US5264201A
Expired / Lapsed
US
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Lithiated nickel dioxide and secondary cells prepared therefrom
Assignee: MOLI ENERGY (1990) Ltd A CANADIAN CORP
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Filing: 1990-07-23
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Granted: 1993-11-23
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Expires: 2010-07-23
Abstract
Abstract Lithiated nickel dioxide cathode-active materials for electrochemical cellsaving the formula Li x Ni 2-x-y M y O 2 , with x being between about 0.8 and about 1.0, M being one or more metals selected from cobalt, iron, chromium, titanium, manganese and vanadium, and y being less than about 0.2, with the proviso that y is less than about 0.5 for cobalt, which material is substantially free of lithium hydroxide and lithium carbonate. The materials are prepared by providing a substantially homogeneous dry intermediate mixture of a starting material containing a nickel compound selected from nickel oxide, nickel hydroxide, and mixtures thereof, and optionally including one or more oxides or hydroxides of a transition metal selected from cobalt, iron, chromium, titanium, manganese and vanadium, together with between about a 10 and about a 25% stoichiometric excess of lithium hydroxide. The mixture is heat treated at a temperature above about 600° C. in an atmosphere substantially free of carbon dioxide and having a partial pressure ratio of oxygen to water vapor greater than about 15, after which any lithium hydroxide or lithium carbonate present in the mixture is removed. Thermally stable lithiated nickel dioxide having a BET surface area less than about 3.0 m 2 /g, and is also disclosed, as well as electrochemical cells prepared from the disclosed lithiated nickel dioxides.
Inventors
- 👤 Jeffery R. Dahn
- 👤 Rosamaria Fong
- 👤 Ulrich Von Sacken
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-27 22:49
CPC Classifications
H; H01; H01M; H01M4/00; H01M4/02; H01M4/36; H01M4/48; H01M4/485; C; C01; C01G; C01G53/00; C01G53/40; C01G53/42; H01M10/00; H01M10/05; H01M10/052; H01M10/0525; H01M4/52; H01M4/525; C01P; C01P2002/00; C01P2002/50; C01P2002/52; C01P2002/54; C01P2006/00; C01P2006/12; C01P2006/40; C01P2006/80; H01M10/058; H01M10/0587; H01M4/58; H01M4/583; H01M4/587; Y; Y02; Y02E; Y02E60/00; Y02E60/10; Y02P; Y02P70/00; Y02P70/50
Claims Analysis
Total Claims: 49
Claim 1
Independent Claim
205 words
A method of making a lithiated nickel dioxide cathode-active material for an electrochemical cell, having a formula Li x Ni 2-x-y M y O 2 , wherein x is between about 0.8 and about 1.0, M is one or more metals selected from the group consisting of cobalt, iron, titanium, manganese, chromium and vanadium, and y is less than about 0.2, with the proviso that y is less than about 0.5 for cobalt, which material is substantially free of lithium hydroxide and lithium carbonate, said method comprising the steps of: providing a substantially homogeneous dry intermediate mixture of a starting material comprising a nickel compound selected from the group consisting of nickel oxide, nickel hydroxide and mixtures thereof, and optionally including one or more oxides or hydroxides of a transition metal selected from the group consisting of cobalt, iron, titanium, manganese, chromium and vanadium, together with between about a 10% and about a 25% stoichiometric excess of lithium hydroxide; and heat treating said mixture at a temperature above about 600° C. in an atmosphere substantially free of carbon dioxide having a partial pressure ratio of oxygen to water vapor greater than about 15; and removing from said mixture any lithium hydroxide or lithium carbonate present.
Claim 2
Independent Claim
205 words
A method of making a lithiated nickel dioxide cathode-active material for an electrochemical cell, having a formula Li x Ni 2-x-y M y O 2 , wherein x is between about 0.8 and about 1.0, M is one or more metals selected from the group consisting of cobalt, iron, titanium, manganese, chromium and vanadium, and y is less than about 0.2, with the proviso that y is less than about 0.5 for cobalt, which material is substantially free of lithium hydroxide and lithium carbonate, said method comprising the steps of: providing a substantially homogeneous dry intermediate mixture of a starting material comprising a nickel compound selected from the group consisting of nickel oxide, nickel hydroxide and mixtures thereof, and optionally including one or more oxides or hydroxides of a transition metal selected from the group consisting of cobalt, iron, titanium, manganese, chromium and vanadium, together with between about a 10% and about a 25% stoichiometric excess of lithium hydroxide; and heat treating said mixture at a temperature above about 600° C. in an atmosphere substantially free of carbon dioxide having a partial pressure ratio of oxygen to water vapor greater than about 15; and removing from said mixture any lithium hydroxide or lithium carbonate present.
