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Synthesis of 2D materials and their applications in advanced sodium ion batteriesZhang, Fan 22 March 2022 (has links)
Sodium-ion batteries (SIBs) are rechargeable batteries analogous to lithium-ion batteries but use sodium ions (Na+) as the charge carriers. They are considered a promising alternative for lithium-ion batteries (LIBs) in renewable large-scale energy storage applications due to their similar electrochemical mechanisms and abundant sodium resources. Two-dimensional (2D) materials, with atomic or molecular thickness and large lateral lengths, have emerged as important functional materials due to their unique structures and excellent properties. These 2D nanosheets have been highly studied as sodium-ion battery anodes. They have large interlayer spacing, which can effectively buffer the big volume expansion and prevent electrode collapse during the charge-discharge process. Different strategies such as preparing composites, heterostructures, expanded structures, and chemical functionalization can greatly improve cycling stability and lead to high reversible capacity. In this dissertation, state-of-the-art SIB based on 2D material electrodes will be presented. In particular, Tin-based 2D materials and laser-scribed graphene anodes are discussed. Different strategies involving engineering both synthesis methods, intrinsic properties of materials, and device architecture are used to optimize the battery performance.
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UNDERSTANDING THE STRUCTURE-PROPERTY-PERFORMANCE RELATIONSHIP OF SILICON NEGATIVE ELECTRODESHu, Jiazhi 01 January 2019 (has links)
Rechargeable lithium ion batteries (LIBs) have long been used to power not only portable devices, e.g., mobile phones and laptops, but also large scale systems, e.g., electrical grid and electric vehicles. To meet the ever increasing demand for renewable energy storage, tremendous efforts have been devoted to improving the energy/power density of LIBs. Known for its high theoretical capacity (4200 mAh/g), silicon has been considered as one of the most promising negative electrode materials for high-energy-density LIBs. However, diffusion-induced stresses can cause fracture and, consequently, rapid degradation in the electrochemical performance of Si-based negative electrodes. To mitigate the detrimental effects of the large volume change, several strategies have been proposed. This dissertation focuses on two promising approaches to make high performance and durable Si electrodes for high capacity LIBs.
First, the effect of polymeric binders on the performance of Si-based electrodes is investigated. By studying two types of polymeric binders, polyvinylidene fluoride (PVDF) and sodium alginate (SA) using peel tests, SEM, XPS, and FTIR, I show that the high cohesive strength at the binder-silicon interface is responsible for the superior cell performance of the Si electrodes with SA as a binder. Hydrogen bonds formed between SA and Si is the main reason for the high cohesive strength since neither PVDF nor SA bonds covalently with Si.
Second, the fabrication of high performance Si/polyacrylonitrile (PAN) composite electrode via oxidative pyrolysis is investigated. We show that high performance Si/polyacrylonitrile (PAN) composite negative electrodes can be fabricated by a robust heat treatment in air at a temperature between 250 and 400oC. Using Raman, SEM, XPS, TEM, TGA, and nanoindention, we established that oxidation, dehydration, aromatization, and intermolecular crosslinking take place in PAN during the heat treatment, resulting in a stable cyclized structure which functions as both a binder and a conductive agent in the Si/PAN composite electrodes. With a Si mass loading of 1 mg/cm2, a discharge capacity of ~1600 mAh/g at the 100th cycle is observed in the 400oC treated Si/PAN composite electrode when cycled at a rate of C/3.
These studies on the structure-property-performance relations of Si based negative electrode may benefit the LIB community by providing (1) a guide for the design and optimization of binder materials for Si electrodes and (2) a facile method of synthesizing Si-based composite negative electrodes that can potentially be applied to other Si/polymer systems for further increasing the power/energy density and lower the cost of LIBs for electric vehicle applications and beyond.
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Modeling and simulation of heat of mixing in li ion batteriesSong, Zhibin January 2015 (has links)
Indiana University-Purdue University Indianapolis (IUPUI) / Heat generation is a major safety concern in the design and development of Li ion batteries (LIBs) for large scale applications, such as electric vehicles. The total heat generation in LIBs includes entropic heat, enthalpy, reaction heat, and heat of mixing. The main objective of this study is to investigate the influence of heat of mixing on the LIBs and to understand whether it is necessary to consider the heat of mixing during the design and development of LIBs. In the previous research,
Thomas and Newman derived methods to compute heat of mixing in LIB cells. Their results show that the heat of mixing cannot be neglected in comparison with the other heat sources at 2 C rate.
