Publications

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Electrical and chemical measurements have been made on 18650-size lithium-ion cells that have been exposed to calendar and cycle life aging at temperatures up to 70 C. Aging times ranged from 2 weeks at the highest temperature to several months under more moderate conditions. After aging, the impedance behavior of the cells was reversed from that found originally, with lower impedance at low state of charge and the total impedance was significantly increased. Investigations using a reference electrode showed that these changes are primarily due to the behavior of the cathode. Measurements of cell impedance as a function of cell voltage reveal a pronounced minimum in the total impedance at approximately 40--50% state-of-charge (SOC). Chemical analysis data are presented to support the SOC assignments for aged and unaged cells. Electrochemical impedance spectroscopy (EIS) data have been recorded at several intermediate states of charge to construct the impedance vs. open circuit voltage curve for the cell. This information has not previously been available for the LiNi{sub 0.85}Co{sub 0.15}O{sub 2} cathode material. Structural and chemical analysis information obtained from cell components removed during postmortems will also be discussed in order to reveal the true state of charge of the cathode and to develop a more complete lithium inventory for the cell.

This paper describes the author's 2- and 3-electrode impedance results of metal oxide cathodes. These results were extracted from impedance data on 18650 Li-ion cells. The impedance results indicate that the ohmic resistance of the cell is very nearly constant with state-of-charge (SOC) and temperature. For example, the ohmic resistance of 18650 Li-ion cells is around 60 m{Omega} for different SOCS (4.1V to 3.0V) and temperatures from 35 C to {minus}20 C. However, the interfacial impedance shows a modest increase with SOC and a huge increase of between 10 and 100 times with decreasing temperature. For example, in the temperature regime (35 C down to {minus}20 C) the overall cell impedance has increased from nearly 200 m{Omega} to 8,000 m{Omega}. Most of the increase in cell impedance comes from the metal oxide cathode/electrolyte interface.

Differential scanning calorimetry (DSC) analysis was used to identify thermal reactions in Sony-type lithium-ion cells and to correlate these reactions with interactions of cell constituents and reaction products. An electrochemical half-cell was used to cycle the anode and cathode materials and to set the state-of-charge (SOC). Three temperature regions of interaction were identified and associated with the SOC (degree of Li intercalation) of the cell. Anodes were shown to undergo exothermic reactions as low as 80 C involving decomposition of the solid electrolyte interphase (SEI) layer. The LiPF{sub 6} salt in the electrolyte (EC:PC:DEC/1M LiPF{sub 6}) was seen to play an essential role in this reaction. DSC analysis of the anodes from disassembled Sony cells showed similar behavior to the half-cell anodes with a strong exotherm beginning in the 80 C--90 C range. Exothermic reactions were also observed in the 200 C--300 C region between the intercalated lithium anodes, the LiPF{sub 6} salt, and the PVDF binder. These reactions were followed by a high-temperature reaction region, 300 C--400 C, also involving the PVDF binder and the intercalated lithium anodes. Cathode exothermic reactions with the PVDF binder were observed above 200 C and increased with the SOC (decreasing Li content in the cathode). No thermal reactions were seen at lower temperatures suggesting that thermal runaway reactions in this type of cell are initiated at the anode. An Accelerating Rate Calorimeter (ARC) was used to perform measurements of thermal runaway on commercial Sony Li-ion cells as a function of SOC. The cells showed sustained thermal output as low as 80 C in agreement with the DSC observations of anode materials but the heating rate was strongly dependent on the SOC.

Electrical characteristics of hybrid power sources consisting of Li-ion cells and double-layer capacitors were studied at 25 C and {minus}20 C. The cells were initially evaluated for pulse performance and then measured in hybrid modes of operation where they were coupled with the high-power capacitors. Cells manufactured by Panasonic measured at 25 C delivered full capacities of 0.76 Ah for pulses up to 3A and cells from A and T delivered full capacities of 0.73 Ah for pulses up to 4A. Measured cell resistances were 0.15 ohms and 0.12 ohms, respectively. These measurements were repeated at {minus}20 C. Direct coupling of the cells and capacitors (coupled hybrid) using 10F Panasonic capacitors in a 8F series/parallel combination extended the full capacity pulse limits (3.0V threshold) to 5.6A for the Panasonic cells and to 9A for the A and T cells. A similar arrangement using 100F capacitors from Elna in a 60F combination increased the Panasonic cell limit to 10 A. Operation in an uncoupled hybrid mode using uncoupled cell/capacitor discharge allowed fill cell capacity usage at 25 C up to the capacitor discharge limit and showed a factor of 5 improvement in delivered capacity at {minus}20 C.

