Sähköautojen akkuteknologioiden tilannekatsaus

Tämän kandidaatintyön tavoitteena oli tutkia sähköautoissa käytettäviä akkuteknologioita ja verrata niiden ominaisuuksia keskenään sekä sähköautojen asettamien akkuvaatimusten kanssa. Akkuteknologiakartoituksen ja ominaisuusvertailun avulla tutkimuksessa oli tarkoitus selvittää sähköautojen akkujen kehitystä menneestä nykyhetkeen ja luoda katsaus akkuteknologian tulevaisuuteen. Tutkimuksessa painotettiin akkujen suorituskykynäkökulmaa, mutta tutkimuksessa otettiin kantaa myös eri akkuteknologioiden turvallisuuteen, ympäristötekijöihin ja hintaan. Työ toteutettiin kirjallisuustutkimuksena ja lähteinä käytettiin alan kirjallisuutta, IEEE artikkeleita, tutkimusraportteja ja verkkodokumentteja. Lisäksi tutkimuksessa hyödynnettiin akku- ja sähköautovalmistajilta saatavaa tietoa, johon suhtauduttiin varauksin. Tutkimuksessa kävi ilmi, että erilaisia litiumioniakkuteknologioita käytetään tällä hetkellä eniten sekä täyssähköautoissa että pistokehybrideissä. Huomattiin, että akkujen suorituskyvyn kehittyminen on nopeutunut viime vuosina. Erityisesti akkujen energianvarastointikykyyn vaikuttavat ominaisenergiatasot ovat kasvaneet selkeästi. Nykyisen kehittyneen litiumioniakkuteknologian todettiin täyttävän jo osittain lähivuosien suorituskykytavoitteet. Tutkimuksessa tultiin siihen tulokseen, että litiumrikkiakkuteknologia voi korvata litiumioniakkuteknologian ainakin täyssähköautoissa parempien ominaisenergiatasojen ja halvempien valmistuskustannuksien takia. Myös litiumilma-akkuteknologialla havaittiin olevan mahdollisuuksia haastaa muut litiumakkuteknologiat seuraavalla vuosikymmenellä. Tutkimuksen johtopäätöksenä todetaan, että sähköautot voivat kaupallistua laajemmin lähivuosina akkujen suorituskykyominaisuuksien kehittyessä jatkuvasti. Suorituskykyominaisuuksien parantuminen tulee todennäköisesti johtamaan siihen, että täyssähköautot yleistyvät enemmän ja pistokehybridit tulevat jäämään sähköautojen välivaiheeksi. Uusien akkuteknologioiden käyttöönotto kaupallisiin sähköautoihin voi viedä kuitenkin odotettua kauemmin, sillä akut tarvitsevat huolellista testausta ja käyttöönotto edellyttää, että kaikki ominaisuudet ovat vaaditulla tasolla.

Kulutuselektroniikan akkujen tekniset ominaisuudet ja markkinaosuudet 2015

Työssä tutkittiin kirjallisuustyönä akkuteknologian nykytilaa ja markkinoita kulutuselektroniikan osalta. Työssä tehtiin myös katsaus potentiaalisiin tulevaisuuden akkuteknologioihin. Työssä havaittiin, että kulutuselektroniikassa ainoat suuresti käytetyt akkutyypit ovat nikkelimetallihybridi- (NiMH) ja litiumioniakut (Li-ion). Tärkeimpänä ominaisuutena kulutuselektroniikassa akuilla yleensä pidetään kapasiteettia, jossa Li-ion akut ovat selvästi parempia jopa kaksinkertaisen energiatiheyden takia. Li-ion akuilla voidaan saavuttaa myös moninkertainen käyttöikä lataussykleinä ja moninkertainen purkausvirta, riippuen käytetystä katodimateriaalista. NiMH akuilla etuna on lähinnä halvempi hinta ja parempi turvallisuus. Toisaalta myös pieni jännite voidaan laskea hyväksi puoleksi, koska NiMH akuilla voidaan korvata kertakäyttöisiä alkaliparistoja. Vuonna 2012 Li-ion akkuja myytiin kapasiteetissa mitattuna jopa kahdeksan kertaa enemmän kuin NiMH akkuja ja myyntimäärien ennustetaan myös kasvavan tulevaisuudessa. Liion akkujen myyntimääristä suurin osa oli kulutuselektroniikan käyttökohteisiin ja jopa kaksi kolmasosaa oli kannettavien tietokoneiden ja kännyköiden akkuja. Uusia akkuteknologioita ja Li-ion akkujen parannuksia on paljon kehitteillä, mutta suurimman potentiaalin ja myös suuret ongelmat kaupallistumiseen omaa litium-ilma akut. Lyhyemmällä aikavälillä potentiaalisia teknologioita ovat litium-rikki akut, sekä nykyisiin Li-ion akkuihin kehitteillä olevat anodimateriaalit kuten esim. pii ja alumiini/titaani, joiden ongelmiin on löydetty ratkaisuja nanoteknologiasta.

