Cycling of β-LiAl in organic electrolytes — effect of electrode contaminations and electrolyte additives

Besenhard, Jürgen; Fritz, Heinz P.; Wudy, E.; Dietz, Kelsey; Meyer, Heinrich

doi:10.1016/0378-7753(85)88030-7

Cited by 16 publications

(3 citation statements)

References 17 publications

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“…Other alloys, containing greater amounts of Li are Li~A12, Li2A1, and LigA14. Although the Li-rich phases have shown some usefulness (4) as alternative anodes, most investigations have focused upon the use of the ~ phase (4,(17)(18)(19)(20)(21)(22)(23). Studies of the thermodynamics and kinetics of LiA1 alloy formation in organic electrolytes (17)(18)(19)(20)(21)(22)(23) show considerable disagreement with regard to the values of parameters such as equilibrium potentials, exchange current density, Li § diffusion coefficients, and the transfer coefficient, c~.…”

Section: ~-Lia1mentioning

confidence: 99%

Preparation and Characterization of Some Lithium Insertion Anodes for Secondary Lithium Batteries

Abraham

Pasquariello

Willstaedt

1990

J. Electrochem. Soc.

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The ambient temperature preparation and characterization of LixFe203, Li=WO2, and ~-LiA1 with potential applications as alternative anodes for secondary Li batteries are described. Both ~ and X forms of Fe203 were found to insert a maximum of six LiJFe203 both electrochemically and chemically. The potential plateaus associated with the electrochemical reduction of the two forms of Fe203 varied slightly. Both ~-Li6Fe203 and ~-Li6Fe203 were amorphous and showed a practically useful rechargeable capacity of about 1 equiv of Li at the moderate rate of 0.5 mA/cm 2. Li=WO2 also loses substantial crystallinity upon Li insertion. However, most of the crystallinity was regained upon removal of this Li. It was found to be capable of cycling nearly I equiv of Li at low rates. Several Li-A1 alloys having the ~-LiA1 structure were prepared at ambient temperature from A1 powder and Li-naphthalide. The rechargeability of the chemically prepared 3-LiA1 was poor.

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Section: ~-Lia1mentioning

confidence: 99%

Preparation and Characterization of Some Lithium Insertion Anodes for Secondary Lithium Batteries

Abraham

Pasquariello

Willstaedt

1990

J. Electrochem. Soc.

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“…4 Studies have also shown that the microstructure and morphology of Li alloys, e.g., the grain size, shape, and orientation of the active materials or the reinforcement by nonactive materials in multiphase alloys strongly affect the cycling behavior of lithium alloy electrodes. [7][8][9] The most popular method for preparing a binary Li alloy electrode is to electroplate a metallic host matrix onto a substrate (e.g., Cu or Ni) from an aqueous solution at room temperature; Li is then deposited on the metal by electrodeposition in a Li + -containing organic electrolyte. This process makes it easy to control the composition, thickness, and morphology of the host matrix, but only a thin layer of the Li alloy can be formed.…”

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confidence: 99%

Electrochemical Properties of Li-Zn Alloy Electrodes Prepared by Kinetically Controlled Vapor Deposition for Lithium Batteries

Zhong

Liu

Gole

1999

Electrochem. Solid-State Lett.