In this study, the heat of mixing in different materials, porosity, particle sizes, and charging/discharging rate was investigated. A COMSOL mathematical model was built to simulate the heat generation of LIBs. The LIB model was based on Newman’s model. LiMn2O4 and LiCoO2 were applied as the cathode materials, and
LiC6 was applied as the anode material. The results of heat of mixing were compared with the other heat sources to investigate the weight of heat of mixing in the total heat generation. The heat of mixing in cathode is smaller than the heat of mixing in anode, because of the diffusivity of LiCoO2 is 1 ×10-13 m2/s, which is larger than LiC6's diffusivity 2.52 × 10-14 m2/s. In the comparison, the heat of mixing is not as much as the irreversible heat and reversible heat, but it still cannot be neglected.
Finally, a special situation will be discussed, which is the heat of mixing under the relaxation status. For instance, after the drivers turn off their vehicles, the entropy, ix enthalpy and reaction heat in LIBs will stop generating, but the heat will still be generated due to the release of heat of mixing. Therefore, it is meaningful to investigate to see if this process has significant influence on the safety and cycle life of LIBs.
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Design and Fabrication of High Capacity Lithium-Ion Batteries using Electro-Spun Graphene Modified Vanadium Pentoxide CathodesAhmadian, Amirhossein 08 1900 (has links)
Indiana University-Purdue University Indianapolis (IUPUI) / Electrospinning has gained immense interests in recent years due to its potential application in various fields, including energy storage application. The V2O5/GO as a layered crystal structure has been demonstrated to fabricate nanofibers with diameters within a range of ~300nm through electrospinning technique. The porous, hollow, and interconnected nanostructures were produced by electrospinning formed by polymers such as Polyvinylpyrrolidone (PVP) and Polyvinyl alcohol (PVA), separately, as solvent polymers with electrospinning technique.
In this study, we investigated the synthesis of a graphene-modified nanostructured V2O5 through modified sol-gel method and electrospinning of V2O5/GO hybrid. Electrochemical characterization was performed by utilizing Arbin Battery cycler, Field Emission Scanning Electron Microscopy (FESEM), X-ray powder diffraction (XRD), Thermogravimetric analysis (TGA), Mercury Porosimetry, and BET surface area measurement.
As compared to the other conventional fabrication methods, our optimized sol-gel method, followed by the electrospinning of the cathode material achieved a high initial capacity of 342 mAh/g at a high current density of 0.5C (171 mA/g) and the capacity retention of 80% after 20 cycles. Also, the prepared sol-gel method outperforms the pure V2O5 cathode material, by obtaining the capacity almost two times higher.
The results of this study showed that post-synthesis treatment of cathode material plays a prominent role in electrochemical performance of the nanostructured vanadium oxides. By controlling the annealing and drying steps, and time, a small amount of pyrolysis carbon can be retained, which improves the conductivity of the V2O5 nanorods. Also, controlled post-synthesis helped us to prevent aggregation of electro-spun twisted nanostructured fibers which deteriorates the lithium diffusion process during charge/discharge of batteries.
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Design Principles for the Cathode/Electrolyte Interfacial Phenomena in Lithium Ion Batteries / リチウムイオン二次電池正極/電解質界面構造の解明と設計Yamamoto, Kentarou 23 March 2015 (has links)
京都大学 / 0048 / 新制・課程博士 / 博士(人間・環境学) / 甲第19072号 / 人博第725号 / 新制||人||174(附属図書館) / 26||人博||725(吉田南総合図書館) / 32023 / 京都大学大学院人間・環境学研究科相関環境学専攻 / (主査)教授 内本 喜晴, 教授 加藤 立久, 教授 吉田 寿雄 / 学位規則第4条第1項該当 / Doctor of Human and Environmental Studies / Kyoto University / DGAM
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Studies on Sodium-containing Transition Metal Phosphates for Sodium-ion Batteries / ナトリウムイオン電池用ナトリウム含有遷移金属リン酸塩に関する研究Nose, Masafumi 23 March 2016 (has links)
京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19739号 / 工博第4194号 / 新制||工||1647(附属図書館) / 32775 / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 安部 武志, 教授 陰山 洋, 教授 作花 哲夫 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM
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Atomistic simulation studies of lithiated MnO2 nanostructuresKgatwane, Kenneth Mompati January 2020 (has links)
Thesis (Ph.D.(Physics)) -- University of Limpopo, 2020 / We employ molecular dynamics simulations, using DL_POLY code, to study the structural behaviour of β-MnO2 cathode material during discharging through lithium-ion intercalation into the bulk, nanoparticle, nanorod, nanosheet, and nanoporous β-MnO2. It is shown that lithium-ions have an average coordination number of about 5.70 and prefer surface sites with high oxygen coordination. The average lattice parameter values at intercalation of 0.85 Li/Mn are found to be under 4% relative to the experimental values obtained at 0.92 Li/Mn. Moreover, all the lithiated β-MnO2 structures did not collapse at 0.85 Li/Mn as observed in the β-MnO2 mesoporous in experimental work. As lithium is limited, sodium is a good alternative charge carrier in lithium-ion batteries. As a result, we have also performed studies on sodium intercalation into bulk, nanoparticle, nanorod, nanosheet and nanoporous β-MnO2. The microstructures and radial distribution functions show that the β-MnO2 structures could be intercalated up to 0.24 Na/Mn without any obvious structural degradation. Beyond this sodium concentration, the microstructure collapses and become amorphous thus predicting a potentially lower capacity for Na-MnO2-β batteries. Also, as the voltage is an important factor in the energy density of lithium-ion batteries, we have studied the trends in the average intercalation potentials in relation to the various nano architectures. The trend, in increasing value of average intercalation potentials, were found to be bulk structure, nanorod, nanosheet, nanoporous and nanoparticle. This suggests that nanostructuring can enhance cell voltage.
