Glassy materials for lithium batteries: electrochemical properties and devices performances (original) (raw)
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Solid State Ionics, 2002
New electrolyte materials, polymers or inorganic glasses, allow the design of flat lithium primary or secondary batteries for miniaturised devices from smart cards to CMOS back up. The so-called ''hybrid plastic electrolytes'' allow the design of thick film cells (1 -3 mm) with a surface capacity of some mA h cm À 2 . For Li-ion secondary batteries, the number of cycles does not currently exceed 500. All solid state thin film batteries are manufactured using sputtering and vacuum evaporation techniques. Their thickness and surface capacity are about one order of magnitude lower than for the polymer electrolyte batteries. In spite of metallic Li anodes, they offer a better cyclability and the solid state of all components guaranties no liquid leakage. D
New amorphous thin-film lithium electrolyte and rechargeable microbattery
IEEE 35th International Power Sources Symposium, 1992
Sputtering of Li3PO4 in pure N2 results in the formation of an amorphous lithium electrolyte that is stable in contact with lithium and has electrical properties that are suitable for application in a thinfilm cell. Thin-film rechargeable lithium cells have been fabricated and characterized using this electrolyte between a lithium anode and an amorphous vanadium oxide cathode. The open circuit voltage of the cell is 3.6 to 3.7 V, and it has a capacity of 130 pAh/cm2 when discharged to 1.5 V. The ac impedance of the cells measured at different stages of discharge indicate a significant decrease in internal resistance at about the midpoint of the discharge.
Liquid electrolytes for lithium and lithium-ion batteries
Journal of Power Sources, 2003
A number of advances in electrolytes have occurred in the past 4 years, which have contributed to increased safety, wider temperature range of operation, better cycling and other enhancements to lithium-ion batteries. The changes to basic electrolyte solutions that have occurred to accomplish these advances are discussed in detail. The solvent components that have led to better low-temperature operation are also considered. Also, additives that have resulted in better structure of the solid electrolyte interphase (SEI) are presented as well as proposed methods of operation of these additives. Other additives that have lessened the flammability of the electrolyte when exposed to air and also caused lowering of the heat of reaction with the oxidized positive electrode are discussed. Finally, additives that act to open current-interrupter devices by releasing a gas under overcharge conditions and those that act to cycle between electrodes to alleviate overcharging are presented. As a class, these new electrolytes are often called ''functional electrolytes''. Possibilities for further progress in this most important area are presented. Another area of active work in the recent past has been the reemergence of ambient-temperature molten salt electrolytes applied to alkali metal and lithium-ion batteries. This revival of an older field is due to the discovery of new salt types that have a higher voltage window (particularly to positive potentials) and also have greatly increased hydrolytic stability compared to previous ionic liquids. While practical batteries have not yet emerged from these studies, the increase in the number of active researchers and publications in the area demonstrates the interest and potentialities of the field. Progress in the field is briefly reviewed. Finally, recent results on the mechanisms for capacity loss on shelf and cycling in lithium-ion cells are reviewed. Progress towards further market penetration by lithium-ion cells hinges on improved understanding of the failure mechanisms of the cells, so that crucial problems can be addressed.
Rechargeable solid state lithium microbatteries
Micro Electro Mechanical …, 1993
A rechargeable thin-film lithium battery that can be used as a miniature power supply for small devices has been recently developed. The battery consists of an amorphous vanadium pentoxide (aV2O5) cathode, an amorphous lithium phosphorus oxynitride (Lipon) electrolyte, and a lithium anode. A thin-film cover layer protects the battery from exposure to air and water vapor. The battery can deliver u p to 60 p A l c m 2 of current between 3.6 V and 1.5 V. Higher voltages can be achieved by fabricating two or more cells in series. A l-cm2 cell with a 1 to 1.5-pmthick cathode discharged from 3.6 to 1.5 V at 12 pA typically yields about 440 mC and delivers about 1 J. Using the combined mass of the cathode, electrolyte, and the anode (3x over capacity), the specific energy of the cell is 1.4 x 106 J/kg and the energy density is 2.1 x 106 J/1.
Rechargeable thin-film lithium batteries
Solid State Ionics, 1994
,._u=,_'_"''°"_'_i _°_=.-SOLIDSTATEDIVISION o = _ .-._-OAK RIDGE NATIONAL LABORATORY _,_ _°_-a =_ .== o Managed by ._ _ _ .. _ MARTIN MARIETTA ENERGY SYSTEMS, INC. _. o_ _ under = o _..-._ _ o= Contract No. DE-AC05-84OR21400 _,_._:_t ==_-with the o _ o.== _" _" U.S. DEPARTMENT OF ENERGY • ._ _ o a _ _ _ _ _ Oak Ridge, Tennessee 37831-6030 = a August 1993 ._ _ ..
