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Behavior Of NbSe3 Cathode In Rechargeable Li Cell

Report discusses series of ac impedance measurements of niobium triselenide cathodes in lithium secondary (rechargeable) cells. Reported work done to improve understanding of intercalation of NbSe3 with Li and to find out whether state of charge of NbSe3 determined nondestructively from impedance parameters. Authors conclude impedance parameters of NbSe3 do not vary in sufficiently regular fashion to be useful as indicators of state of charge.

Bugga, Ratnakumar V.↗

Materials Data on NbSe3 by Materials Project

NbSe3 crystallizes in the monoclinic P2_1/m space group. The structure is two-dimensional and consists of one NbSe3 sheet oriented in the (1, 0, 0) direction. there are three inequivalent Nb5+ sites. In the first Nb5+ site, Nb5+ is bonded in a 8-coordinate geometry to eight Se+1.67- atoms. There are a spread of Nb–Se bond distances ranging from 2.66–2.78 Å. In the second Nb5+ site, Nb5+ is bonded in a 8-coordinate geometry to eight Se+1.67- atoms. There are a spread of Nb–Se bond distances ranging from 2.65–2.95 Å. In the third Nb5+ site, Nb5+ is bonded in a 8-coordinate geometry to eight Se+1.67- atoms. There are a spread of Nb–Se bond distances ranging from 2.66–2.77 Å. There are nine inequivalent Se+1.67- sites. In the first Se+1.67- site, Se+1.67- is bonded in a 2-coordinate geometry to two equivalent Nb5+ atoms. In the second Se+1.67- site, Se+1.67- is bonded in a 4-coordinate geometry to four Nb5+ atoms. In the third Se+1.67- site, Se+1.67- is bonded in a 2-coordinate geometry to two equivalent Nb5+ atoms. In the fourth Se+1.67- site, Se+1.67- is bonded in a 4-coordinate geometry to four Nb5+ atoms. In the fifth Se+1.67- site, Se+1.67- is bonded in a 2-coordinate geometry to two equivalent Nb5+ atoms. In the sixth Se+1.67- site, Se+1.67- is bonded in a distorted L-shaped geometry to two equivalent Nb5+ atoms. In the seventh Se+1.67- site, Se+1.67- is bonded in a distorted L-shaped geometry to two equivalent Nb5+ atoms. In the eighth Se+1.67- site, Se+1.67- is bonded in a distorted trigonal non-coplanar geometry to three Nb5+ atoms. In the ninth Se+1.67- site, Se+1.67- is bonded in a 3-coordinate geometry to three Nb5+ atoms.

36 MATERIALS SCIENCE↗

NbSe3 Cathodes For Li Rechargeable Cells

Report describes experimental studies involving preparation, characterization, and measurements of performance of NbSe3, intended for use as cathode material in lithium rechargeable electrochemical cells. Characteristics superior to those of other intercalating cathode materials, including high volumetric and gravimetric energy densities and ability to sustain discharges at high rates.

Bugga, Ratnakumar V.↗

Kinetics of intercalation of lithium into NbSe3 and TiS2 cathodes

Titanium disulfide and niobium triselenide are two well-studied candidate materials for positive electrodes in rechargeable lithium cells. A comparative study of the kinetics of intercalation of lithium in both the cathodes is made here based on various electrochemical techniques, i.e., linear polarization, potentiodynamic polarization, and ac impedance under different experimental conditions such as prismatic or disk configuration of fresh, partially discharged, or cycled electrode. Further, the diffusion coefficients of lithium ions in these cathodes are estimated under these conditions using conventional techniques, i.e., ac impedance, chronocoulometry, chronoamperometry, and current pulse relaxation. Based on the values of the diffusion coefficients, the applicability of these methods for the determination of diffusion coefficients is discussed.

Ratnakumar, B. V.↗

Electrochemical studies on niobium triselenide cathode material for lithium rechargeable cells

The electrochemical behavior of NbSe3 in the battery electrolyte 1.5M LiAsF6/2Me-THF is reported. A detailed study has been carried out using various ac and dc electrochemical techniques to establish the mechanism of intercalation of three equivalents of Li with NbSe3 as well as the rate governing processes in the reduction of NbSe3. An equivalent circuit has been formulated to represent the NbSe3-solution interface. The kinetic parameters for the reduction of NbSe3 were evaluated from the ac and dc measurements. The structural change in NbSe3 on lithiation during initial discharge which results in higher cell voltages and different electrochemical response as compared to virgin NbSe3 was identified to be a loss of crystallographic order.

