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Électrodes négatives pour batteries Li-ion à base de FeSn2 : performances, Mécanismes et Vieillissement. / Negatives electrodes feSn2 based for Li-ion Batteries : performances mechanisms and aging.Chamas, Mohamad 16 December 2010 (has links)
Comme dispositif de stockage de l'énergie, les batteries Li-ion possèdent de nombreux avantages et en particulier une densité d'énergie élevée. Toutefois, la recherche de nouveaux matériaux d'électrode reste nécessaire pour améliorer les performances. Ce travail concerne les matériaux d'électrode négative avec pour objectif l'augmentation de leur capacité. Dans ce but nous nous sommes intéressés à un composé intermétallique à base d'étain : FeSn2. Nous avons effectué la synthèse de ce matériau par différents procédés afin d'obtenir des microparticules et un matériau nanostructuré. L'étude des mécanismes électrochimiques a montré que pour ces deux types de matériaux la première décharge constituait une étape essentielle de restructuration de l'électrode aboutissant à la formation in situ d'un nanocomposite Fe/Li7Sn2. Le suivi quantitatif de la réaction de conversion, responsable de cette transformation, a été effectué par spectrométrie Mössbauer in situ et operando grâce à une nouvelle cellule électrochimique que nous avons développée. D'autres techniques ont été utilisées : DRX et spectrométrie d'impédance in situ, SQUID et XPS. En associant ces différentes techniques nous avons montré que les cycles de charge/décharge étaient basés sur une réaction réversible entre Li7Sn2 et LixSn riche en étain sans reformation de FeSn2. Ce résultat diffère des mécanismes observés pour CoSn2 et Ni3Sn4 et pourrait expliquer la perte progressive de capacité généralement observée avec FeSn2. Toutefois, les performances sont intéressantes avec une capacité de 400-500mAh/g sur 50 cycles entre C/10 et 10C. Enfin, nous avons mis en évidence un phénomène de vieillissement de l'électrode en fin de décharge qui provoque sa délithiation irréversible. / Li-ion batteries are rechargeable energy storage systems with high energy density. However, new electrode materials are needed in order to improve the electrochemical performances. This thesis is devoted to a tin based intermetallic compound as negative electrode for Li-ion batteries: FeSn2. Different synthesis methods were used in order to obtain microsized particles and nanostructured materials. The study of the electrochemical mechanisms shows that for both types of materials the first discharge is an essential restructuring step leading to the in situ formation of a Fe/Li7Sn2 nanocomposite. This transformation is due to a conversion reaction that was quantitatively characterized by Mössbauer spectroscopy from in situ and operando measurements. A new cheap and reliable electrochemical cell was developed for these measurements. Other techniques have also been used: in situ XRD and impedance spectroscopy, XPS and SQUID. By combining these tec hniques we have shown that the charge/discharge cycles were based on a reversible reaction between Li7Sn2 and tin-rich LixSn without back reaction with iron nanoparticles. This result is rather surprising because it differs from the mechanisms observed for CoSn2 and Ni3Sn4 but could explain the progressive loss of capacity usually observed with FeSn2. However, interesting performances were obtained with a capacity of 400-500mAh/g for 50 cycles and lithium rates between C/10 and 10C. Finally, we have identified aging process for the electrode at the end of discharge that causes irreversible delithiation.
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Synthesis and characterization of nanostructure electrodes for lithium ion batteries. / 鋰離子電池納米電極的製備和表徵 / CUHK electronic theses & dissertations collection / Synthesis and characterization of nanostructure electrodes for lithium ion batteries. / Li li zi dian chi na mi dian ji de zhi bei he biao zhengJanuary 2013 (has links)
Liu, Hao = 鋰離子電池納米電極的製備和表徵 / 劉昊. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2013. / Includes bibliographical references (leaves 99-103). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese. / Liu, Hao = Li li zi dian chi na mi dian ji de zhi bei he biao zheng / Liu Hao.
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Designing Solid Electrolytes for Rechargeable Solid-State BatteriesZhai, Haowei January 2019 (has links)
Lithium-ion battery (LIB) is an indispensable energy storage device in portable electronics, and its applications in electric vehicles and grid-level energy storage are increasing dramatically in recent years due to high demands. To meet energy demands and address fire hazards, next generation batteries with better safety, higher energy density, and longer cycle life have been actively investigated. In this thesis, works on polymer and ceramic solid electrolytes to improve safety and energy density of rechargeable solid-state batteries are discussed.