A number of fluoro-carbonate solvents were evaluated as electrolytes for Li-ion cells. These solvents are fluorine analogs of the conventional electrolyte solvents such as dimethyl carbonate, ethylene carbonate, diethyl carbonate in Li-ion cells. Conductivity of single and mixed fluoro carbonate electrolytes containing 1 M LiPF{sub 6} was measured at different temperatures. These electrolytes did not freeze at -40 C. We are evaluating currently, the irreversible 1st cycle capacity loss in carbon anode in these electrolytes and the capacity loss will be compared to that in the conventional electrolytes. Voltage stability windows of the electrolytes were measured at room temperature and compared with that of the conventional electrolytes. The fluoro-carbon electrolytes appear to be more stable than the conventional electrolytes near Li voltage. Few preliminary electrochemical data of the fluoro-carbonate solvents in full cells are reported in the literature. For example, some of the fluorocarbonate solvents appear to have a wider voltage window than the conventional electrolyte solvents. For example, methyl 2,2,2 trifluoro ethyl carbonate containing 1 M LiPF{sub 6} electrolyte has a decomposition voltage exceeding 6 V vs. Li compared to <5 V for conventional electrolytes. The solvent also appears to be stable in contact with lithium at room temperature.

Two and three electrode impedance measurements were made on 18650 Li-ion cells at different QB temperatures ranging from 35 C to {minus}40 C. The ohmic resistance of the cell is nearly constant the temperature range studied although the total cell impedance increases by an order of magnitude in the same temperature range. In contrast to what is commonly believed, we show from our three-electrode impedance results that, the increase in cell impedance comes mostly from the cathode and not from the anode. Further, the anode and cathode contribute to both the impedance loops (in the NyQuist plot).

Low temperature electrical performance characteristics of A and T, Moli, and Panasonic 18650 Li-ion cells are described. Ragone plots of energy and power data of the cells for different temperatures from 25 C to {minus}40 C are compared. Although the electrical performance of these cells at and around room temperature is respectable, at temperatures below 0 C the performance is poor. For example, the delivered power and energy densities of the Panasonic cells at 25 C are {approximately}800 W/l and {approximately}100 Wh/l respectively and those at {minus}40 C are <10 W/l and {approximately}5 Wh/l. In order to identify the source for this poor performance at subambient temperatures, both 2- and 3-electrode impedance studies were made on these cells. The 2-electrode impedance data suggests that the cell ohmic resistance remains nearly constant from 25 C to {minus}20 C but increases modestly at {minus}40 C while the overall cell impedance increases by an order of magnitude over the same temperature range. The 3-electrode impedance data of the A and T cells show that the increase in cell resistance comes mostly from the cathode electrolyte interface and very little either from the anode electrolyte interface or from the ohmic resistance of the cell. This suggests that the poor performance of the cells comes mainly from the high cathode/electrolyte interfacial impedance.

A two-dimensional model is developed to simulate discharge of a lithium/thionyl chloride primary battery. The model accounts for not only transport of species and charge, but also the electrode porosity variations and the electrolyte flow induced by the volume reduction caused by electrochemical reactions. Numerical simulations are performed using a finite volume method of computational fluid dynamics. The predicted discharge curves for various temperatures are compared to the experimental data with excellent agreement. Moreover, the simulation results. in conjunction with computer visualization and animation techniques, confirm that cell utilization in the temperature and current range of interest is limited by pore plugging or clogging of the front side of the cathode as a result of LiCl precipitation. The detailed two-dimensional flow simulation also shows that the electrolyte is replenished from the cell header predominantly through the separator into the front of the cathode during most parts of the discharge, especially for higher cell temperatures.

Advanced rechargeable lithium-ion batteries are presently being developed and commercialized worldwide for use in consumer electronics, military and space applications. The motivation behind these efforts involves, among other things, a favorable combination of energy and power density. For some of the applications the power sources may need to perform at a reasonable rate at subambient temperatures. Given the nature of the lithium-ion cell chemistry the low temperature performance of the cells may not be very good. At Sandia National Laboratories, we have used different electrochemical techniques such as impedance and charge/discharge at ambient and subambient temperatures to probe the various electrochemical processes that are occurring in Li-ion cells. The purpose of this study is to identify the component that reduces the cell performance at subambient temperatures. We carried out 3-electrode impedance measurements on the cells which allowed us to measure the anode and cathode impedances separately. Our impedance data suggests that while the variation in the electrolyte resistance between room temperature and -20°C is negligible, the cathode electrolyte interfacial resistance increases substantially in the same temperature span. We believe that the slow interfacial charge transfer kinetics at the cathode electrolyte may be responsible for the increase in cell impedance and poor cell performance. © Copyright 1999 Society of Automotive Engineers, Inc.

Advanced rechargeable lithium-ion batteries are presently being developed and commercialized worldwide for use in consumer electronics, military and space applications. At Sandia National Laboratories we have used different electrochemical techniques such as impedance and charge/discharge at ambient and subambient temperatures to probe the various electrochemical processes that are occurring in Li-ion cell. The purpose of this study is to identify the component that reduces the cell performance at subambient temperatures. Our impedance data suggest that while the variation in the electrolyte resistance between room temperature and {minus}20 C is negligible the anode electrolyte interfacial resistance increases by an order of magnitude in the same temperature regime. We believe that the solid electrolyte interface (SEI) layer on the carbon anode may be responsible for the increase in cell impedance. We have also evaluated the cells in hybrid mode with capacitors. High-current operation in the hybrid mode allowed fill usage of the Li-ion cell capacity at 25 C and showed a factor of 5 improvement in delivered capacity at {minus}20 C.

