B. V. Ratnakumar

Electrolytes for Low‐Temperature Lithium Batteries Based on Ternary Mixtures of Aliphatic Carbonates

The low-temperature performance of lithium-ion cells is mainly limited by the electrolyte solution, which not only determines the ionic mobility between electrodes but also strongly affects the nature of surface films formed on the carbonaceous anode. The surface films provide kinetic stability to the electrode (toward electrolyte) and permit charge (electron) transfer across them, which in turn determine the cycle life and rate capability of lithium-ion cells. Aiming at enhancing low-temperature cell performance, the authors have studied electrolyte solutions based on different ratios of alkyl carbonate solvent mixtures, i.e., ethylene carbonate (EC), dimethyl carbonate (DMC), and diethyl carbonate (DEC), in terms of electrolyte conductivity, film resistance, film stability, and kinetics of lithium intercalation and deintercalation, at various temperatures. Electrolytes based on the ternary mixtures of EC, DEC, and DMC emerged as preferred combination compared to the binary analogues both in terms of conductivity and surface film characteristics, especially at low temperatures. These studies are further corroborated in sealed AA cells, which showed a synergistic effect of high durability from the DMC-based solutions and improved low-temperature performance from the DEC-based electrolytes.

Electrochemical Studies on LaNi5 − x Sn x Metal Hydride Alloys

Electrochemical studies were performed on LaNi(sub 5-x)Sn(sub x) with 0(less than or equal to)x(less than or equal to)0.5. We measured the effect of the Sn substituent on the kinetics of charge transfer and diffusion during hydrogen absorption and desorption, and the cyclic lifetimes of LaNi(sub 5-x)Sn(sub x) electrodes in 250 mAh laboratory test cells. We report beneficial effects of making small substitutions of Sn for Ni in LaNi(sub 5) on the performance of metal hydride alloy anode in terms of cyclic lifetime, capacity and kinetics. The optimal concentration of Sn in LaNi(sub 5-x)Sn(sub x) alloys for negative electrodes in alkaline rechargable secondary cells was found to lie in the range 0.25(less than or equal to)x(less than or equal to)0.3.

Irreversible Capacities of Graphite in Low‐Temperature Electrolytes for Lithium‐Ion Batteries

Carbonaceous anode materials in lithium-ion rechargeable cells exhibit irreversible capacity, mainly due to reaction of lithium during the formation of passive surface films. The stability and kinetics of lithium intercalation into the carbon anodes are determined by these films. The nature, thickness, and morphology of these films are in turn affected by the electrolyte components, primarily the solvent constituents. In this work, the films formed on graphite anodes in low-temperature electrolytes, i.e., solutions with different mixtures of alkyl carbonates and low-viscosity solvent additives, are examined using electrochemical impedance spectroscopy (EIS) and solid-state ^(7)Li nuclear magnetic resonance techniques. In addition, other ex situ studies such as X-ray diffraction, transmission electron microscopy, and electron energy loss spectroscopy were carried out on the graphite anodes to understand their microstructures.

Use of Organic Esters as Cosolvents in Electrolytes for Lithium-Ion Batteries with Improved Low Temperature Performance

The electrolyte composition plays a strong role in determining the low temperature performance of lithium-ion cells, both in terms of ionic mobility in the electrolyte solution, as well as forming suitable surface films on the electrode surfaces A series of ester solvents was chosen for incorporation into multicomponent electrolyte formulations due to their favorable physiochemical properties (i.e., low viscosity, low melting point, and high permittivity), as well as good compatibility with carbonaceous anodes and mixed metal cathodes (i.e LiCoO 2 and LiNiCoO 2 ). In addition to determining the relative facility of lithium intercalation and deintercalation in Li-carbon cells as a function of temperature, a number of conventional electrochemical methods were employed to further enhance the understanding of the nature of the electrode surface films in these ester-based electrolytes, including do polarization and ac impedance measurements A distinct trend was observed with respect to the stability of the surface films formed. In solutions containing low molecular weight cosolvents (i.e., methyl acetate and ethyl acetate) the surface films appear resistive and inadequately protective, whereas electrolytes containing higher molecular weight esters resulted in surface films with more desirable attributes. Promising electrolyte formulations were further evaluated in prototype lithium-ion cells (AA-size) and fully characterized in terms of their low temperature discharge performance.

Fabrication and testing of all solid-state microscale lithium batteries for microspacecraft applications

A microfabrication process has been developed to prepare thin film solid-state lithium batteries as small as 50 μm × 50 μm. Individual cells operate nominally at 3.9 V with 10 μA h cm−2 for a 0.25 μm thick cathode film. The cells are easily fabricated in series and parallel arrangement to yield batteries with higher voltage and/or capacity. Multiple charge/ discharge cycles are possible, though an apparent reaction of the in situ plated Li film with water or oxygen decreases cycle life several orders of magnitude from expected results. Further optimization of an encapsulating film will likely extend the cell cyclability. These microbattery arrays will be useful for providing on-chip power for low current, high voltage applications for microspacecraft and other miniaturized systems.