Materiais cerâmicos de inserção aplicados a baterias de íons lítio

Esta revisão visa ser uma introdução à aplicação de materiais cerâmicos em dispositivos de armazenamento de energia, em especial baterias secundárias de íons lítio, dispositivos nos quais os materiais cerâmicos, especialmente óxidos, são muito importantes em todas as partes do dispositivo. A revisão está focada nos materiais cerâmicos para catodos e anodos, partes chaves destes dispositivos. Ela tem por principal finalidade ser uma fonte de informação para aqueles que desejem trabalhar com o desenvolvimento de materiais cerâmicos para tais tipos de dispositivos. Aspectos relacionados à nanotecnologia e materiais óxidos nanoestruturados para esta área são discutidos ao final do artigo.

Polyol-mediated synthesis of ultrafine tin oxide nanoparticles for reversible Li-ion storage

A simple, cheap and versatile, polyol-mediated fabrication method has been extended to the synthesis of tin oxide nanoparticles on a large scale. Ultrafine SnO2 nanoparticles with crystallite sizes of less than 5 nm were realized by refluxing SnCl2 . 2H(2)O in ethylene glycol at 195 degrees C for 4 h under vigorous stirring in air. The as-prepared SnO2 nanoparticles exhibited enhanced Li-ion storage capability and cyclability, demonstrating a specific capacity of 400 mAh g(-1) beyond 100 cycles. (c) 2006 Elsevier B.V. All rights reserved.

Preparação e caracterização de óxido de zinco nanoestruturado

Pós-graduação em Ciência e Tecnologia de Materiais - FC

A New Crystalline LiPON Electrolyte: Synthesis, Properties, and Electronic Structure

The new crystalline compound, Li2PO2N, was synthesized using high temperature solid state methods starting with a stoichiometric mixture of Li2O, P2O5, and P3N5. Its crystal structure was determined ab initio from powder X-ray diffraction. The compound crystallizes in the orthorhombic space group Cmc2(1) (# 36) with lattice constants a = 9.0692(4) angstrom, b = 53999(2) angstrom, and c = 4.6856(2) angstrom. The crystal structure of SD-Li2PO2N consists of parallel arrangements of anionic chains formed of corner sharing (PO2N2) tetrahedra. The chains are held together by Li+ cations. The structure of the synthesized material is similar to that predicted by Du and Holzwarth on the basis of first principles calculations (Phys. Rev. B 81,184106 (2010)). The compound is chemically and structurally stable in air up to 600 degrees C and in vacuum up to 1050 degrees C. The Arrhenius activation energy of SD-Li2PO2N in pressed pellet form was determined from electrochemical impedance spectroscopy measurements to be 0.6 eV, comparable to that of the glassy electrolyte LiPON developed at Oak Ridge National Laboratory. The minimum activation energies for Li ion vacancy and interstitial migrations are computed to be 0.4 eV and 0.8 eV, respectively. First principles calculations estimate the band gap of SD-Li2PO2N to be larger than 6 eV. (C) 2013 Elsevier B.V. All rights reserved.

