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Long life lithium batteries with stabilized electrodes

A technology of electrodes and stabilizing additives, used in lithium batteries, non-aqueous electrolyte batteries, battery electrodes, etc.

Active Publication Date: 2010-11-24
UCHICAGO ARGONNE LLC
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although these approaches show some promise at room temperature, none prevent significant electrochemical degradation at elevated temperatures due to the dissolution of manganese.

Method used

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  • Long life lithium batteries with stabilized electrodes
  • Long life lithium batteries with stabilized electrodes
  • Long life lithium batteries with stabilized electrodes

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0088] EXAMPLE 1 This particular example referred to here utilizes an electrochemical cell such as figure 1 The electrochemical cell shown. refer to figure 1 , electrochemical cell 10 includes an anode 12 and a cathode 16 separated by an electrolyte / separator 14 , all housed within an insulating housing 18 . The anode is separated from the cathode by an electrolyte and suitable terminals (not shown) are provided to make electrical contact with the anode 12 and cathode 16 respectively. Binders (eg, polyvinylidene fluoride) associated with each electrode are well known in the art and will not be described here. In this particular embodiment, the electrochemical cell comprises a graphite anode, such as natural graphite, artificial graphite, meso-carbon microspheres, carbon fibers, or hard carbon, a manganese spinel cathode, and About 1.2M LiPF in 3:7 by weight 6 electrolyte. figure 2 Depicts the resulting capacity retention when the battery is cycled between 3.0 and 4.1V. ...

Embodiment 2

[0089] Example 2 1 wt % 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane (TOS-1, available from SIGMA-ALDRICH, Milwaukee) was added to Example 1 in the electrolyte of an electrochemical cell. Then, the cell was cycled at 55°C for more than 150 cycles at 100% DOD. image 3 The results of cycling the battery between 3.0 and 4.1V are shown. This cell demonstrates improved capacity retention compared to the electrochemical cell of Example 1 (compare figure 2 and 3 ). It is believed that this improvement comes from the formation of a thin film on the electrode by the additive. Figure 4 The results of cyclic voltammetry with TOS-1 are shown over the range of voltages encountered within the electrochemical cell. The increase in current is consistent with oxidation and / or polymerization of the additive.

Embodiment 3

[0090] Example 3 In order to study that although Mn 2+ The dissolution of ions was suppressed, but the reason for the significant degradation of the graphite / substituted spinel cell was that the AC impedance of the cell was measured using a specially designed Li-Sn reference electrode during cycling at 55 °C. Figure 5 Results are shown. After one formation cycle at room temperature [ Figure 5 A], and after 25 cycles at 55 °C [ Figure 5 B] Measure the AC impedance. In the initial stage of cycling, the impedance of the negative electrode was much smaller than that of the positive electrode; however, after 25 cycles at 55 °C, the impedance of the negative electrode increased significantly and overwhelmingly surpassed that of the positive electrode.

[0091] Graphite anodes cycled in manganese spinel-based Li-ion cells at 55°C were examined by energy dispersive spectroscopy (EDS). The EDS spectrum clearly shows the presence of Mn metal on the graphite surface. It is believ...

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Abstract

The present invention relates to non-aqueous electrolytes having electrode stabilizing additives, stabilized electrodes, and electrochemical devices containing the same. Thus the present invention provides electrolytes containing an alkali metal salt, a polar aprotic solvent, and an electrode stabilizing additive. In some embodiments the additives include a substituted or unsubstituted cyclic or spirocyclic hydrocarbon containing at least one oxygen atom and at least one alkenyl or alkynyl group. When used in electrochemical devices with, e.g., lithium manganese oxide spinel electrodes or olivine or carbon-coated olivine electrodes, the new electrolytes provide batteries with improved calendar and cycle life.

Description

[0001] This application is a divisional application of Chinese patent application 200580043191.9 with a filing date of December 8, 2005 and an invention title of "Long-Life Lithium Battery with Stable Electrodes". technical field [0002] The present invention relates to nonaqueous electrolytes containing electrode stabilizing additives, stable electrodes and electrochemical devices comprising the same. In particular, the invention relates to long-life lithium batteries with stable spinel, olivine, or other electrodes. Background technique [0003] Lithium-ion batteries utilize a carbon anode, a lithiated transition metal oxide cathode, and a conductive salt with dissolved properties such as lithium hexafluorophosphate (LiPF 6 ) of organic solvent electrolytes. These batteries currently dominate the battery market in the field of mobile phones, cam-recorders, computers and other electronic equipment. However, attempts to implement these battery technologies into electric a...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M10/0567H01M4/13H01M10/0525H01M10/0568H01M4/50H01M4/505H01M4/58H01M10/052H01M10/0569H01M10/36
CPCH01M4/5825Y02E60/122H01M10/0569H01M10/0568H01M4/505H01M10/052H01M10/0525H01M10/0567H01M4/13H01M4/366Y02E60/10Y02P70/50H01M10/05
Inventor K·艾美尼柳俊D·R·威瑟斯陆文全
Owner UCHICAGO ARGONNE LLC
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