Mechanical properties studies on the pure and lithiated bulk and nanorod β-MnO2 were also performed through uniaxial compressive and tensile strain application. The results show that under compressive strain the bulk structure and nanorod mitigate stress through the contraction and collapse of the inherent tunnel structures, known to cause electrochemical inactivity, and also through the shifting of the MnO6 octahedral planes. The collapsing of tunnels was found to occur more on the bulk structure and less on the nanorod, while the MnO6 octahedral plane shifts were found to occur more on the nanorod and less on the bulk structure. Unoccupied 1x2 or conjoined 1x2 were found to result in structural collapse irrespective of the host nanoarchitecture. The X-ray diffraction pattern
(v)
plots suggest that lithium intercalation and compressive stress application have a similar impact on the underlying structure of the various nanostructures. The microstructure analysis for bulk β-MnO2 under tensile strain reveals that fracture occurred in the brookite region and along the dislocation/stacking fault. The nanorod β-MnO2 mitigated stress through a rutile-to-brookite phase transition which occurred in the unstrained Li0.73MnO2-β and under tensile strain in LixMnO2-β for x = 0.00, 0.03, 0.12, and 0.24. In both the bulk and nanorod β-MnO2 the brookite phase was succeeded by structural breakdown leading to fracture and served as an indicator for imminent structural failure upon more tensile strain application. / National Research Foundation (NRF)
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Computer simulation studies of spinel LiMn2O4 and spinel LiNiXMn2-XO4 (0≤x≤2)Malatji, Kemeridge Tumelo January 2019 (has links)
Thesis (Ph.D. (Physics)) -- University of Limpopo, 2019 / LiMn2O4 spinel (LMO) is a promising cathode material for secondary lithium-ion
batteries which, despite its high average voltage of lithium intercalation, suffers
crystal symmetry lowering due to the Jahn-Teller active six-fold Mn3+ cations.
Although Ni has been proposed as a suitable substitutional dopant to improve the
energy density of LiMn2O4 and enhance the average lithium intercalation voltage,
the thermodynamics of Ni incorporation and its effect on the electrochemical
properties of this spinel are not fully understood.
Firstly, structural, electronic and mechanical properties of spinel LiMn2O4 and
LiNixMn2-xO4 have been calculated out using density functional theory employing the
pseudo-potential plane-wave approach within the generalised gradient
approximation, together with Virtual Cluster Approximation. The structural
properties included equilibrium lattice parameters; electronic properties cover both
total and partial density of states and mechanical properties investigated elastic
properties of all systems. Secondly, the pressure variation of several properties was
investigated, from 0 GPa to 50 GPa. Nickel concentration was changed and the
systems LiNi0.25Mn1.75O4, LiNi0.5Mn1.5O4 LiNi0.75Mn1.25O4 and LiNi0.875Mn1.125O4 were
studied. Calculated lattice parameters for LiMn2O4 and LiNi0.5Mn1.5O4 systems are
consistent with the available experimental and literature results. The average
Mn(Ni)-O bond length for all systems was found to be 1.9 Å. The bond lengths
decreased with an increase in nickel content, except for LiNi0.75Mn1.25O4, which gave
the same results as LiNi0.25Mn1.75O4. Generally, analysis of electronic properties
predicted the nature of bonding for both pure and doped systems with partial density
of states showing the contribution of each metal in our systems. All systems are
shown to be metallic as it has been previously observed for pure spinel LiMn2O4,
and mechanical properties, as deduced from elastic properties, depicted their
stabilities.
Furthermore, the cluster expansion formalism was used to investigate the nickel
doped LiMn2O4 phase stabilities. The method determines stable multi-component
crystal structures and ranks metastable structures by the enthalpy of formation while iv
maintaining the predictive power and accuracy of first-principles density functional
methods. The ground-state phase diagram with occupancy of Mn 0.81 and Ni 0.31
generated various structures with different concentrations and symmetries. The
findings predict that all nickel doped LMO structures on the ground state line are
most likely stable. Relevant structures (Li4Ni8O16, Li12MnNi17O48, Li4Mn6Ni2O16,
Li4Mn7NiO16 and Li4Mn8O16) were selected on the basis of how well they weighed
the cross-validation (CV) score of 1.1 meV, which is a statistical way of describing
how good the cluster expansion is at predicting the energy of each stable structure.
