBSD pole figures and electrical resistivity measurements, which are showed discrepancies between the a and c-directions. Another important finding is that increased graphite ratio improved both electrical conductivity electrochemical performance due to increased electron transfer during charge and discharge. The obtained charge and discharge profile in ~20-30wt% of graphite contents showed a typical plateau of MoS2 with increased capacity and cycling performance. The electrochemical performance was further increased by introducing a solid electrolyte, Li1.5Al0.5Ge1.5(PO4 )3(LAGP), to the system, which is improved Li+ ion intercalation capabilities of the electrodes. As a result, electrochemically active MoS2 and Graphite electrodes are produced with ~1000 mAh/g specific capacity using the cold sintering method.