Ratnakumar, B. V.↗

Studies on niobium triselenide cathode material for lithium rechargeable cells

NbSe3 exhibits superior characteristics such as high capacity, high volumetric and gravimetric energy densities, and high discharge rate capability, as compared to other intercalating cathodes. This paper reports the preparation, characterization, and performance of NbSe3. Several electrochemical techniques, such as cyclic voltammetry, constant-current/constant-potential discharges, dc potentiodynamic scans, ac impedance, and ac voltammetry, have been used to give insight to the mechanisms of intercalation of three lithiums with NbSe3 and also into the rate determining process in the reduction of NbSe3.

Ratnakumar, B. V.↗

Electrochemical behavior of niobium triselenide cathode in lithium secondary cells

Niobium triselenide cathodes in Li ambient-temperature rechargeable batteries for space applications undergo a topotactic reaction, with three equivalents of Li at high positive potential furnishing high energy density. It also yields good electronic conductivity, a long life cycle, and high diffusivity for Li. An attempt is presently made to characterize the intercalation mechanism between Li and NbSe3 by means of an ac impedance study conducted at various charge stages in the process of SbSe3 reduction. An effort is also made to predict the charge state of NbSe3 nondestructively, on the basis of the impedance parameters.

Ratnakumar, B. V.↗

Advances in ambient temperature secondary lithium cells

The Jet Propulsion Laboratory is involved in a Research and Development program sponsored by NASA/OAST on the development of ambient temperature secondary lithium cells for future space applications. Some of the projected applications are planetary spacecraft, planetary rovers, and astronaut equipment. The main objective is to develop secondary lithium cells with greater than 100 Wh/kg specific energy while delivering 1000 cycles at 50 percent Depth of Discharge (DOD). To realize these ambitious goals, the work was initially focused on several important basic issues related to the cell chemistry, selection of cathode materials and electrolytes, and component development. The performance potential of Li-TiS2, Li-MoS3, Li-V6O13 and Li-NbSe3 electrochemical systems was examined. Among these four, the Li-TiS2 system was found to be the most promising system in terms of realizable specific energy and cycle life. Some of the major advancements made so far in the development of Li-TiS2 cells are in the areas of cathode processing technology, mixed solvent electrolytes, and cell assembly. Methods were developed for the fabrication of large size high performance TiS2 cathodes. Among the various electrolytes examined, 1.5M LiAsF6/EC + 2-MeTHF mixed solvent electrolyte was found to be more stable towards lithium. Experimental cells activated with this electrolyte exhibited more than 300 cycles at 100 percent Depth of Discharge. Work is in progress in other areas such as selection of lithium alloys as candidate anode materials, optimization of cell design, and development of 5 Ah cells. The advances made at the Jet Propulsion Laboratory on the development of secondary lithium cells are summarized.

Subbarao, S.↗

Performance characteristics of ambient temperature secondary lithium cells

State of art ambient temperature secondary lithium cells were evaluated to determine their performance capability and limitations and to assess the present status of the technology of these cells. Li-MoS2, Li-NbSe3 and Li-TiS2 cells were evaluated for their charge/discharge characteristics, rate capability, and cycle life performance. The cells evaluated have a cycle life of 100-250 cycles at moderate discharge rates (C/5). The specific energy of these cells is between 50 and 100 Wh/Kg, depending upon the system. This paper describes the details of the cell designs, the test procedures, and the results of the evaluation studies.

Deligiannis, F.↗

Advances in ambient temperature secondary lithium cells

The goal is to develop secondary lithium cells with a 100 Wh/kg specific energy capable of 1000 cycles at 50 percent DOD. The approach towards meeting this goal initially focused on several basic issues related to the cell chemistry, selection of cathode materials and electrolytes and component development. The performance potential of Li-TiS2, Li-MoS3, Li-V6O13 and Li-NbSe3 electrochemical systems was examined. Among these four, the Li-TiS2 system was found to be the most promising system in terms of achievable specific energy and cycle life. Major advancements to date in the development of Li-TiS2 cells are in the areas of cathode processing technology, mixed solvent electrolytes, and cell assembly. A summary is given of these advances.

Subbarao, S.↗

Advances in ambient temperature secondary lithium cells

The goal of the NASA/OAST sponsored program on the development of ambient-temperature secondary lithium cells for future space applications is to develop cells with a 100 W h/kg specific energy and capable of 1000 cycles at 50-percent depth of discharge. This paper examines the performance potentials of Li-TiS2, Li-MoS3, Li-V6O13, and Li-NbSe3 electrochemical systems at ambient temperature, together with cycle life and safety characteristics. Of these four, the Li-TiS2 system was found to be the most promising in terms of achievable specific energy and cycle life. Major advances made on the development of secondary lithium cells, which are in the areas of cathode processing technology, mixed solvent electrolytes, and cell assembly, are summarized.

Subbarao, S.↗