Although the structures have different symmetries and space groups they were
further investigated by calculating the mechanical and vibrational properties, where
the elastic constants and phonon vibrations indicated that the structures are stable
in accordance with stability conditions of mechanical properties and phonon
dispersions.
Lastly, a computer program that identifies different site occupancy configurations for
any structure with arbitrary supercell size, space group or composition was
employed to investigate voltage profiles for LiNixMn2-xO4. The density functional
theory calculations, with a Hubbard Hamiltonian (DFT+U), was used to study the
thermodynamics of mixing for Li(Mn1-xNix)2O4 solid solution. The results suggested
that LiMn1.5Ni0.5O4 is the most stable composition from room temperature up to at
least 1000K, which is in excellent agreement with experiments. It was also found
that the configurational entropy is much lower than the maximum entropy at 1000K,
indicating that higher temperatures are required to reach a fully disordered solid
solution. The maximum average lithium intercalation voltage of 4.8 eV was
calculated for the LiMn1.5Ni0.5O4 composition which correlates very well with the
experimental value. The temperature has a negligible effect on the Li intercalation
voltage of the most stable composition. The approach presented here shows that
moderate Ni doping of the LiMn2O4 leads to a substantial change in the average
voltage of lithium intercalation, suggesting an attractive route for tuning the cathode
properties of this spinel. / National Research Foundation (NRF)
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Synthesis And Properties Of Self-assembled C/sicn Nanocomposite Derived From Polymer PrecursorsLi, Cheng 01 January 2012 (has links)
The properties of C/SiCN nanocomposites synthesized by thermal decomposition of polymer precursors were studied in this work. The novel polymer-to-ceramic process enables us to tailor the ceramic structure in atomic level by designing the starting chemicals and pyrolysis procedures. It is of both fundamental and practical significance to investigate the properties and structures relationship of the nanocomposites. In this work, we explored their application potential in using as anode of lithium-ion secondary batteries. The structure and structural evolution of C/SiCN nanocomposite were investigated by using XRD, FTIR, SEM, TEM, Solid state NMR and Raman spectroscopy. The results revealed the nanocomposites consisted of amorphous SiCxNx-4 matrix and carbon nanoclusters distributed within it. The size of the carbon was measured by Raman spectroscopy, varied with starting chemicals and pyrolysis temperature. The electronic properties of the C/SiCN nanocomposite were studied by measuring the IV curves and a.c. impedance. The d.c. conductivity increased with carbon content and pyrolysis temperatures. The impedance spectra and fitted equivalent circuit results confirmed the existence of two phases in the nanocomposite. The possibility of using C/SiCN as anode in lithium-ion secondary batteries was investigated by electrochemical measurements, namely cyclic voltammetry, galvanostatic cyclic test and electrochemical impedance spectroscopy. The galvanostatic measurements showed that the nanocomposite with 26% of carbon nanoclusters exhibited a specific capacity of 480 mAh/g, iv which is 30% higher than that of commercial graphite anode. The high capacity of the nanocomposites is attributed to the formation of a novel structure around C/SiCN interface. The excellent electrochemical properties, together with the simple, low-cost processing, make the nanocomposites very promising for Li-ion battery applications
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3D Printing of Zinc Anode for Zinc Ion BatteriesAmoko, Stephen Adot Oyo 12 1900 (has links)
Recently, 3D printing has received increasing attention for the fabrication and assembly of electrodes for batteries due to the freedom of creating structures in any shape or size, porosity, flexibility, stretchability, and chemistry. Particularly, zinc ion batteries (ZIBs) are favored due to high safety, cheap materials cost, and high volumetric capacity (5,849 mAh/cm3), however, rapid evaporation of Zn due to low melting temperature has limited its 3D printability via conventional laser-based additive manufacturing technique. Here, we develop a printable ink for the fabrication of flexible and 3D printed Zn anode with varied surface areas using the direct ink writing (DIW) method. Our 3D printed porous and high surface area Zn anode structures effectively suppressed the dendrite growth while providing high Zn ion diffusion towards the cathode to significantly enhance the performance of ZIB. By varying filament distancing and path, we 3D printed zinc anode structures with different active surface areas, surface area to volume ratio, porosity, flexible and multiple layer structures that can be incorporated on any device. Carbon in the composite improved conductivity, and mechanical stability of 3D printed zinc anode. Our 3D printed composite anodes allowed flexible designing of batteries surpassing conventional battery designs such as coin cells or pouch cells and can be used to design printed energy storage systems.
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