In the first section, a flexible composite solid electrolyte is presented. Since ceramic electrolytes have high conductivities but are fragile, and polymer electrolytes are easy to process but have low conductivities, we propose a composite structure that combines these advantages. A vertically aligned and connected ceramic electrolyte is realized through the ice-templating method to improve the ionic conduction. Then a polyether-based polymer electrolyte is added to make the composite electrolyte flexible. Specifically, vertically aligned and connected LATP and LAGP nanoparticles (NPs) in the polyethylene oxide (PEO) matrix are made. The conductivity reaches 0.52 × 10-4 S/cm for LATP/PEO, and 1.67 × 10-4 S/cm for aligned LAGP/PEO composite electrolytes, which are several times higher than that with randomly dispersed LATP/LAGP NPs in PEO. Compared to the pure PEO electrolyte, the mechanical and thermal stabilities of the composite solid electrolyte are higher. The LFP-LAGP/PEO-Li cell with 148.7 mAh/g during the first discharge at 0.3C has over 95% capacity retention after 200 cycles. This method opens a new approach to optimize ion conduction in composite solid electrolytes for solid-state batteries.
In the next section, polyether-based polymer electrolytes such as PEO and PEG are studied. Polyether-based electrolytes are electrochemically unstable above 4 V, restricting their use with high voltage cathodes such as NMC for high energy density. A technique involving atomic layer deposition (ALD) of Al2O3 to stabilize the polyether-based electrolyte with 4 V class cathodes is described. With a 2 nm Al2O3 coating, the capacity retention stays at 84.7% after 80 cycles and 70.3% after 180 cycles for the polyether-based electrolyte. Without the coating, the capacity drops more than 50% after only 20 cycles. This study opens new opportunity to develop safe electrolytes for lithium batteries with high energy density.
In the final section, we propose a new polymer electrolyte, a poly(vinylidene fluoride) (PVDF) polymer electrolyte with organic plasticizer dimethylformamide (DMF), which possesses compatibility with 4V cathode for high energy density and high ionic conductivity (1.2×10-4 S/cm) at room temperature. This polymer electrolyte can be used as a supplement for the polyether-based electrolytes we discussed in the first two sections. In this polymer electrolyte, palygorskite ((Mg,Al)2Si4O10(OH)) nanowires are introduced to form composite solid electrolytes (CPE) to enhance both stiffness and toughness of PVDF/DMF-based polymer electrolyte. With 5 wt % of palygorskite nanowires, the elastic modulus of the PVDF-DMF CPE increases from 9.0 MPa to 96 MPa, and its yield stress increases by 200%. We further demonstrate that full cells composed of Li(Ni1/3Mn1/3Co1/3)O2 (NMC 111) cathode, PVDF-DMF/palygorskite CPE, and lithium metal anode, can be cycled over 200 times at 0.3 C, with 97% capacity retention. Moreover, the PVDF-DMF electrolyte is nonflammable, making it a safer alternative to the conventional liquid electrolyte. Our work illustrates that the PVDF-DMF/palygorskite CPE is a promising electrolyte for solid state batteries with better safety and cycling performance.
Collectively, we study the polyether-based polymer electrolyte and ceramic electrolyte to combine their advantages through the ice-templating method in a battery, use ALD technique to stabilize polyether-based electrolyte for high energy density, and propose an alternative PVDF/DMF-based polymer electrolyte with nanowire additives for high energy density and stable cycling, contributing to the rechargeable solid-state batteries, with better safety, higher energy density and better cycling stability.