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A Li-Zn alloy electrode prepared by a kinetically controlled vapor deposition (KCVD) is examined for use as the negative electrode for rechargeable lithium batteries. Results indicate that filamentary or dendritic growth of lithium on a Li-Zn alloy electrode prepared by the KCVD technique are dramatically suppressed due to fast diffusion of lithium in the alloy electrode, suggesting that the Li-Zn prepared by the KCVD method may be used effectively to improve the rechargeability of negative electrodes.Lithium alloy electrodes have been studied over the last two decades for use as negative electrodes for room-temperature secondary lithium batteries. 1,2 A renewed interest has arisen in lithium alloy electrodes as alternatives to carbon-based intercalation materials following the development of tin-based composite oxides as negative electrodes for Li batteries. 3 Compared with carbonaceous compounds, lithium alloys have a high energy density (both volumetric and gravimetric) and high power density due to their high lithium diffusivity. 4-6 The major drawbacks associated with Li alloys as negative electrodes include Li dendrite formation during charging and large volume change during alloying-de-alloying of Li into/from metallic matrices. This usually results in a fast disintegration (cracking and crumbling) of the alloy electrode. 4 Studies have also shown that the microstructure and morphology of Li alloys, e.g., the grain size, shape, and orientation of the active materials or the reinforcement by nonactive materials in multiphase alloys strongly affect the cycling behavior of lithium alloy electrodes. [7][8][9] The most popular method for preparing a binary Li alloy electrode is to electroplate a metallic host matrix onto a substrate (e.g., Cu or Ni) from an aqueous solution at room temperature; Li is then deposited on the metal by electrodeposition in a Li + -containing organic electrolyte. This process makes it easy to control the composition, thickness, and morphology of the host matrix, but only a thin layer of the Li alloy can be formed. Another method for preparing a Li alloy is to heat two metals of interest to a predetermined temperature. Using this method, it is relatively easy to form the desired composition of the product alloy. However, it is difficult to control the microstructure and morphology of the alloy because it is usually necessary to melt both metals. Recently, we have developed a system to produce Li alloy films using a variation of the physical vapor deposition process called kinetically controlled vapor deposition (KCVD) method. 10,11 The kinetically controlled lithiation process was developed for the preparation of Li-Mg alloys with controlled microstructure including grain size, orientation, composition, and porosity. By independently controlling the temperature of a molten Li source and a source of solid metal soluble in Li (e.g., Mg, Zn, etc.), films of specific composition can be fabricated. Further, the temperature of the substrate can be varied to control the morphology of the gra...

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“…0.8V for n > 1 (64a, 118). Therefore, these electrodes have to be regarded as alternatives to Li anodes, as do Li-A1 (119) and LixPb/poly(p-phenylene) composite electrodes (75b). The cycling behavior of a Li6Fe2OjV20~ cell has been investigated by 'Morzilli etal.…”

Section: Manganesementioning

confidence: 99%

Metal Oxide Cathode Materials for Electrochemical Energy Storage: A Review

Desilvestro

Haas

1990

J. Electrochem. Soc.

233

114

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Due to their rather low molecular weight and their favorable electrochemical and solid-state properties, first row transition metal oxides seem to be specially attractive as cathode materials in electrochemical energy storage systems. Therefore, we undertook a detailed overview, covering electrochemical, conductivity, ion diffusivity, spectroscopic, and other physico-chemical data on metal oxides in relation to their behavior in batteries. Metal oxide-based primary batteries have achieved a high technological level and yield energy densities of up to 300 Wh kg-' or 880 Wh 1 1. Oxide-based secondary batteries, on the other hand, typically yield less than 100 Wh kg-L Based on the present review, V, Cr, Mn, and Co oxides seem to be the most promising solid-state cathode materials for future high performance secondary batteries. gElectrochemical energy storage will become increasingly important with increasing complexity of our power distribution systems, increasing environmental pollution, and decreasing resources of fossil fuels. Rechargeable batteries seem to be prime candidates for storing renewable energies, e.g., solar or wind, over periods of hours to days, for load leveling, and for delivering rather unpolluting power to electric cars and to remote areas. Unfortunately, energy densities of commercial secondary batteries (typically <50 Wh kg-') are well below energy densities of nonrenewable and polluting fuels such as gas or oil (ca. 12,000 Wh kg-'). In addition, energy densities of electrochemical power sources are much lower than those calculated from the weight and the thermodynamic properties of battery active material (up to > 1000 Wh kg-1). Hopefully, the large discrepancy between theoretical and practical energy densities of batteries will be lowered considerably by future research.Any chemically founded selection of suitable active material for batteries should start with the Periodic Table.

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Cycling of β-LiAl in organic electrolytes — effect of electrode contaminations and electrolyte additives

Cited by 16 publications

References 17 publications

Preparation and Characterization of Some Lithium Insertion Anodes for Secondary Lithium Batteries

Preparation and Characterization of Some Lithium Insertion Anodes for Secondary Lithium Batteries

Electrochemical Properties of Li-Zn Alloy Electrodes Prepared by Kinetically Controlled Vapor Deposition for Lithium Batteries

Metal Oxide Cathode Materials for Electrochemical Energy Storage: A Review

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