Improved performance of lithium-ion cells with the use of fluorinated carbonate-based electrolytes

Abstract There has been increasing interest in developing lithium-ion electrolytes that possess enhanced safety characteristics, while still able to provide the desired stability and performance. Toward this end, our efforts have been focused on the development of lithium-ion electrolytes which contain partially and fully fluorinated carbonate solvents. The advantage of using such solvents is that they possess the requisite stability demonstrated by the hydrocarbon-based carbonates, while also possessing more desirable physical properties imparted by the presence of the fluorine substituents, such as lower melting points, increased stability toward oxidation, and favorable SEI film forming characteristics on carbon. Specifically, we have demonstrated the beneficial effect of electrolytes which contain the following fluorinated carbonate-based solvents: methyl-2,2,2-trifluoroethyl carbonate (MTFEC), ethyl-2,2,2-trifluoroethyl carbonate (ETFEC), propyl-2,2,2-trifluoroethyl carbonate (PTFEC), methyl-2,2,2,2′,2′,2′-hexafluoro- i -propyl carbonate (MHFPC), ethyl-2,2,2,2′,2′,2′-hexafluoro- i -propyl carbonate (EHFPC), and di -2,2,2-trifluoroethyl carbonate (DTFEC). These solvents have been incorporated into multi-component ternary and quaternary carbonate-based electrolytes and evaluated in lithium–carbon and carbon–LiNi 0.8 Co 0.2 O 2 cells (equipped with lithium reference electrodes). In addition to determining the charge/discharge behavior of these cells, a number of electrochemical techniques were employed (i.e. Tafel polarization measurements, linear polarization measurements, and electrochemical impedance spectroscopy (EIS)) to further characterize the performance of these electrolytes, including the SEI formation characteristics and lithium intercalation/de-intercalation kinetics.

Li ion batteries for aerospace applications

Rechargeable Li ion batteries are perceived as likely substitutes for conventional nickel systems in an effort to minimize the mass and volume of the power subsystems in aerospace applications. The on-going consortium of NASA and DoD, after 2 years of existence, has propelled the advancement of aerospace Li ion technology in the US. Prototype cells of different sizes have been built by domestic manufacturers and are being evaluated both by NASA and Air Force. The early versions of these prototypes catered to needs of imminent NASA missions, i.e. Mars landers and rovers. Developmental efforts are underway to further improve the technology to meet the demands of long calendar life, as in the geosynchronous earth orbit (GEO) and the outer planets missions, and long cycle life as in the low earth orbit (LEO) missions. In this paper, we will briefly describe the objective and progress of this joint effort.

Effects of SEI on the kinetics of lithium intercalation

The electrochemical stability of electrolytes at lithium, or lithium-intercalating anodes, is achieved via ionically conducting surface films termed as solid electrolyte interphase (SEI). Since the lithium deposition or intercalation process occurs on the electrode covered with the SEI, the characteristics of the SEI determine the kinetics of lithiation/delithiation, stability of the interface, and thus, the overall cell performance, especially at low temperatures. In this paper, we have reiterated the significance of the SEI characteristics over the solution properties, using a few illustrative examples from our research on low temperature Li ion battery electrolytes at JPL. The examples specifically include the beneficial aspects of a ternary carbonate mixture of ethylene carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) compared to the binary mixtures (of EC and either DMC or DEC) and quaternary solutions with appropriate co-solvents, such as alkyl esters.

LITHIUM BATTERIES FOR AEROSPACE APPLICATIONS: 2003 MARS EXPLORATION ROVER

Future NASA\ planetary exploration missions require batteries that can operate at extreme temperatures and with high specific energy and energy densities. Conventional aerospace rechargeable battery systems, such as Ni-Cd, Ni-H;! and Ag-Zn, are inadequate to meet these demands. Lithium ion rechargeable batteries are therefore being chosen as the baseline for these missions. The 2003 Mars Exploration Rover mission plans to deploy twin rovers onto Mars, with the objectives of understanding its geology, climate conditions and possibility of life on Mars. The spacecraft contain various batteries, i.e., primary batteries on the lander, thermal batteries on the back shell and rechargeable batteries on the Rovers. Significant among them are the Li ion rechargeable batteries, which are being utilized for the first time in a major NASA mission. The selection of the Li ion battery has been dictated by various factors, including mass and volume constraints, cycle life, and its ability to operate well at sub-zero temperatures (down to -30°C), at moderate rates. This paper describes the selection criteria, design and performance of the three battery systems on 2003 MER mission.

Development of low temperature Li-ion electrolytes for NASA and DoD applications

Abstract Both NASA and the US Army have interest in developing secondary energy storage devices with improved low temperature performance to meet the demanding requirements of space missions and man-portable applications. Lithium-ion systems have been identified as having the most promise due to their high specific energy density and wide operational temperature ranges from the use of organic solvent-based electrolytes, rather than aqueous-based systems. Initially, the SOA lithium-ion technology was limited to operation above −10°C, due primarilly to the fact that the electrolytes employed had high melting points and were highly viscous at low temperatures, resulting in low ionic conductivity. However, due to recent developments in electrolyte formulations at the Army and at JPL, improved low temperature performance of lithium-ion cells have been demonstrated, with efficient cell operation to temperatures as low as −30°C. This was achieved by developing multi-component solvent systems, based on mixtures of cyclic and aliphatic alkyl carbonates. In the course of investigating the viability of a number of advanced electrolyte systems, it was identified that the protective surface films which form on the carbonaceous-based anodes can strongly influence the low temperature capabilities of lithium-ion cells, in addtion to the ionic conductivity of the electrolyte. Thus, in order to optimize an electrolyte for low temperature applications, it is necessary to balance the inherent physical properties of the formulations (i.e. freezing point, viscosity, and ionic conductivity) with the observed compatibility with the chosen cell chemistry (i.e. the nature of the passivating films formed on the electrodes).