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Towards A Better Understanding of Lithium Ion Local Environment in Pure, Binary and Ternary Mixtures of Carbonate Solvents : A Numerical Approach / Etude théorique et numérique de l'interaction des ions lithium dans les solvants carbonates et leurs mélangesPonnuchamy, Veerapandian 23 January 2015 (has links)
En raison de l'augmentation de la demande d'énergie, ressources écologiques respectueux de l'environnement et durables (solaires, éoliennes) doivent être développées afin de remplacer les combustibles fossiles. Ces sources d'énergie sont discontinues, étant corrélés avec les conditions météorologiques et leur disponibilité est fluctuant dans le temps. En conséquence, les dispositifs de stockage d'énergie à grande échelle sont devenus incontournables, pour stocker l'énergie sur des échelles de temps longues avec une bonne compatibilité environnementale. La conversion d'énergie électrochimique est le mécanisme clé pour les développements technologiques des sources d'énergie alternatives. Parmi ces systèmes, les batteries Lithium-ion (LIB) ont démontré être les plus robustes et efficaces et sont devenus la technologie courante pour les systèmes de stockage d'énergie de haute performance. Ils sont largement utilisés comme sources d'énergie primaire pour des applications populaires (ordinateurs portables, téléphones cellulaires, et autres). La LIB typique est constitué de deux électrodes, séparés par un électrolyte. Celui-ci joue un rôle très important dans le transfert des ions entre les électrodes fournissant la courante électrique. Ce travail de thèse porte sur les matériaux complexes utilisés comme électrolytes dans les LIB, qui ont un impact sur les propriétés de transport du ion Li et les performances électrochimiques. Habituellement l'électrolyte est constitué de sels de Li et de mélanges de solvants organiques, tels que les carbonates cycliques ou linéaires. Il est donc indispensable de clarifier les propriétés structurelles les plus importantes, et leurs implications sur le transport des ions Li+ dans des solvants purs et mixtes. Nous avons effectué une étude théorique basée sur la théorie du fonctionnelle densité (DFT) et la dynamique moléculaire (MD), et nous avons consideré des carbonates cyclique (carbonate d'éthylène, EC, et carbonate de propylène, PC) et le carbonate de diméthyle, DMC, linéaire. Les calculs DFT ont fourni une image détaillée des structures optimisées de molécules de carbonate et le ion Li+, y compris les groupes pures Li+(S)n (S =EC,PC,DMC et n=1-5), groupes mixtes binaires, Li+(S1)m(S2)n (S1,S2=EC,PC,DMC, m+n=4), et ternaires Li+(EC)l(DMC)m(PC)n (l+m+n=4). L'effet de l'anion PF6 a également été étudié. Nous avons aussi étudié la structure de la couche de coordination autour du Li+, dans tous les cas. Nos résultats montrent que les complexes Li+(EC)4, Li+(DMC)4 et Li+(PC)3 sont les plus stables, selon les valeurs de l'énergie libre de Gibbs, en accord avec les études précédentes. Les énergies libres de réactions calculés pour les mélanges binaires suggèrent que l'ajout de molécules EC et PC aux clusters Li+ -DMC sont plus favorables que l'addition de DMC aux amas Li+-EC et Li+-PC. Dans la plupart des cas, la substitution de solvant aux mélanges binaires sont défavorables. Dans le cas de mélanges ternaires, la molécule DMC ne peut pas remplacer EC et PC, tandis que PC peut facilement remplacer EC et DMC. Notre étude montre que PC tend à substituer EC dans la couche de solvation. Nous avons complété nos études ab-initio par des simulations MD d'une ion Li immergé dans les solvants purs et dans des mélanges de solvants d'intérêt pour les batteries, EC:DMC(1: 1) et EC:DMC:PC(1:1:3). MD est un outil très puissant et nous a permis de clarifier la pertinence des structures découvertes par DFT lorsque le ion est entouré par des solvants mélangés. En effet,la DFT fournit des informations sur les structures les plus stables de groupes isolés, mais aucune information sur leur stabilité ou de la multiplicité (entropie) lorsqu'il est immergé dans un environnement solvant infinie. Les données MD, ainsi que les calculs DFT nous ont permis de donner une image très complète de la structure locale de mélanges de solvants autour le ion lithium, sensiblement amélioré par rapport aux travaux précédents. / Due to the increasing global energy demand, eco-friendly and sustainable green resources including solar, or wind energies must be developed, in order to replace fossil fuels. These sources of energy are unfortunately discontinuous, being correlated with weather conditions and their availability is therefore strongly fluctuating in time. As a consequence, large-scale energy storage devices have become fundamental, to store energy on long time scales with a good environmental compatibility. Electrochemical energy conversion is the key mechanism for alternative power sources technological developments. Among these systems, Lithium-ion (Li+) batteries (LIBs) have demonstrated to be the most robust and efficient, and have become the prevalent technology for high-performance energy storage systems. These are widely used as the main energy source for popular applications, including laptops, cell phones and other electronic devices. The typical LIB consists of two (negative and positive) electrodes, separated by an electrolyte. This plays a very important role, transferring ions between the electrodes, therefore providing the electrical current. This thesis work focuses on the complex materials used as electrolytes in LIBs, which impact Li-ion transport properties, power densities and electrochemical performances. Usually, the electrolyte consists of Li-salts and mixtures of organic solvents, such as cyclic or linear carbonates. It is therefore indispensable to shed light on the most important structural (coordination) properties, and their implications on transport behaviour of Li+ ion in pure and mixed solvent compositions. We have performed a theoretical investigation based on combined density Functional Theory (DFT) calculations and Molecular Dynamics (MD) simulations, and have focused on three carbonates, cyclic ethylene carbonate (EC) and propylene carbonate (PC), and linear dimethyl carbonate (DMC). DFT calculations have provided a detailed picture for the optimized structures of isolated carbonate molecules and Li+ ion, including pure clusters Li+(S)n (S=EC, PC, DMC and n=1-5), mixed binary clusters, Li+(S1)m(S2)n (S1, S2 =EC, PC, DMC, with m+n=4), and ternary clusters Li+(EC)l(DMC)m(PC)n with l+m+n=4. Pure solvent clusters were also studied including the effect of PF6- anion. We have investigated in details the structure of the coordination shell around Li+ for all cases. Our results show that clusters such as Li+(EC)4, Li+(DMC)4 and Li+(PC)3 are the most stable, according to Gibbs free energy values, in agreement with previous experimental and theoretical studies. The calculated Gibbs free energies of reactions in binary mixtures suggest that the addition of EC and PC molecules to the Li+-DMC clusters are more favourable than the addition of DMC to Li+-EC and Li+-PC clusters. In most of the cases, the substitution of solvent to binary mixtures are unfavourable. In the case of ternary mixtures, the DMC molecule cannot replace EC and PC, while PC can easily substitute both EC and DMC molecules. Our study shows that PC tends to substitute EC in the solvation shell. We have complemented our ab-initio studies by MD simulations of a Li-ion when immersed in the pure solvents and in particular solvents mixtures of interest for batteries applications, e.g. , EC:DMC (1:1) and EC:DMC:PC(1:1:3). MD is a very powerful tool and has allowed us to clarify the relevance of the cluster structures discovered by DFT when the ion is surrounded by bulk solvents. Indeed, DFT provides information about the most stable structures of isolated clusters but no information about their stability or multiplicity (entropy) when immersed in an infinite solvent environment. The MD data, together the DFT calculations have allowed us to give a very comprehensive picture of the local structure of solvent mixtures around Lithium ion, which substantially improve over previous work.
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Rechargeable lithium-sulfur batteries with novel electrodes, cell configurations, and recharge strategiesSu, Yu-Sheng, 1983- 07 November 2013 (has links)
Entering a new era of green energy, several criteria such as cost, cycle life, safety, efficiency, energy, and power need to be considered in developing electrical energy storage systems for transportation and grid storage. Lithium-sulfur (Li-S) batteries are one of the prospective candidates in this regard as sulfur offers a high theoretical capacity of 1675 mAh g⁻¹ at a safer operating voltage range of ~ 2.1 V and low-cost benefit. This dissertation explores various original designs of novel electrodes, new cell configurations, and recharge strategies that can boost the cycle performance of Li-S cells. An in situ sulfur deposition route has been developed for synthesizing sulfur-carbon composites as cathode materials. This facile synthesis method involves the precipitation of elemental sulfur at the interspaces between carbon nanoparticles in aqueous solution at room temperature. Thus, a sulfur/multi-wall carbon nanotube (MWCNT) composite cathode with high-rate cyclability has been synthesized by the same process. Due to the self-weaving behavior of MWCNTs, extra cell components such as binders and current collectors are rendered unnecessary, thereby streamlining the electrode manufacturing process and decreasing the cell weight. A novel Li-S cell configuration with a carbon interlayer inserted between the separator and cathode has been designed to enhance the battery cyclability as well. A conductive MWCNT interlayer acting as a pseudo-upper current collector not only reduces