Claim 3
Dependent Claim
43 words
A method as claimed in claim 1, wherein said step of providing said intermediate mixture includes the steps of contacting said starting material with a saturated aqueous solution of lithium hydroxide so as to form a slurry and evaporating water from said slurry.
Claim 4
Dependent Claim
26 words
A method as claimed in claim 2, wherein said evaporating step is continued at least until an intermediate mixture substantially devoid of free water is provided.
Claim 5
Dependent Claim
18 words
A method as claimed in claim 3, wherein said evaporating step comprises the step of spray-drying said slurry.
Claim 6
Dependent Claim
18 words
A method as claimed in claim 1, wherein said heat-treating step is conducted for at least one-half hour.
Claim 7
Dependent Claim
18 words
A method as claimed in claim 5, wherein said heat-treating step is conducted for at least one hour.
Claim 8
Dependent Claim
21 words
A method as claimed in claim 1, wherein said heat-treating step is conducted at a temperature between above about 700° C.
Claim 9
Dependent Claim
20 words
A method as claimed in claim 7, wherein said heat-treating step is conducted at a temperature above about 800° C.
Claim 10
Dependent Claim
28 words
A method as claimed in claim 1, wherein in said heat-treating step, said partial pressure of said carbon dioxide in said atmosphere is less than about 0.3 Torr.
Claim 11
Dependent Claim
28 words
A method as claimed in claim 9, wherein in said heat-treating step, said partial pressure of said carbon dioxide in said atmosphere is less than about 0.1 Torr.
Claim 12
Dependent Claim
28 words
A method as claimed in claim 10, wherein in said heat-treating step, said partial pressure of said carbon dioxide in said atmosphere is less than about 0.05 Torr.
Claim 13
Dependent Claim
29 words
A method as claimed in claim 1, wherein in said heat-treating step, said partial pressure ratio of oxygen to water vapor in said atmosphere is greater than about 15.
Claim 14
Dependent Claim
29 words
A method as claimed in claim 12, wherein in said heat-treating step, said partial pressure ratio of oxygen to water vapor in said atmosphere is greater than about 30.
Claim 15
Dependent Claim
29 words
A method as claimed in claim 13, wherein in said heat-treating step, said partial pressure ratio of oxygen to water vapor in said atmosphere is greater than about 100.
Claim 16
Dependent Claim
25 words
A method as claimed in claim 1, wherein said removing step comprises the steps of extracting said mixture with neutral water and recovering said mixture.
Claim 17
Dependent Claim
18 words
A method as claimed in claim 15, wherein said recovering step comprises filtering said water from said mixture.
Claim 18
Dependent Claim
23 words
A method as claimed in claim 16, wherein said removing step further comprises the step of drying said mixture after said filtering step.
Claim 19
Dependent Claim
21 words
A method as claimed in claim 17, wherein said drying step comprises drying said filtered mixture at 600° C. in air.
Claim 20
Dependent Claim
16 words
A method as claimed in claim 17, wherein said drying step comprises freeze-drying said filtered mixture.
Claim 21
Dependent Claim
24 words
A method as claimed in claim 15, wherein said mixture is extracted with one liter of water for every 300 g of said mixture.
Claim 22
Dependent Claim
12 words
A cathode-active material made by a process as claimed in claim 1.
Claim 23
Dependent Claim
24 words
An electrochemical cell comprising a cathode containing the cathode-active material as claimed in claim 21, a counter-electrode capable of intercalating lithium, and an electrolyte.
Claim 24
Dependent Claim
22 words
An electrochemical cell comprising an electrode comprising lithium, an electrolyte, and a cathode containing the cathode-active material as claimed in claim 21.
Claim 25
Dependent Claim
78 words
A lithiated nickel dioxide cathode-active material for an electrochemical cell, substantially free of lithium hydroxide or lithium carbonate, having a stoichiometric formula Li x Ni 2-x-y M y O 2 , wherein x is between about 0.80 and about 1.00, M is one or more metals selected from the group consisting of cobalt, iron, chromium, titanium, manganese and vanadium, and y is less than about 0.2, with the proviso that y is less than about 0.5 for cobalt.
Claim 26
Dependent Claim
78 words
A lithiated nickel dioxide cathode-active material for an electrochemical cell, substantially free of lithium hydroxide or lithium carbonate, having a stoichiometric formula Li x Ni 2-x-y M y O 2 , wherein x is between about 0.80 and about 1.00, M is one or more metals selected from the group consisting of cobalt, iron, chromium, titanium, manganese and vanadium, and y is less than about 0.2, with the proviso that y is less than about 0.5 for cobalt.
Claim 27
Dependent Claim
27 words
The lithiated nickel dioxide of claim 24, having the stoichiometric formula Li x Ni 2-x O 2 , wherein x is between about 0.80 and about 1.00.