NANOSCALE ELECTROCHEMISTRY BY IN-SITU TRANSMISSION ELECTRON MICROSCOPY

Nanoscale research in energy storage has recently focused on investigating the properties of nanostructures in order to increase energy density, power rate, and capacity. To better understand the intrinsic properties of nanomaterials, a new and advanced in situ system was designed that allows atomic scale observation of materials under external fields. A special holder equipped with a scanning tunneling microscopy (STM) probe inside a transmission electron microscopy (TEM) system was used to perform the in situ studies on mechanical, electrical, and electrochemical properties of nanomaterials. The nanostructures of titanium dioxide (TiO2) nanotubes are characterized by electron imaging, diffraction, and chemical analysis techniques inside TEM. TiO2 nanotube is one of the candidates as anode materials for lithium ion batteries. It is necessary to study their morphological, mechanical, electrical, and electrochemical properties at atomic level. The synthesis of TiO2 nanotubes showed that the aspect ratio of TiO2 could be controlled by processing parameters, such as anodization time and voltage. Ammonium hydroxide (NH4OH) treated TiO2 nanotubes showed unexpected instability. Observation revealed the nanotubes were disintegrated into nanoparticles and the tubular morphology was vanished after annealing. The nitrogen compounds incorporated in surface defects weaken the nanotube and result in the collapse of nanotube into nanoparticles during phase transformation. Next, the electrical and mechanical properties of TiO2 nanotubes were studied by in situ TEM system. Phase transformation of anatase TiO2 nanotubes into rutile nanoparticles was studied by in situ Joule heating. The results showed that single anatase TiO2 nanotubes broke into ultrafine small anatase nanoparticles. On further increasing the bias, the nanoclusters of anatase particles became prone to a solid state reaction and were grown into stable large rutile nanoparticles. The relationship between mechanical and electrical properties of TiO2 nanotubes was also investigated. Initially, both anatase and amorphous TiO2 nanotubes were characterized by using I-V test to demonstrate the semiconductor properties. The observation of mechanical bending on TiO2 nanotubes revealed that the conductivity would increase when bending deformation happened. The defects on the nanotubes created by deformation helped electron transportation to increase the conductivity. Lastly, the electrochemical properties of amorphous TiO2 nanotubes were characterized by in situ TEM system. The direct chemical and imaging evidence of lithium-induced atomic ordering in amorphous TiO2 nanotubes was studied. The results indicated that the lithiation started with the valance reduction of Ti4+ to Ti3+ leading to a LixTiO2 intercalation compound. The continued intercalation of Li ions in TiO2 nanotubes triggered an amorphous to crystalline phase transformation. The crystals were formed as nano islands and identified to be Li2Ti2O4 with cubic structure (a = 8.375 Å). This phase transformation is associated with local inhomogeneities in Li distribution. Based on these observations, a new reaction mechanism is proposed to explain the first cycle lithiation behavior in amorphous TiO2 nanotubes.

Developing Autonomous Microgrids: A Theoretical Case Study

Microgrids are autonomously operated, geographically clustered electricity generation and distribution systems that supply power in closed system settings; they are highly compatible with renewable energy sources and distributed generation technologies. Mocrogrids are currently a serially underutilized and underappreciated commodity in the energy infrastructure portfolio worldwide. To demonstrate feasibility under poor conditions (little renewable energy potential and high demand) this capstone project develops a theoretical case study in which a renewable microgrid is employed to power rural communities of southern Montgomery County, Arkansas. Utilizing commercially manufactured 1.5-megawatt wind turbines and a 1-megawatt solar panel generation system, 4-megawatts of lithium ion battery storage, and demand response technology, a microgrid is designed that supplies 235 households with reliable electricity supply.

Hybrid Power System Intelligent Operation and Protection Involving Plug-in Electric Vehicles