We are currently evaluating large capacity (20 - 40 Ah) Bluestar (cylindrical) and Yardney (prismatic) Li-ion cells for their electrical and electrochemical performance characteristics at different temperatures. The cell resistance was nearly constant from room temperature to -20{degrees}C but increased by over 10 times at -40{degrees}C. The specific energy and power as well as the energy density and power density are high and didn't reach a plateau even at the highest discharge rates tested. For example, the prismatic Li-ion cells gave close to 280 Wh l{sup -1} at 4-amp discharge and 249 Wh l{sup -1} at 20-amp discharge at room temperature. For the same current range the specific power values are 102 Wh kg{sup -1} and 91 Wh kg{sup -1}. Cycle life and other electrical and electrochemical properties of the cells will be presented.

A mathematical model of a spirally wound lithium/thionyl chloride primary battery has been developed ~d used for parameter estimation and design studies. The model formulation is based on the fimdarnental Consemation laws using porous electrode theory and concentrated solution theory. The model is used to estimate the difision coefficient and the kinetic parameters for the reactions at the anode and the cathode as a function of temperature. These parameters are obtained by fitting the simulated capacity and average cell voltage to experimental data over a wide range of temperatures (-55 to 49"C) and discharge loads (10 to 250 ohms). The experiments were performed on D-sized, cathode-limited, spirally wound lithium/thionyl chloride cells. The model is also used to study the effkct of cathode thickness on the cell capacity as a finction of temperature, and it was found that the optimum thickness for the cathode- limited design is temperature and load dependent.

At Sandia National Laboratories the authors are evaluating the energy and power characteristics of commercially available Li-ion cells. Cells of several different sizes (20 Ah, 1.1 Ah, 0.750 Ah and {approximately}0.5 Ah) and geometries (cylindrical and prismatic) from several manufacturers were studied. The cells were pulsed discharged at increasing currents (50 mA to 1,000 mA) over a range of temperatures (+35 C to {minus}40 C) and at different states of charge (4.1 V, open circuit voltage (OCV), fully charged, 3.6 V OCV partially discharged and 3.1 V OCV nearly discharged) and the voltage drop was recorded. The voltage drop was small at ambient and near ambient temperatures indicating that the total cell internal impedance was small under these conditions. However, at {minus} 40 C the voltage drop was significant due to an increase in the cell internal impedance. At a given temperature, the voltage drop increases with decreasing state-of-charge (SOC) or OCV. The cell impedance and other electrochemical properties as a function of temperature and SOC were also measured. The Ragone data indicate that the specific power and specific energy of Li-ion cells of different sizes are comparable and therefore scaling up to {approximately}20 Ah does not affect either the energy or the power.

The authors describe below the electrochemical performance characteristics, including charge-discharge characteristics at different rates, of cylindrical 18650 (18 mm diameter, 65 mm high) and prismatic lithium ion cells at ambient and sub-ambient temperatures. Ragone plots of power and energy data for these cells are compared and indicate that at room temperature the prismatic lithium ion cells (approx. 500 mAh) exhibit higher specific power and power density than the 18650 cells (approx. 1,100 mAhr). The cell impedance was measured between 35 C and {minus}40 C at three open circuit voltages: 4.1 v (fully charged), 3.6 v (partially discharged), and 3.1 v (almost completely discharged). Over the temperature range from 35 C to {minus}20 C, the cell impedance is nearly constant for both cell types and increases by 2 to 3 times at {minus}40 C. The impedance doesn`t vary significantly with open circuit voltage (OCV). These cells show very little voltage drop at room temperature for current pulses up to 1 A. The charge-discharge characteristics of the cells are being studied at different rates as a function of temperature to compute the power, energy, and capacity outputs. This will not only broaden the database on lithium ion cells, but will also allow us to evaluate the suitability of the cells as power sources for low temperature applications. Other electrochemical characteristics of these cells including pulse response are being evaluated. Impedance measurements of the cells under load are planned to make meaningful correlations between the voltage drop and the current pulse amplitude.

This paper reviews the evolution of polymer electrolytes from the conventional PEO-LiX salt complexes to the more conducting polyphosphazene and copolymers, gelled electrolytes etc. It also reviews the various chemical approaches including modifying PEO to synthesizing complicated polymer architecture. In addition, it discusses the effect of various lithium salts on the conductivity of PEO-based polymers. Charge/discharge and cycle life data of polymer cells containing oxide and chalcogenide cathodes and lithium (Li) anode will be reviewed. Finally, future research directions to improve the electrolyte properties will be presented.