CA2543784A1 - Cathode materials comprising rhombohedral nasicon for secondary (rechargeable) lithium batteries - Google Patents

Cathode materials comprising rhombohedral nasicon for secondary (rechargeable) lithium batteries Download PDF

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Publication number
CA2543784A1
CA2543784A1 CA002543784A CA2543784A CA2543784A1 CA 2543784 A1 CA2543784 A1 CA 2543784A1 CA 002543784 A CA002543784 A CA 002543784A CA 2543784 A CA2543784 A CA 2543784A CA 2543784 A1 CA2543784 A1 CA 2543784A1
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Prior art keywords
cathode material
formula
cathode
battery
gamma
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Granted
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CA002543784A
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French (fr)
Other versions
CA2543784C (en
Inventor
John B. Goodenough
Akshaya Padhi
K.S. Nanjundaswamy
Christian Masquelier
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Hydro Quebec
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Individual
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Priority to CA2755356A priority Critical patent/CA2755356C/en
Publication of CA2543784A1 publication Critical patent/CA2543784A1/en
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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

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 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.

Claims (28)

1. A cathode material for a rechargeable electrochemical cell, said cell also comprising an anode and an electrolyte, the cathode material comprising a rhombohedral NASICON material having the formula Y x M2(PO4)3, where M is at least one first-row transition-metal canon and 0 <= × <= 5 and Y is Li or Na.
2. The cathode material of claim 1, where M is selected from the group consisting of Fe, V, Mn, and Ti.
3. The cathode material of claim 2, wherein the cathode material has the formula Li3+x Fe2(PO4)3, where 0 <= × <= 2.
4. The cathode material of claim 2, wherein the cathode material has the formula Li3Fe2(PO4)3.
5. The cathode material of claim 2, having the formula Li1+x Ti2(PO4)3.
6. The cathode material of claim 2, having the formula Li2FeTi(PO4)3.
7. The cathode material of claim 2, having the formula Li x TiNb(PO4)3, where 0 <= × <= 2.
8. The cathode material of claim 2, having the formula Li1+x FeNb(PO4)3, where 0 <= × <= 2.
9. The cathode material of claim 2, prepared by the process comprising the steps:

(a) preparing Na2Fe2(PO4)3; and (b) contacting said Na2Fe2(PO4)3 with a molten lithium salt, such that an ionic exchange reaction occurs.
10. The cathode material of claim 2, prepared by a direct solid state reaction.
11. A cathode material for a rechargeable electrochemical cell, said cell also comprising an anode and an electrolyte, the cathode material comprising a rhombohedral NASICON material having the formula Y x M2(PO4).gamma.(XO4)3-.gamma., where 0 < .gamma. <= 3, M is a transition-metal atom, 0 <= ×
<= 5, Y is Li or Na, and X = Si, As, or S.
12. The cathode material of claim 11, wherein the cathode material has the formula Li1+x Fe2(SO4)2(PO4), where 0 <= × <= 2.
13. The cathode material of claim 12, prepared by the process comprising the steps:

(a) preparing an aqueous solution comprising FeCl3, (NH4)2SO4, and LiH2PO4;
(b) evaporating the solution to obtain dry material; and (c) heating the dry material to about 500°C.
14. A cathode material for a rechargeable electrochemical cell also comprising an anode and an electrolyte, the cathode comprising an rhombohedral NASICON
material the formula A3-x V2(PO4)3, where A may be Li, Na or a combination thereof and 0 <= × <= 2.
15. The cathode material of claim 14, wherein the cathode material has the formula Li2-x NaV2(PO4)3, where 0<= × <= 2.
16. The cathode material of claim 14, prepared by the process comprising the steps:

(a) preparing Na3V2(PO4)3; and (b) contacting said Na3V2(PO4)3 with a molten lithium salt, such that an ionic exchange reaction occurs.
17. The cathode material of claim 14, prepared by a direct solid-state reaction.
18. A secondary battery comprising an anode, a cathode and an electrolyte, said cathode comprising a rhombohedral NASICON material having the formula Y x M2(PO4)3, where M is at least one first-row transition-metal cation and 0<= × <= 5 and Y is Li or Na, other than Li2+x FeTi(PO4)3.
19. The battery of claim 18, where M is selected from the group consisting of Fe, V, Mn, and Ti.
20. The battery of claim 19, wherein the cathode material has the formula Li3+x Fe2(PO4)3, where 0 <= × <= 2.
21. The battery of claim 20, wherein the cathode material has the formula Li3Fe2(PO4)3.
22. The battery of claim 19, wherein the cathode material has the formula Li2FeTi(PO4)3.
23. The battery of claim 19, wherein the cathode material has the formula Li x TiNb(PO4)3, where 0 <= × <=2.
24. The battery of claim 19, wherein the cathode material has the formula Li1+x FeNb(PO4)3, 0 <= × <= 2.
25. A secondary battery comprising an anode, a cathode and an electrolyte, said cathode comprising a rhombohedral NASICON material having the formula Y x M2(PO4).gamma.(XO4)3-.gamma., where 0 <= .gamma. <= 3, M is a transition-metal atom, 0 <= × <= 5, Y is Li or Na, and X = Si, As, or S.
26. The battery of claim 25, wherein said cathode material has the formula Li1+x Fe2(PO4)(SO4)2, where 0 <= × <= 2.
27. A secondary battery comprising an anode, a cathode and an electrolyte, said cathode comprising a rhombohedral NASICON material having the formula A3-x V2(PO4)3, where A may be Li, Na or a combination thereof and 0 <=
× <= 2.
28. The battery of claim 27, wherein the cathode material has the formula Li2+x NaV2(PO4)3, where 0 <= × <= 2.
CA2543784A 1996-04-23 1997-04-23 Cathode materials comprising rhombohedral nasicon for secondary (rechargeable) lithium batteries Expired - Lifetime CA2543784C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CA2755356A CA2755356C (en) 1996-04-23 1997-04-23 Cathode materials comprising rhombohedral nasicon for secondary (rechargeable) lithium batteries

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US1606096P 1996-04-23 1996-04-23
US60/016,060 1996-04-23
US3234696P 1996-12-04 1996-12-04
US60/032,346 1996-12-04
CA002251709A CA2251709C (en) 1996-04-23 1997-04-23 Cathode materials for secondary (rechargeable) lithium batteries

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CA002251709A Division CA2251709C (en) 1996-04-23 1997-04-23 Cathode materials for secondary (rechargeable) lithium batteries

Related Child Applications (1)

Application Number Title Priority Date Filing Date
CA2755356A Division CA2755356C (en) 1996-04-23 1997-04-23 Cathode materials comprising rhombohedral nasicon for secondary (rechargeable) lithium batteries

Publications (2)

Publication Number Publication Date
CA2543784A1 true CA2543784A1 (en) 1997-10-30
CA2543784C CA2543784C (en) 2012-01-03

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ID=26688119

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CA002251709A Expired - Lifetime CA2251709C (en) 1996-04-23 1997-04-23 Cathode materials for secondary (rechargeable) lithium batteries
CA2803760A Expired - Lifetime CA2803760C (en) 1996-04-23 1997-04-23 Cathode materials comprising rhombohedral nasicon for secondary (rechargeable) lithium batteries
CA2755356A Expired - Lifetime CA2755356C (en) 1996-04-23 1997-04-23 Cathode materials comprising rhombohedral nasicon for secondary (rechargeable) lithium batteries
CA2543784A Expired - Lifetime CA2543784C (en) 1996-04-23 1997-04-23 Cathode materials comprising rhombohedral nasicon for secondary (rechargeable) lithium batteries

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CA002251709A Expired - Lifetime CA2251709C (en) 1996-04-23 1997-04-23 Cathode materials for secondary (rechargeable) lithium batteries
CA2803760A Expired - Lifetime CA2803760C (en) 1996-04-23 1997-04-23 Cathode materials comprising rhombohedral nasicon for secondary (rechargeable) lithium batteries
CA2755356A Expired - Lifetime CA2755356C (en) 1996-04-23 1997-04-23 Cathode materials comprising rhombohedral nasicon for secondary (rechargeable) lithium batteries

Country Status (6)

Country Link
US (2) US5910382A (en)
EP (6) EP1755183A1 (en)
JP (8) JP4369535B2 (en)
CA (4) CA2251709C (en)
DE (6) DE06020470T1 (en)
WO (1) WO1997040541A1 (en)

Cited By (2)

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US7955733B2 (en) 1996-04-23 2011-06-07 Hydro-Quebec Cathode materials for secondary (rechargeable) lithium batteries
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