US5702679A
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Method of preparing Li1+X- Mn2-X O4 for use as secondary battery
Assignee: Tronox LLC
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Filing: 1995-10-06
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Granted: 1997-12-30
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Expires: 2015-10-06
Abstract
Abstract A continuous method of preparing a single phase lithiated manganese oxide intercalation compound of the formula Li1+xMn2-xO4 comprising the steps of: mixing intimately a lithium hydroxide or a lithium salt and a manganese oxide or a manganese salt; feeding the intimately mixed salts to a reactor; continuously agitating the mixed salts in the reactor; heating the agitated mixed salts in the reactor at a temperature of from about 650 DEG C. to about 800 DEG C. for a time not in excess of about 4 hours in an oxygen-containing atmosphere; and cooling the reacted product to less than about 200 DEG C. in an oxygen-containing atmosphere for a time not in excess of about 2 hours.
Inventors
- 👤 Stephen W. Sheargold
- 👤 Terrell N. Andersen
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-27 16:27
CPC Classifications
H; H01; H01M; H01M4/00; H01M4/02; H01M4/36; H01M4/48; H01M4/50; H01M4/505; C; C01; C01G; C01G45/00; C01G45/12; C01G45/1221; C01G45/1242; C01P; C01P2002/00; C01P2002/30; C01P2002/32; C01P2002/70; C01P2002/72; C01P2002/77; C01P2006/00; C01P2006/40; H01M10/00; H01M10/05; H01M10/052; H01M4/13; H01M4/131; Y; Y02; Y02E; Y02E60/00; Y02E60/10
Claims Analysis
Total Claims: 64
Claim 1
Independent Claim
154 words
A continuous method of preparing a single phase lithiated manganese oxide intercalation compound of the formula Li 1+x Mn 2-x O 4 having a spinel-type structure comprising the steps of: (a) mixing intimately in amounts, based on said lithiated manganese oxide compound, a lithium hydroxide or a lithium salt and a manganese oxide or a manganese salt; (b) feeding the intimately mixed compounds to a reactor; (c) continuously agitating the mixed compounds in the reactor; (d) heating the agitated mixed compounds in the reactor in the presence of air or an oxygen-enriched atmosphere at a temperature of from about 650° C. to about 800° C. for a time not in excess of about 4 hours to form; (e) cooling the reacted product to less than about 200° C. in less than about 2 hours; wherein x is from about 0.0328 to about 0.125 and the a-axis lattice parameter is about 8.235 Å or less.
Claim 2
Dependent Claim
154 words
A continuous method of preparing a single phase lithiated manganese oxide intercalation compound of the formula Li 1+x Mn 2-x O 4 having a spinel-type structure comprising the steps of: (a) mixing intimately in amounts, based on said lithiated manganese oxide compound, a lithium hydroxide or a lithium salt and a manganese oxide or a manganese salt; (b) feeding the intimately mixed compounds to a reactor; (c) continuously agitating the mixed compounds in the reactor; (d) heating the agitated mixed compounds in the reactor in the presence of air or an oxygen-enriched atmosphere at a temperature of from about 650° C. to about 800° C. for a time not in excess of about 4 hours to form; (e) cooling the reacted product to less than about 200° C. in less than about 2 hours; wherein x is from about 0.0328 to about 0.125 and the a-axis lattice parameter is about 8.235 Å or less.
Claim 3
Dependent Claim
18 words
The method according to claim 1 further including cooling the reacted product to less than about 100° C.
Claim 4
Dependent Claim
22 words
The method according to claim 1 further including after the cooling step the step of removing the cooled product from the reactor.
Claim 5
Dependent Claim
16 words
The method according to claim 1 wherein step (a) is performed by a rotating drum mixer.
Claim 6
Dependent Claim
15 words
The method according to claim 1 wherein step (a) is performed by a ball mill.
Claim 7
Dependent Claim
15 words
The method according to claim 1 wherein step (a) is performed by a vibratory mill.