Two key solutions to reduce the greenhouse gas emissions and increase the overall energy efficiency are to maximize the utilization of renewable energy resources (RERs) to generate energy for load consumption and to shift to low or zero emission plug-in electric vehicles (PEVs) for transportation. The present U.S. aging and overburdened power grid infrastructure is under a tremendous pressure to handle the issues involved in penetration of RERS and PEVs. The future power grid should be designed with for the effective utilization of distributed RERs and distributed generations to intelligently respond to varying customer demand including PEVs with high level of security, stability and reliability. This dissertation develops and verifies such a hybrid AC-DC power system. The system will operate in a distributed manner incorporating multiple components in both AC and DC styles and work in both grid-connected and islanding modes. The verification was performed on a laboratory-based hybrid AC-DC power system testbed as hardware/software platform. In this system, RERs emulators together with their maximum power point tracking technology and power electronics converters were designed to test different energy harvesting algorithms. The Energy storage devices including lithium-ion batteries and ultra-capacitors were used to optimize the performance of the hybrid power system. A lithium-ion battery smart energy management system with thermal and state of charge self-balancing was proposed to protect the energy storage system. A grid connected DC PEVs parking garage emulator, with five lithium-ion batteries was also designed with the smart charging functions that can emulate the future vehicle-to-grid (V2G), vehicle-to-vehicle (V2V) and vehicle-to-house (V2H) services. This includes grid voltage and frequency regulations, spinning reserves, micro grid islanding detection and energy resource support. The results show successful integration of the developed techniques for control and energy management of future hybrid AC-DC power systems with high penetration of RERs and PEVs.

Zinc regeneration in rechargeable zinc-air fuel cells:a review

Zinc-air fuel cells (ZAFCs) present a promising energy source with a competing potential with the lithium-ion battery and even with proton-exchange membrane fuel cells (PEMFCs) for applications in next generation electrified transport and energy storage. The regeneration of zinc is essential for developing the next-generation, i.e., electrochemically rechargeable ZAFCs. This review aims to provide a comprehensive view on both theoretical and industrial platforms already built hitherto, with focus on electrode materials, electrode and electrolyte additives, solution chemistry, zinc deposition reaction mechanisms and kinetics, and electrochemical zinc regeneration systems. The related technological challenges and their possible solutions are described and discussed. A summary of important R&D patents published within the recent 10 years is also presented.

Bottom-up growth of fully transparent contact layers of indium tin oxide nanowires for light-emitting devices

Thin layers of indium tin oxide are widely used as transparent coatings and electrodes in solar energy cells, flat-panel displays, antireflection coatings, radiation protection and lithium-ion battery materials, because they have the characteristics of low resistivity, strong absorption at ultraviolet wavelengths, high transmission in the visible, high reflectivity in the far-infrared and strong attenuation in the microwave region. However, there is often a trade-off between electrical conductivity and transparency at visible wavelengths for indium tin oxide and other transparent conducting oxides. Here, we report the growth of layers of indium tin oxide nanowires that show optimum electronic and photonic properties and demonstrate their use as fully transparent top contacts in the visible to near-infrared region for light-emitting devices.

Synthesis and Characterization of Nanostructured Electro-active Materials

Thesis (Ph.D.)--University of Washington, 2016-08

DEVELOPMENT OF LI+ AND NA+ CONDUCTING CERAMICS AND CERAMIC STRUCTURES FOR USE IN SOLID STATE BATTERIES

A solid state lithium metal battery based on a lithium garnet material was developed, constructed and tested. Specifically, a porous-dense-porous trilayer structure was fabricated by tape casting, a roll-to-roll technique conducive to high volume manufacturing. The high density and thin center layer (< 20 μm) effectively blocks dendrites even over hundreds of cycles. The microstructured porous layers, serving as electrode supports, are demonstrated to increase the interfacial surface area available to the electrodes and increase cathode loading. Reproducibility of flat, well sintered ceramics was achieved with consistent powderbed lattice parameter and ball milling of powderbed. Together, the resistance of the LLCZN trilayer was measured at an average of 7.6 ohm-cm2 in a symmetric lithium cell, significantly lower than any other reported literature results. Building on these results, a full cell with a lithium metal anode, LLCZN trilayer electrolyte, and LiCoO2 cathode was cycled 100 cycles without decay and an average ASR of 117 ohm-cm2. After cycling, the cell was held at open circuit for 24 hours without any voltage fade, demonstrating the absence of a dendrite or short-circuit of any type. Cost calculations guided the optimization of a trilayer structure predicted that resulting cells will be highly competitive in the marketplace as intrinsically safe lithium batteries with energy densities greater than 300 Wh/kg and 1000 Wh/L for under $100/kWh. Also in the pursuit of solid state batteries, an improved Na+ superionic conductor (NASICON) composition, Na3Zr2Si2PO12, was developed with a conductivity of 1.9x10-3 S/cm. New super-lithiated lithium garnet compositions, Li7.06La3Zr1.94Y0.06O12 and Li7.16La3Zr1.84Y0.16O12, were developed and studied revealing insights about the mechanisms of conductivity in lithium garnets.