Solid-state batteries: Unlocking lithium's potential with ceramic solid electrolytes
Recent progress indicates that ceramic materials may soon supplant liquid electrolytes in batteries, offering improved energy capacity and safety. W idespread adoption of electric vehicles (EV) will require dramatic changes to the energy storage market. Total worldwide lithium-ion (Li-ion) battery production was 221 GWh in 2018, while EV demand alone is projected to grow to more than 1,700 GWh by 2030. 1 As economies of scale have been met in Li-ion battery production, price at the pack level has fallen and is expected to break $100/kWh within the next few years. Li-ion batteries are expected to address near-term energy storage needs, with advances in cell chemistry providing steady improvement in cell capacity. Yet Li-ion batteries will eventually approach the practical limits of their energy storage capacity , and the volatile flammable liquid electrolyte in Li-ion cells requires thermal management systems that add cost, mass, and complexity to EV battery packs. Recent progress demonstrates that Li-ion conducting solid electrolytes have fundamental properties to supplant current Li-ion liquid electrolytes. Moreover, using solid electrolytes enables all-solid-state batteries, a new class of lithium batteries that are expected to reach storage capacities well beyond that of today's Li-ion batteries. The promise of a safer high-capacity battery has attracted enormous attention from fundamental research through start-up companies, with significant investment from venture capitalists and automakers. The Li-ion battery The 1970s marked development of the first Li-ion cathode intercalation materials. Cells with a metallic lithium anode were commercialized in the 1980s, but it was soon discovered Solid-state batteries: Unlocking lithium's potential with ceramic solid electrolytes that lithium deposits in dendritic structures upon battery cycling. These dendrites eventually grow through the separa-tor, connecting the anode and cathode and causing a dangerous short circuit of the cell. The solution was to replace the lithium anode with a graphite Li-ion host material, thereby producing the modern Li-ion battery. First introduced by Sony in 1991, the graphite anode is paired with a LiCoO 2 cathode and flooded with a liquid organic electrolyte with dissolved lithium salt. The dissolved lithium provides Li-ion transport within the cell. A thin and porous polymer separator prevents physical contact between the anode and cathode while allowing ionic transport between electrodes. This basic cell structure remains unchanged today, albeit with numerous energy-boosting innovations, including silicon anode additions, electrolyte additives to increase cycle life, and high nickel-content cathodes. These innovations have led to an average of 8% annualized energy density improvement in Li-ion batteries. 2 Despite this progress, the volumetric energy density of Li-ion batteries can only reach a practical limit of about 900 Wh/L at the cell level. For Li-ion batteries, active cathode and anode powders are mixed with binder and cast on a current collector using doctor blade, reverse comma, or slot die coating. These electrodes are slit into desired dimensions, interleaved with a separator, and either wound-as is the case of an 18650 (18 mm diameter; 65 mm length) cylindrical cell-or stacked or folded to produce a prismatic pouch cell. Figure 1 shows 18650 cylindrical wound cells and 10-Ah pouch cells. For EV applications, cells are arranged into modules, which are placed into a battery pack. For example, a Tesla Model 3 contains more than 4,000 individual cylindrical cells, producing about 80 kWh of storage. Other manufacturers , such as GM, use pouch-type cells, with 288 cells producing 60 kWh of storage in the Chevy Bolt. Li-ion battery packs contain significant battery management systems to keep cells within a safe operating range. Heat generated within the pack must be removed by cooling systems to protect both the performance and lifetime of Li-ion cells. Credit: Evan Dougherty/University of Michigan Engineering Communications and Marketing Induction coils heat a die for rapid densification of Li-ion conducting Li 7 La 3 Zr 2 O 12 ceramic solid electrolyte.
A remarkable improvement of ionic conduction in an environmental friendly glassy lithium electrolyte
2016
A new modified lithium-phosphate glass has been obtained by environmentally friendly components. This glass has provided a remarkable lithium ion solid electrolyte. Frequency-dependent electrical data of several lithium-phosphate glass compositions has been discussed in the framework of the electric modulus representation. The origin of the non-Debye behaviour of relaxations (distribution of relaxation times) has been discussed in terms of inter-ionic Coulombic interactions. Structural properties studied by X-ray diffraction, density and FTIR are correlated to the electrical behaviour of the glass. The material electrical behaviour suggests an exceptional candidate for being solid electrolyte in all solid state lithium ion batteries.Fil: Di Pratula, Pablo Emmanuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química d...
Investigation of new types of lithium-ion battery materials
Journal of Power Sources, 2002
This paper reports part of the activities in progress in our laboratory in the investigation of electrode and electrolyte materials which may be of interest for the development of lithium-ion batteries with improved characteristics and performances. This investigation has been directed to both anode and cathode materials, with particular attention to convertible oxides and defect spinel-framework Li-insertion compounds in the anode area and layered mixed lithium±nickel±cobalt oxide and high voltage, metal type oxides in the cathode area. As for the electrolyte materials, we have concentrated the efforts on composite polymer electrolytes and gel-type membranes. In this work we report the physical, chemical and electrochemical properties of the defect spinel-framework Li-insertion anodes and of the high voltage, mixed metal type oxide cathodes, by describing their electrochemical properties in cells using either``standard'' liquid electrolytes and`a dvanced'' gel-type, polymer electrolytes.
A facile route to thin-film solid state lithium microelectronic batteries
Journal of Power Sources, 2000
We describe the synthesis and characterization of a thin-film solid state lithium rechargeable battery. This battery was designed for integration into a multi-chip module (MCM). The battery consists of a spin-on Ag2WO4 — polymer cathode, a lithium hexaflurophosphate — polymer-impregnated microporous nylon membrane electrolytic separator, and a lithium foil anode. Kapton™ was used as the substrate and encapsulating top layer of the battery. The battery had a total area of approximately 4.0 cm2, thickness of 0.6 mm, and weighed 0.4 g. The battery had an open circuit voltage of 3.5 V and was able to deliver a current density of 0.05 mA/cm2 for 1.5 h while maintaining a voltage above 2.0 V. The battery was cycled over 12,000 times between 3.5 and 2.0 V using a constant discharging current density of 0.1 mA/cm2 and charging current density of 0.05 mA/cm2. The battery was designed for integration into a standard 96 pin Kovar/Glass Bead quad-flatpack programmable MCM (1.42×1.42×0.16 in.). The charging and discharging characteristics of this battery are presented and discussed in terms of its intended application.