Claim 8
Dependent Claim
15 words
The method according to claim 1 wherein step (a) is performed by a jet mill.
Claim 9
Dependent Claim
16 words
The method according to claim 1 wherein feeding step (b) is performed by a screw feeder.
Claim 10
Dependent Claim
16 words
The method according to claim 1 wherein feeding step (b) is performed by a pneumatic conveyor.
Claim 11
Dependent Claim
17 words
The method according to claim 1 wherein feeding step (b) is performed by a pulsed air jet.
Claim 12
Dependent Claim
24 words
The method according to claim 1 wherein the atmosphere is continuously purged with a flow of air, oxygen or oxygen-enriched air during step (c).
Claim 13
Dependent Claim
23 words
The method according to claim 1 wherein the atmosphere is continuously purged with a countercurrent flow of oxygen enriched atmosphere during step (c).
Claim 14
Dependent Claim
24 words
The method according to claim 1 wherein the reactor is a horizontal rotary tube with the exit end slightly lower than the entrance end.
Claim 15
Dependent Claim
17 words
The method according to claim 1 wherein the reactor is a horizontal calciner with a rotating screw.
Claim 16
Dependent Claim
13 words
The method according to claim 1 wherein the reactor is a fluidized bed.
Claim 17
Dependent Claim
15 words
The method according to claim 1 wherein the reactor is a heated vibratory conveyor belt.
Claim 18
Dependent Claim
16 words
The method according to claim 1 wherein the reactor is a cascade of vertical rotating hearths.
Claim 19
Dependent Claim
18 words
The method according to claim 1 wherein the heating step is performed in about 2 hours or less.
Claim 20
Dependent Claim
20 words
The method according to claim 1 wherein the heating step is performed in about one and one-half hours or less.
Claim 21
Dependent Claim
20 words
The method according to claim 19 wherein the heating step temperature is from about 700° C. to about 800° C.
Claim 22
Dependent Claim
21 words
The method according to claim 1 including continuous purging with a flow of air, oxygen or oxygen-enriched atmosphere during step (d).
Claim 23
Dependent Claim
17 words
The method according to claim 21 wherein the continuous purging is with a countercurrent flow of air.
Claim 24
Dependent Claim
20 words
The method according to claim 1 wherein the cooling step is performed in a horizontal calciner with a rotating screw.
Claim 25
Dependent Claim
16 words
The method according to claim 1 wherein the cooling step is performed in a fluidized bed.
Claim 26
Dependent Claim
16 words
The method according to claim 1 wherein the cooling step is performed in a rotary kiln.
Claim 27
Dependent Claim
18 words
The method according to claim 1 wherein the cooling step is performed in a heated vibratory conveyor belt.
Claim 28
Dependent Claim
19 words
The method according to claim 1 wherein the cooling step is performed in a cascade of vertical rotating hearths.
Claim 29
Dependent Claim
20 words
The method according to claim 1 wherein the cooling step is performed in about one and one-half hours or less.
Claim 30
Dependent Claim
20 words
The method according to claim 1 wherein said cooling step is performed in less than about 1 and 1/2 hours.
Claim 31
Dependent Claim
18 words
The method according to claim 1 wherein the cooling step is performed in zones of progressively cooler temperatures.
Claim 32
Dependent Claim
17 words
The method according to claim 30 wherein the cooling step is performed in at least two zones.
Claim 33
Dependent Claim
26 words
The method according to claim 31 wherein the temperature in each progressive cooling zone is at least about 90° C. lower than the immediately previous zone.
Claim 34
Dependent Claim
23 words
The method according to claim 32 wherein the temperatures in the progressive cooling zones are about: 725° C., 625° C., and 525° C.
Claim 35
Dependent Claim
23 words
The method according to claim 32 wherein the temperatures in the progressive cooling zones are about: 800° C., 650° C., and 500° C.
Claim 36
Dependent Claim
23 words
The method according to claim 32 wherein the temperatures in the progressive cooling zones are about: 750° C., 600° C., and 450° C.