the charge transfer resistance of sulfur cathodes significantly, but also localizes and retains the dissolved active material during cycling. Moreover, with a bi-functional microporous carbon paper intrerlayer, we observe a significant improvement not only in the active material utilization but also in capacity retention, without involving complex synthesis or surface modification. The kinetics of the sulfur/long-chain polysulfide redox couple (S₈ [double-sided arrow] Li₂S₄, theoretical capacity = 419 mAh g⁻¹) is experimentally proven to be very fast in the Li-S system. The Li-S cell with a blended carbon interlayer retains excellent cycle stability and possesses a high percentage of active material utilization over 250 cycles at high C rates (up to 15C). The meso-/micro- pores in the interlayer are in charge of accommodating the shuttling polysulfides and offering sufficient electrolyte accessibility. An appropriate and applicable way to recharge Li-S cells within the lower plateau region has been designed to offer tremendous improvement with various Li-S battery systems. Adjusting the charging condition led to long cycle life (over 500 cycles) with excellent capacity retention (> 99%) by inhibiting the electrochemical reactions along with polysulfide dissolution. In addition, the redox products determined by ex situ x-ray photoelectron spectroscopy (XPS) further clarify the mechanism of polysulfide formation upon cycling, which is partially different from the general consensus. These approaches of novel electrode designs, new cell configurations, charging strategy, and understanding of the reactions in different discharge steps could progress the development and advancement of Li-S batteries. / text
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Functional Binders at the Interface of Negative and Positive Electrodes in Lithium BatteriesJeschull, Fabian January 2015 (has links)
In this thesis, electrode binders as vital components in the fabrication of composite electrodes for lithium-ion (LIB) and lithium-sulfur batteries (LiSB) have been investigated. Poly(vinylidene difluoride) (PVdF) was studied as binder for sulfur-carbon positive electrodes by a combination of galvanostatic cycling and nitrogen absorption. Poor binder swelling in the electrolyte and pore blocking in the porous carbon were identified as origins of low discharge capacity, rendering PVdF-based binders an unsuitable choice for LiSBs. More promising candidates are blends of poly(ethylene oxide) (PEO) and poly(N-vinylpyrrolidone) (PVP). It was found that these polymers interact with soluble lithium polysulfide intermediates generated during the cell reaction. They can increase the discharge capacity, while simultaneously improving the capacity retention and reducing the self-discharge of the LiSB. In conclusion, these binders improve the local electrolyte environment at the electrode interface. Graphite electrodes for LIBs are rendered considerably more stable in ‘aggressive’ electrolytes (a propylene carbonate rich formulation and an ether-based electrolyte) with the poorly swellable binders poly(sodium acrylate) (PAA-Na) and carboxymethyl cellulose sodium salt (CMC-Na). The higher interfacial impedance seen for the conventional PVdF binder suggests a protective polymer layer on the particles. By reducing the binder content, it was found that PAA-Na has a stronger affinity towards electrode components with high surface areas, which is attributed to a flexible polymer backbone and a higher density of functional groups. Lastly, a graphite electrode was combined with a sulfur electrode to yield a balanced graphite-sulfur cell. Due to a more stable electrode-electrolyte interface the self-discharge of this cell could be reduced and the cycle life was extended significantly. This example demonstrates the possible benefits of replacing the lithium metal negative electrode with an alternative electrode material.
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Investigating the stability of sodium couple in the ionic electrolytes and cathode materialsPark, Sea Hoon 05 1900 (has links)
No description available.
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Organic Negative Electrode Materials For Li-ion and Na-ion BatteriesOltean, Alina January 2015 (has links)
No description available.
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Eco battery exchange system /Kasetsuwan, Rit. January 1992 (has links)
Thesis (M.S.)--Rochester Institute of Technology, 1992. / Typescript. Includes bibliographical references (leaf 41).
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Investigating paste additives to improve the specific energy performance of lead-acid batteries /Zhang, Song, January 1900 (has links)
Thesis (Ph. D.)--University of Idaho, 2005. / Also available online in PDF format. Abstract. "July, 2005." Includes bibliographical references (leaves 94-98).
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