Triazine Compounds For Removing Acids And Water From Nonaqueous Electrolytes For Electrochemical Cells

• US 20100192363A1
• Filed: 04/14/2010
• Published: 08/05/2010
• Est. Priority Date: 05/26/2005
• Status: Active Grant

• Current Assignee: Shenzhen Capchem Technology Co., Ltd.
• Original Assignee: Ferro Corporation
• Inventors: Decker, Jerry L., Xu, Wu, Sans, John R., Deng, Zhongyi, Bolomey, Pascal
• Granted Patent: US 7,867,294 B2
• Time in Patent Office: Days
• US Class Current: 29/623.2
• CPC Class Codes: H01M 10/0431 Cells with wound or folded electrodes H01M10/045 takes precedence
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 10/0568 characterised by the solutes
• CPC Class Codes: H01M 10/0569 characterised by the solvents
• CPC Class Codes: H01M 10/0587 of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
• CPC Class Codes: H01M 10/4235 Safety or regulating additives or arrangements in electrodes, separators or electrolyte H01M10/4242 takes precedence
• CPC Class Codes: H01M 2300/0025 Organic electrolyte
• CPC Class Codes: H01M 2300/004 Three solvents
• CPC Class Codes: H01M 4/405 Alloys based on lithium
• CPC Class Codes: H01M 4/485 of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take precedence
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y02T 10/70 Energy storage systems for electromobility, e.g. batteries
• CPC Class Codes: Y10T 29/49108 Electric battery cell making
• CPC Class Codes: Y10T 29/4911 including sealing
• CPC Class Codes: Y10T 29/49112 including laminating of indefinite length material
• CPC Class Codes: Y10T 29/49115 including coating or impregnating

Abstract

A process is provided to produce non-aqueous electrolytic solution for use in batteries having low acid content and low water content. The invention involves removing acids and water from non-aqueous electrolytic solutions typically found in lithium or lithium-ion batteries by using nitrogen-containing compounds such as triazines. After treatment by a triazine such as melamine, the concentrations of acids and water in the electrolytic solutions are substantially decreased. The present invention provides a process to prepare extremely pure electrolytic solutions having low (<20 ppm) concentrations of both water and acids.

Claims

1-11. -11. (canceled)

12. A method of making a secondary battery comprising:

providing an electrolytic solution comprising

i. a non-aqueous electrolytic solvent and

ii. a lithium containing salt;

contacting the electrolytic solution with a triazine compound;

removing substantially all of the triazine compound from the electrolytic solution;

aminating and winding a cathode, a first porous separator, an anode, and a second porous separator;

placing the wound laminated electrodes and separators in a battery case;

infusing the electrolytic solution into the battery case; and

,

sealing the battery case containing the electrodes, electrolytic solution and separators.

13. The method of claim 12 wherein the triazine compound has the formula 2-R¹-4-R²-6-R³-1,3,5-triazine, wherein R¹, R², and R³ are independently selected from the group consisting of hydrogen, halogen, C₁-C₂₀ alkyl, C₁-C₂₀ alkenyl, phenyl, and substituted phenyl.

14. The method of claim 12 wherein the triazine compound is selected from the group consisting of

2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl)-s-triazine,

2,6-bis(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine;

2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine;

2,4-bis(2-hydroxy(2-hydroxyethoxy)phenyl)-6-(4-chlorophenyl)-s-triazine;

2,4-bis(2-hydroxy-4-(2-hydroxyethoxy)phenyl)-phenyl-s-triazine;

2,4-bis(2-hydroxy-4-(2-hydroxyethoxy)-phenyl)-6-(2,4-dimethylphenyl)-s-triazine;

2,4-bis(2-hydroxy(2-hydroxyethoxy)phenyl)-6-(4-bromophenyl)-s-triazine;

2,4-bis(2-hydroxy-4-(2-acetoryethoxy)phenyl)-6-(4-chlorophenyl)-s-triazine;

2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-1-s-triazine;

melamine;

2,4,6-trimethoxy-1,3,5-triazine;

2,4,6-triphenyoxy-1,3,5-triazine;

2,4,6-triethoxy-1,3,5-triazine,

2,4,6-tripropoxy-1,3,5-triazine;

2,4,6-tributoxy-1,3,5-triazine, and combinations thereof.

15. The method of claim 12 wherein the non-aqueous solvent is selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, tetrahydrofuran, 2-methyl tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, acetonitrile, dimethylformamide, methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, γ

-butyrolactone, 2-methyl-γ

-butyrolactone, 3-methyl-γ

-butyrolactone, 4-methyl-γ

-butyrolactone, β

-propiolactone, δ

-valerolactone, trimethyl phosphate, triethyl phosphate, tris(2-chloroethyl)phosphate, tris(2,2,2-trifluoroethyl)phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, trihexyl phosphate, triphenyl phosphate, tritolyl phosphate, and combinations thereof.

16. The method of claim 12 wherein the lithium containing salt is selected from the group consisting of LiPF₆, LiBF₄, LiSbF₆, LiAsF₆, LiTaF₆, Li₂B₁₀Cl₁₀, LiBMB, LiBMB, LiBDFMB, LiMOB, LiDFMOB, LiTOP, LiTDFMP, LiClO₄, LiCF₃SO₃;

LiN(SO₂C_mF_2m+1)(SO₂C_nF_2n+1), and LiC(SO₂C_kF_2k+1)(SO₂C_mF_2m+1)(SO₂C_nF_2n+1), wherein k=1-10, m=1-10, and n=1-10, respectively;

LiN(SO₂C_pF_2pSO₂), and LiC(SO₂C_pF_2pSO₂)(SO₂C_qF_2q+1) wherein p=1-10 and q=1-10; and

LiPF_x(R_F)<sub>6−

x</sub> and LiBF_y(R_F)<sub>4−

y</sub>, wherein R_F represents perfluorinated C₁-C₂₀ alkyl groups or perfluorinated aromatic groups, x=0-5, and y=0-3.

21. The method of claim 12 wherein the triazine compound is melamine.

22. The method of claim 13 wherein R¹, R², and R³ are each hydrogen.

19. A method of preparing a non-aqueous electrolytic solution for a lithium battery wherein the method comprises:

contacting a non aqueous electrolyte with a triazine compound to produce an electrolytic solution comprising less than about 20 ppm water and less than about 50 ppm acids.

20. The method of claim 19 wherein the method produces an electrolytic solution comprising less than about 10 ppm water and less than about 20 ppm acids.

23. The method of claim 19 wherein the triazine compound is melamine.