Tin Oxide Based Composites Derived Using Electrostatic Spray Deposition Technique as Anodes for Li-Ion Batteries

Recent advances in the electric & hybrid electric vehicles and rapid developments in the electronic devices have increased the demand for high power and high energy density lithium ion batteries. Graphite (theoretical specific capacity: 372 mAh/g) used in commercial anodes cannot meet these demands. Amorphous SnO2 anodes (theoretical specific capacity: 781 mAh/g) have been proposed as alternative anode materials. But these materials have poor conductivity, undergo a large volume change during charging and discharging, large irreversible capacity loss leading to poor cycle performances. To solve the issues related to SnO2 anodes, we propose to synthesize porous SnO2 composites using electrostatic spray deposition technique. First, porous SnO2/CNT composites were fabricated and the effects of the deposition temperature (200,250, 300 oC) & CNT content (10, 20, 30, 40 wt %) on the electrochemical performance of the anodes were studied. Compared to pure SnO2 and pure CNT, the composite materials as anodes showed better discharge capacity and cyclability. 30 wt% CNT content and 250 oC deposition temperature were found to be the optimal conditions with regard to energy capacity whereas the sample with 20% CNT deposited at 250 oC exhibited good capacity retention. This can be ascribed to the porous nature of the anodes and the improvement in the conductivity by the addition of CNT. Electrochemical impedance spectroscopy studies were carried out to study in detail the change in the surface film resistance with cycling. By fitting EIS data to an equivalent circuit model, the values of the circuit components, which represent surface film resistance, were obtained. The higher the CNT content in the composite, lower the change in surface film resistance at certain voltage upon cycling. The surface resistance increased with the depth of discharge and decreased slightly at fully lithiated state. Graphene was also added to improve the performance of pure SnO2 anodes. The composites heated at 280 oC showed better energy capacity and energy density. The specific capacities of as deposited and post heat-treated samples were 534 and 737 mAh/g after 70 cycles. At the 70th cycle, the energy density of the composites at 195 °C and 280 °C were 1240 and 1760 Wh/kg, respectively, which are much higher than the commercially used graphite electrodes (37.2-74.4 Wh/kg). Both SnO2/CNTand SnO2/grapheme based composites with improved energy densities and capacities than pure SnO2 can make a significant impact on the development of new batteries for electric vehicles and portable electronics applications.

Hybrid power system intelligent operation and protection involving plug-in electric vehicles

Two key solutions to reduce the greenhouse gas emissions and increase the overall energy efficiency are to maximize the utilization of renewable energy resources (RERs) to generate energy for load consumption and to shift to low or zero emission plug-in electric vehicles (PEVs) for transportation. The present U.S. aging and overburdened power grid infrastructure is under a tremendous pressure to handle the issues involved in penetration of RERS and PEVs. The future power grid should be designed with for the effective utilization of distributed RERs and distributed generations to intelligently respond to varying customer demand including PEVs with high level of security, stability and reliability. This dissertation develops and verifies such a hybrid AC-DC power system. The system will operate in a distributed manner incorporating multiple components in both AC and DC styles and work in both grid-connected and islanding modes. ^ The verification was performed on a laboratory-based hybrid AC-DC power system testbed as hardware/software platform. In this system, RERs emulators together with their maximum power point tracking technology and power electronics converters were designed to test different energy harvesting algorithms. The Energy storage devices including lithium-ion batteries and ultra-capacitors were used to optimize the performance of the hybrid power system. A lithium-ion battery smart energy management system with thermal and state of charge self-balancing was proposed to protect the energy storage system. A grid connected DC PEVs parking garage emulator, with five lithium-ion batteries was also designed with the smart charging functions that can emulate the future vehicle-to-grid (V2G), vehicle-to-vehicle (V2V) and vehicle-to-house (V2H) services. This includes grid voltage and frequency regulations, spinning reserves, micro grid islanding detection and energy resource support. ^ The results show successful integration of the developed techniques for control and energy management of future hybrid AC-DC power systems with high penetration of RERs and PEVs.^