IP Library Granted Patent US 8,133,616
Granted Patent B2
US 8,133,616 · App. 12/279,469 · Granted Mar 13, 2012

Lithium manganese phosphate positive material for lithium secondary battery

Assignee: Dow Global Technologies LLC
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Quick Facts
Patent No.
US 8,133,616
App. No.
12/279,469
Granted
Mar 13, 2012
Kind
B2
Abstract

A process for the production of nano-structured olivine lithium manganese phosphate (LiMnPO 4 ) electrode material comprising of the following steps: sol gel preparation in a chelating environment; preparation of lithium manganese phosphate/carbon composite by ball-milling; and electrode preparation.

Claims (20)

1. A process for the production of electro-active nanostructured olivine lithium manganese phosphate in the form of particles including the steps of mixing and gel formation, drying and calcination characterized in that the mixing of precursors is done in this order manganese (II) acetate tetrahydrate, lithium acetate dihydrate and ammonium dihydrogen phosphate.

2. A process according to claim 1 , wherein a chelating agent is added during the mixing step and the chelating agent used is an organic acid having a pK a value in the range of from about 1.0 to about 5.0 selected from the group consisting of acetic acid, ascorbic acid, benzoic acid, citric acid, lactic acid, malic acid, malonic, acid, oxalic acid, salicylic acid, glycolic acid, tartaric acid and mixtures thereof.

3. A process according to claim 2 characterized in that the concentration of the chelating agent is 1 to 10 times the concentration of the manganese precursor on a mole basis.

4. A process according to claim 3 characterized in that after the addition of the chelating agent the pH is adjusted in a range of 1.5 to 4.

5. A process for the production of electro-active nanostructured olivine lithium manganese phosphate in the form of particles including the steps of mixing and gel formation, drying and calcination, wherein a chelating agent is added during the mixing step and the chelating agent used is an organic acid having a pK a value in the range of from about 1.0 to about 5.0 selected from the group consisting of acetic acid, ascorbic acid, benzoic acid, citric acid, lactic acid, malic acid, malonic, acid, oxalic acid, salicylic acid, glycolic acid, tartaric acid and mixtures thereof.

6. A process according to claim 5 wherein the particle size is in the range 90-300 nm.

7. A process according to claim 6 wherein the particle size is in the range 90-150 nm.

8. A process according to claim 5 wherein the organic acid is selected from the group consisting of acetic acid, glycolic acid, citric acid, oxalic acid and tartaric acid.

9. A process according to claim 5 characterized in that the concentration of the chelating agent is 1 to 10 times the concentration of the manganese precursor on a mole basis.

10. A process according to claim 9 wherein the concentration of the chelating agent is comprised in the range of 4 to 6 times the concentration of the manganese precursor on a mole basis.

11. A process according to claim 5 characterized in that after the addition of the chelating agent the pH is adjusted in a range of 1.5 to 4.5.

12. A process according to claim 11 wherein, after the addition of the chelating agent the pH is adjusted to 2.0.

13. A process according to claim 5 characterized in that the gel is stabilized by a drying process at 80° C. for 12 to 48 hours followed by drying at 120° C. for 6 to 24 hours.

14. A process according to claim 5 characterized in that a pre-calcination step is done on the gel at 350° C. for several hours to remove most of the organics present in the gel.

15. A process according to claim 5 , characterized in that the calcination step is done on the gel from 400° C. to 900° C. for 1 to 5 hours.

16. A process according to claim 15 wherein the temperature of calcination is between 450° C. and 600° C.

17. An electrode material prepared by the process according to claim 5 , further comprising the step of ball milling the nanostructured olivine lithium manganese phosphate with carbon to produce lithium manganese phosphate/carbon composite having a particle size in the range of 90 to 150 nm and carbon covering the surface of the nanostructured olivine lithium manganese phosphate.

18. An electrode material according to claim 17 wherein the carbon is acetylene black.

19. An electrode material according to claim 17 wherein the carbon concentration is 1-30 ww %.

20. A electrochemical cell comprising a cathode, an anode and an electrolyte wherein the cathode is made from a material according to claim 17 .

Assignments (6)
CORRECTIVE ASSIGNMENT TO CORRECT THE ADDRESS OF THE ASSIGNEE. PREVIOUSLY RECORDED ON REEL 024869 FRAME 0831. ASSIGNOR(S) HEREBY CONFIRMS THE CORRECTED ADDRESS SHOULD BE LUASANNE, SWITZERLAND. Recorded Jan 26, 2012
From: EXNAR, IVAN; DREZEN, THIERRY; KWON-ROTH, NAM-HEE; ISONO, MOTOSHI
To: HPL (HIGH POWER LITHIUM)
Reel/Frame 027599/0201 →
CHANGE OF NAME Recorded Mar 30, 2011
From: HPL (HIGH POWER LITHIUM) AG
To: DOW GLOBAL TECHNOLOGIES LLC
Reel/Frame 026050/0166 →
CHANGE OF NAME Recorded Mar 25, 2011
From: HPL (HIGH POWER LITHIUM) SA
To: HPL (HIGH POWER LITHIUM) AG
Reel/Frame 026019/0720 →
CORRECTIVE ASSIGNMENT TO CORRECT THE ASSIGNEE: HIGH POWER LITHIUM SA TO THE CORRECT COMPANY PREVIOUSLY RECORDED ON REEL 021762 FRAME 0574. ASSIGNOR(S) HEREBY CONFIRMS THE CORRECTED ASSIGNEE SHOULD BE HPL (HIGH POWER LITHIUM) SA. Recorded Aug 23, 2010
From: EXNAR, IVAN; DREZEN, THIERRY; KWON-ROTH, NAM-HEE; ISONO, MOTOSHI
To: HPL (HIGH POWER LITHIUM) SA
Reel/Frame 024869/0831 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 2, 2010
From: HIGH POWER LITHIUM S.A.
To: DOW GLOBAL TECHNOLOGIES INC.
Reel/Frame 023884/0566 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 23, 2008
From: EXNAR, IVAN; DREZEN, THIERRY; KWON-ROTH, NAM HEE; ISONO, MOTOSHI
To: HIGH POWER LITHIUM S.A.; TOYOTA JIDOUSHA KABUSHIKI KAISHA
Reel/Frame 021762/0574 →
Continuity (1)
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