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Cathode materials for secondary (rechargeable) lithium batteries

a lithium battery and cathode material technology, applied in the direction of sulfur compounds, phosphorus compounds, peroxides/peroxyhydrates/peroxyacids/superoxides/ozonides, etc., can solve the problems of reducing the output voltage of an elementary cell, limiting the power capability of the electrode, and reducing the output voltage of the elementary cell

Inactive Publication Date: 2005-01-06
HYDRO QUEBEC CORP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

The present invention provides new electrode materials for rechargeable batteries that meet environmental requirements. These materials have an ordered olivine structure with larger tetrahedraol oxide polyanions forming a 3D framework host structure with octahedral site-occupying transition-metal oxide cations. The materials can be used in a rechargeable electrochemical cell with an anode, cathode, and electrolyte. The new materials have improved lithium ion diffusivity and electronic conductivity, making them better suited for use in batteries. The invention also provides methods for modifying the structure of the materials to further improve their performance. Overall, the invention provides new electrode materials that are more effective and environmentally friendly than previously known alternatives.

Problems solved by technology

Layered oxides using Co and / or Ni are expensive and may degrade due to the incorporation of unwanted species from the electrolyte.
However, the small size of the O2− ion restricts the free volume available to the Li+ ions, which limits the power capability of the electrodes.
Although substitution of a larger S2− ion for the O2− ion increases the free volume available to the Li+ ions, it also reduces the output voltage of an elementary cell.

Method used

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  • Cathode materials for secondary (rechargeable) lithium batteries
  • Cathode materials for secondary (rechargeable) lithium batteries
  • Cathode materials for secondary (rechargeable) lithium batteries

Examples

Experimental program
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Effect test

example 1

Ordered Olivine LiMPO4 Compounds

The ordered-olivine compound LiFePO4 was prepared from intimate mixtures of stoichiometric proportions of Li2CO3 or LiOH.H2O, Fe(CH3CO2)2 and NH4H2PO4.H2O; the mixtures were calcined at 300-350° C. to eliminate NH3, H2O, and CO2 and then heated in Ar at about 800° C. for 24 hours to obtain LiFe PO4. Similar solid-state reactions were used to prepare LiMnPO4, LiFe1-xMnxPO4, LiCoPO4 and LiNiPO4. FePO4 was obtained from LiFePO4 by chemical extraction of Li from LiFePO4. Charge / discharge curves for Li1-xFePO4 and discharge / charge cycles for LixFePO4 gave similar results with a voltage of almost 3.5 V vs. lithium for a capacity of 0.6 Li / formula unit at a current density of 0.05 mA·cm2− (See FIG. 2A and FIG. 2C). The electrolyte used had a window restricting voltages to V<4.3 V. Li extraction was not possible from LiNnPO4, LiCoPO4, and LiNiPO4 with the electrolyte used because these require a voltage V>4.3 V to initiate extraction. However, Li extra...

example 2

Modified Olivine LiMPO4 Compounds

The modified olivine compounds, LiMPO4, were prepared from intimate mixtures of stoichiometric proportions of Fe(C2O4).2H2O (Aldrich), LiH2PO4, Li2C2O4 (Alpha Inorganics), (NH4)2TiO(C2O4)2.H2O and polydiethoxysiloxane (Gelest) in isopropanol. In particular, 12.95 grams of iron oxalate (Fe(C2O4).2H2O), 8.31 grams of lithium dihydrogen phosphate (LiH2PO4), 1.52 grams of lithium oxalate (Li2C2O4), 2.94 grams of ammonium titanyl oxalate monohydrate ((NH4)2TiO(C2O4)2.H2O) and 2.68 grams of polydiethyoxysiloxane in 120 milliliters (ml) of isopropanol were ball-milled in a polyethylene container with sintered zirconia balls for two days. The resulting slurry was evaporated to dryness and treated in a vacuum furnace at 350° C., the 700° C. under argon (<6 ppm oxygen) to yield a compound with olivine structure of formula Li1.1Fe0.8TiP0.8Si2O4.

The compound was delithiated with a solution of bromine in acetonitrile to Li0.1Fe0.8TiP0.8Si0.2O4.

A solid-...

example 3

Rhombohedral NASICON LixM2(PO4)3 Structures

The inventors compared redox energies in isostructural sulfates with phosphates to obtain the magnitude of the change due to the different inductive effects of sulfur and phosphorus. Rhombohedral Li1+xTi2(PO4)3 has been shown to exhibit a flat open-circuit voltage Voc=2.5 V vs. lithium, which is roughly 0.8 V below the Ti4+ / Ti3+ level found for FeTi(SO4)3. The flat voltage V(x) is indicative of a two-phase process. A coexistence of rhombohedral and orthorhombic phases was found for x=0.5 (Delmas and Nadiri 1988; Wang and Hwu 1992). Li2+xFeTi(PO4)3 of the present invention remains single phase on discharge.

All three phosphates Li3M2(PO4)3, where M=Fe, Fe / V, or V, have the monoclinic Fe2(SO4)3 structure if prepared by solid-state reactionr. The inventors have found that these compounds exhibit a rhombohedral structure when prepared by ion exchange in LiNO3 at 300° C. from the sodium analog Na3Fe2(PO4)3. The discharge / charge curve of FIG. ...

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Abstract

The invention relates to materials for use as electrodes in an alkali-ion secondary (rechargeable) battery, particularly a lithium-ion battery. The invention provides transition-metal compounds having the ordered-olivine, a modified olivine, or the rhombohedral NASICON structure and the polyanion (PO4)3− as at least one constituent for use as electrode material for alkali-ion rechargeable batteries.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to secondary (rechargeable) alkali-ion batteries. More specifically, the invention relates to materials for use as electrodes for an alkali-ion battery. The invention provides transition-metal compounds having the ordered olivine, the modified olivine or the rhombohedral NASICON structure and containing the polyanion (PO4)3− as at least one constituent for use as electrode material for alkali-ion rechargeable batteries. 2. Description of the Related Art Present-day lithium batteries use a solid reductant as the anode and a solid oxidant as the cathode. On discharge, the metallic anode supplies Li+ ions to the Li+-ion electrolyte and electrons to the external circuit. The cathode is typically an electronically conducting host into which Li+ ions are inserted reversibly from the electrolyte as a guest species and charge-compensated by electrons from the external circuit. The chemical reactions at t...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): C01B25/45H01M4/02H01M4/136H01M4/48H01M4/485H01M4/50H01M4/505H01M4/52H01M4/525H01M4/58H01M4/583H01M10/052H01M10/0525H01M10/36
CPCH01M4/5825C01B25/45H01M4/583H01M4/485H01M4/136H01M2004/028Y02E60/122H01M4/525H01M10/052H01M4/505Y10T29/49108H01M10/0525Y02E60/10G02F1/155H01M4/049H01M4/1397H01M4/622H01M4/625H01M2300/0068
Inventor ARMAND, MICHELGOODENOUGH, JOHN B.PADHI, AKSHAYA K.NANJUNDASWAMY, KIRAKODU S.MASQUELIER, CHRISTIAN
Owner HYDRO QUEBEC CORP
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