Claim 37
Dependent Claim
36 words
The method according to claim 32 for preparing a spinel structure lithiated intercalation compound of the formula Li 1+x Mn 2-x O 4 wherein said cooled product is annealed by allowing the product to uptake oxygen.
Claim 38
Dependent Claim
23 words
The method according to claim 36 wherein said cooled product is annealed by allowing the product to uptake the maximum amount of oxygen.
Claim 39
Dependent Claim
26 words
The method according to claim 1 wherein the atmosphere is continuously purged with a flow of air, oxygen or an oxygen-enriched atmosphere during the cooling step.
Claim 40
Dependent Claim
22 words
The method according to claim 38 wherein the atmosphere is continuously purged with a countercurrent flow of air during the cooling step.
Claim 41
Dependent Claim
42 words
The method according to claim 1 wherein the manganese oxide or manganese salt is selected from the group consisting of MnO 2 , MnCO 3 , Mn 2 O 3 , Mn 3 O 4 , MnO, manganese acetate and mixtures thereof.
Claim 42
Dependent Claim
18 words
The method according to claim 1 wherein the manganese oxide has been heat treated prior to step (a).
Claim 43
Dependent Claim
33 words
The method according to claim 1 wherein the lithium hydroxide or lithium salt is selected from the group consisting of LiOH, Li 2 CO 3 , LiNO 3 and mixtures and hydrates thereof.
Claim 44
Dependent Claim
20 words
The method of claim 41 wherein the MnO 2 is neutralized by LiOH or NH 4 OH during its synthesis.
Claim 45
Dependent Claim
34 words
The method according to claim 1 which comprises the additional steps, prior to said cooling step, of: (i) removing the product from the reactor; and (ii) transferring the reacted product to a separate vessel.
Claim 46
Dependent Claim
18 words
The method according to claim 1 wherein heating step (d) is performed in zones of progressively warmer temperatures.
Claim 47
Dependent Claim
17 words
The method according to claim 45 wherein the heating step is performed in at least four zones.
Claim 48
Dependent Claim
24 words
The method according to claim 46 wherein the temperature in each progressive heating zone is at least 25° higher than the immediately previous zone.
Claim 49
Dependent Claim
20 words
The method according to claim 45 wherein the agitated mixed compounds remain in each zone at least about 30 minutes.
Claim 50
Independent Claim
175 words
A method of synthesizing a lithium manganese oxide of the formula Li 1+x Mn 2-x O 4 having a spinel-type crystal structure with an a-axis lattice parameter of about 8.235 Å or less, and wherein x is from about 0.0328 to about 0.125 comprising forming an intimate mixture in finely divided solid form of at least one lithium hydroxide or lithium salt reactant selected from the group consisting of LiOH, Li 2 CO 3 , LiNO 3 and mixtures thereof and at least one manganese oxide or manganese salt reactant selected from the group consisting of MnO 2 , Mn 2 O 3 , MnCO 3 , Mn 3 O 4 , MnO, manganese acetate and mixtures thereof and continuously agitating and heating the mixure in a reactor under a continuous purge of countercurrent air at a temperature in the range of from about 650° C. to about 800° C. for a period not in excess of about 4 hours to cause said reactants to react with each other to form said lithium manganese oxide.
Claim 51
Independent Claim
175 words
A method of synthesizing a lithium manganese oxide of the formula Li 1+x Mn 2-x O 4 having a spinel-type crystal structure with an a-axis lattice parameter of about 8.235 Å or less, and wherein x is from about 0.0328 to about 0.125 comprising forming an intimate mixture in finely divided solid form of at least one lithium hydroxide or lithium salt reactant selected from the group consisting of LiOH, Li 2 CO 3 , LiNO 3 and mixtures thereof and at least one manganese oxide or manganese salt reactant selected from the group consisting of MnO 2 , Mn 2 O 3 , MnCO 3 , Mn 3 O 4 , MnO, manganese acetate and mixtures thereof and continuously agitating and heating the mixure in a reactor under a continuous purge of countercurrent air at a temperature in the range of from about 650° C. to about 800° C. for a period not in excess of about 4 hours to cause said reactants to react with each other to form said lithium manganese oxide.
