Publications

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Magnesium batteries are alternatives to the use of lithium ion and nickel metal hydride secondary batteries due to magnesium's abundance, safety of operation, and lower toxicity of disposal. The divalency of the magnesium ion and its chemistry poses some difficulties for its general and industrial use. This work developed a continuous and fibrous nanoscale network of the cathode material through the use of electrospinning with the goal of enhancing performance and reactivity of the battery. The system was characterized and preliminary tests were performed on the constructed battery cells. We were successful in building and testing a series of electrochemical systems that demonstrated good cyclability maintaining 60-70% of discharge capacity after more than 50 charge-discharge cycles.

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Even after decades of research, Li-ion cells still lack thermal stability. A number of approaches, including adding fire retardants or fluoro compounds to the electrolyte to mitigate fire, have been investigated. These additives improved the thermal stability of the cells (only marginally) but not enough for use in transportation applications. Recent investigations indicate that hydrofluoro-ethers are promising as nonflammable additives1. We describe here the results of our studies on electrolytes containing the hydrofluoro-ethers in cells fabricated at Sandia. In particular, we are investigating two solvents as nonflammable additives. These are: (1) 2-trifluoromethyl-3-methoxyperfluoropentane {l_brace}TMMP{r_brace} and (2) 2-trifluoro-2-fluoro-3-difluoropropoxy-3-difluoro-4-fluoro-5-trifluoropentane {l_brace}TPTP{r_brace}. These electrolytes not only have good thermal stability compared to the conventional electrolytes but respectable ionic conductivity. Sandia made 18650 cells successfully completed the formational cycle. The impedance behavior is typical of Li-ion cells.

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In this study, (CF_x)_n cathode reaction during discharge has been investigated using in situ X-ray diffraction (XRD). Mathematical treatment of the in situ XRD data set was performed using multivariate curve resolution with alternating least squares (MCR–ALS), a technique of multivariate analysis. MCR–ALS analysis successfully separated the relatively weak XRD signal intensity due to the chemical reaction from the other inert cell component signals. The resulting dynamic reaction component revealed the loss of (CF_x)_n cathode signal together with the simultaneous appearance of LiF by-product intensity. Careful examination of the XRD data set revealed an additional dynamic component which may be associated with the formation of an intermediate compound during the discharge process.

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At Sandia National Laboratories, we have built 18650 Li-ion cells with Li reference electrode for in situ characterization of electrodes including impedance and other electrochemical properties. At a 200 mA ({approx}C/5 rate) discharge, the cell gave {approx}900 mAh. Impedance measurements indicate that the anode dominates the cell impedance. For example, at 0 C, the anode and cathode impedances at 10 mHz were around 149 and 53 m{Omega}, respectively, and the total cell impedance at 10 mHz was {approx}203 m{Omega}. The three-electrode configuration also permits measurement of individual electrode voltages during charge and discharge. During discharge, while the cell voltage drops from 4.1 to 3 V, the cathode and the anode voltages change from 4.1 to 3.7 and from {approx}0 to 0.7 V, respectively. During charge, the cathode and anode voltages trace back to their initial values before discharging. The voltage swing for the anode is higher than that for the cathode. This also indicates that the impedance for the anode is higher than for the cathode. Pulse measurements on the cells indicate the voltage drop of the full-cell is equal to the sum of the anode and cathode voltage drops for a 2 A discharge pulse.

Battery life is an important, yet technically challenging, issue for battery development and application. Adequately estimating battery life requires a significant amount of testing and modeling effort to validate the results. Integrated battery testing and modeling is quite feasible today to simulate battery performance, and therefore applicable to predict its life. A relatively simple equivalent-circuit model (ECM) is used in this work to show that such an integrated approach can actually lead to a high-fidelity simulation of a lithium-ion cell's performance and life. The methodology to model the cell's capacity fade during thermal aging is described to illustrate its applicability to battery calendar life prediction. © 2004 Elsevier B. V. All rights reserved.

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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.

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.

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.

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.