Claim 28
Dependent Claim
16 words
The lithiated nickel dioxide of claim 25, wherein x is between about 0.90 and about 1.00.
Claim 29
Dependent Claim
19 words
The lithiated nickel dioxide of claim 24, having a lithium carbonate content less than about 20,000 ppm by weight.
Claim 30
Dependent Claim
17 words
The lithiated nickel dioxide of claim 27, having a lithium carbonate content less than about 10,000 ppm.
Claim 31
Dependent Claim
17 words
The lithiated nickel dioxide of claim 28, having a lithium carbonate content less than about 5,000 ppm.
Claim 32
Dependent Claim
19 words
The lithiated nickel dioxide of claim 24, having a lithium hydroxide content less than about 20,000 ppm by weight.
Claim 33
Dependent Claim
17 words
The lithiated nickel dioxide of claim 30, having a lithium hydroxide content less than about 10,000 ppm.
Claim 34
Dependent Claim
17 words
The lithiated nickel dioxide of claim 31, having a lithium hydroxide content less than about 5,000 ppm.
Claim 35
Dependent Claim
27 words
An electrochemical cell comprising a cathode containing the lithiated nickel dioxide cathode-active material as claimed in claim 24, an electrolyte, and a counter-electrode capable of intercalating lithium.
Claim 36
Dependent Claim
23 words
A lithiated nickel dioxide cathode-active material for an electrochemical cell having a BET surface area of less than about 3.0 m 2 /g.
Claim 37
Dependent Claim
23 words
A lithiated nickel dioxide cathode-active material for an electrochemical cell having a BET surface area of less than about 3.0 m 2 /g.
Claim 38
Dependent Claim
20 words
The lithiated nickel dioxide of claim 34, having a BET surface area of less than about 1.0 m 2 /g.
Claim 39
Dependent Claim
20 words
The lithiated nickel dioxide of claim 35, having a BET surface area of less than about 0.3 m 2 /g.
Claim 40
Dependent Claim
24 words
An electrochemical cell comprising a cathode containing the cathode-active material as claimed in claim 34, an electrolyte, and a counter-electrode capable of intercalating lithium.
Claim 41
Dependent Claim
22 words
The electrochemical cell of claim 22, or claim 33 or claim 37, wherein said counter-electrode capable of intercalating lithium, comprises graphitic carbon.
Claim 42
Dependent Claim
12 words
The electrochemical cell of claim 38, wherein said carbon is poorly graphitic.
Claim 43
Dependent Claim
13 words
The electrochemical cell of claim 39, wherein said poorly graphitic carbon comprises coke.
Claim 44
Dependent Claim
12 words
The electrochemical cell of claim 40, wherein said coke comprises petroleum coke.
Claim 45
Dependent Claim
25 words
An electrochemical cell comprising an electrode comprising lithium, an electrolyte and a cathode containing a cathode-active material as claimed in claim 24 or claim 34.
Claim 46
Dependent Claim
92 words
An electrochemical cell comprising a cathode containing a cathode-active material having a stoichiometric formula Li x Ni 2-x-y M y O 2 , wherein x is between about 0.8 and about 1.00, M is one or more metals selected from the group consisting of cobalt, iron, chromium, titanium, manganese and vanadium, and y is less than about 0.2, with the proviso that y is less than about 0.5 for cobalt, an electrolyte, and a counter-electrode capable of intercalating lithium, wherein said cathode-active material is substantially free of lithium hydroxide or lithium carbonate.
Claim 47
Dependent Claim
92 words
An electrochemical cell comprising a cathode containing a cathode-active material having a stoichiometric formula Li x Ni 2-x-y M y O 2 , wherein x is between about 0.8 and about 1.00, M is one or more metals selected from the group consisting of cobalt, iron, chromium, titanium, manganese and vanadium, and y is less than about 0.2, with the proviso that y is less than about 0.5 for cobalt, an electrolyte, and a counter-electrode capable of intercalating lithium, wherein said cathode-active material is substantially free of lithium hydroxide or lithium carbonate.
Claim 48
Dependent Claim
35 words
An electrochemical cell comprising a cathode containing a cathode-active material comprising lithiated nickel dioxide having a BET surface area less than about 3.0 m 2 /g., an electrolyte, and a counterelectrode capable of intercalating lithium.
Claim 49
Dependent Claim
35 words
An electrochemical cell comprising a cathode containing a cathode-active material comprising lithiated nickel dioxide having a BET surface area less than about 3.0 m 2 /g., an electrolyte, and a counterelectrode capable of intercalating lithium.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1996-11-22 | 1997-05-24 | 1997-11-23 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2000-11-22 | 2001-05-24 | 2001-11-23 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2004-11-22 | 2005-05-24 | 2005-11-23 | $7700.00 | Window Closed / Lapsed |