Claim 52
Dependent Claim
44 words
The method according to claim 49, wherein the heating of the mixture is in air at a temperature of from about 700° C. to about 800° C., the mixture being held at the maximum temperature for a period of less than about 2 hours.
Claim 53
Dependent Claim
19 words
The method according to claim 49 wherein the manganese oxide has been heat treated prior to forming the mixture.
Claim 54
Dependent Claim
39 words
The method according to claim 49, wherein the Li 1+x Mn 2-x O 4 has a (Mn 2 )O 4 (Mn 2 )O 4 n-1 framework structure in which the quantity of Mn cations varies from the stoichiometric value.
Claim 55
Dependent Claim
16 words
A lithium manganese oxide having a spinel crystal structure, synthesized by the method of claim 49.
Claim 56
Independent Claim
174 words
A method of preparing a single phase lithiated manganese oxide intercalation compound of the formula Li 1+x Mn 2-x O 4 having a spinel-type structure by a batch process comprising the steps of (a) fixing intimately in stoichiometric mounts, based on said lithiated manganese oxide compound, a lithium hydroxide or a lithium salt and a manganese oxide or a manganese salt; (b) feeding the intimately mixed compounds to a reactor; (c) agitating the mixed compounds in the reactor; (d) heating the agitated mixed compounds in the reactor in the presence of air or an oxygen-enriched atmosphere at a temperature of from about 650° C. to about 800° C. for a time not in excess of about 4 hours to form an oxygen deficient spinel structure intercalation compound; and (e) cooling the oxygen deficient product to less than about 100° C. in about 2 hours or less; to form Li 1+x Mn 2-x O 4 wherein x is from about 0.0328 to about 0.125 and the a-axis lattice parameter is about 8.235 Å or less.
Claim 57
Independent Claim
174 words
A method of preparing a single phase lithiated manganese oxide intercalation compound of the formula Li 1+x Mn 2-x O 4 having a spinel-type structure by a batch process comprising the steps of (a) fixing intimately in stoichiometric mounts, based on said lithiated manganese oxide compound, a lithium hydroxide or a lithium salt and a manganese oxide or a manganese salt; (b) feeding the intimately mixed compounds to a reactor; (c) agitating the mixed compounds in the reactor; (d) heating the agitated mixed compounds in the reactor in the presence of air or an oxygen-enriched atmosphere at a temperature of from about 650° C. to about 800° C. for a time not in excess of about 4 hours to form an oxygen deficient spinel structure intercalation compound; and (e) cooling the oxygen deficient product to less than about 100° C. in about 2 hours or less; to form Li 1+x Mn 2-x O 4 wherein x is from about 0.0328 to about 0.125 and the a-axis lattice parameter is about 8.235 Å or less.
Claim 58
Dependent Claim
18 words
The method according to claim 54 wherein the cooling vessel is a horizontal calciner with a rotating screw.
Claim 59
Dependent Claim
14 words
The method according to claim 54 wherein the cooling vessel is a fluidized bed.
Claim 60
Dependent Claim
16 words
The method according to claim 54 wherein the cooling vessel is a heated vibratory conveyor belt.
Claim 61
Dependent Claim
17 words
The method according to claim 54 wherein the cooling vessel is a cascade of vertical rotating hearths.
Claim 62
Dependent Claim
14 words
The method according to claim 54 wherein the cooling vessel is a rotary kiln.
Claim 63
Dependent Claim
20 words
The method according to claim 54 wherein the cooling step is performed in about one and one-half hours or less.
Claim 64
Dependent Claim
18 words
The method according to claim 54 wherein said cooling step is performed in less than about 1 hour.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 2000-12-29 | 2001-06-30 | 2001-12-30 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2004-12-29 | 2005-06-30 | 2005-12-30 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2008-12-29 | 2009-06-30 | 2009-12-30 | $7700.00 | Window Closed / Lapsed |