Polyvinylpyridine additives for nonaqueous electrolytes activating lithium rechargeable electrochemical cells
View Patent ↗An electrolyte comprising an organic solvent, a lithium salt, and a polymer additive comprised of repeating vinyl units joined to one or more heterocyclic amine moieties is described. The heterocyclic amine contains five to ten ring atoms, inclusive. An electrochemical cell is also disclosed. The preferred cell comprises a negative electrode which intercalates with lithium, a positive electrode comprising an electrode active material which intercalates with lithium, and the electrolyte of the present invention activating the negative and the positive electrodes.
1. An electrolyte for an electrochemical cell, the electrolyte comprising:
a) a linear carbonate mixture of dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), and diethyl carbonate (DEC), wherein by volume percent, DMC is in the range of from about 5% to about 75%; EMC is in the range of from about 5% to about 50%; and DEC is in the range of from about 3% to about 45%;
b) ethylene carbonate (EC) as a cyclic carbonate, wherein the EC is in the range of from about 10% to about 50% by volume percent;
c) a lithium salt; and
d) poly(2-vinylpyridine-co-styrene) at a concentration of from about 0.05 to less than 1.0 weight percent.
2. The electrolyte of claim 1 wherein the poly(poly(2-vinylpyridine-co-styrene) comprises a molecular weight of 5,000.
3. The electrolyte of claim 1 wherein the lithium salt is selected from the group consisting of LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 , LiClO 4 , LiAlCl 4 , LiGaCl 4 , LiC(SO 2 CF 3 ) 3 , LiNO 3 , LiN (SO 2 CF 3 ) 2 , LiSCN, LiO 3 SCF 2 CF 3 , LiC 6 F 5 SO 3 , LiO 2 CCF 3 ,Li SO 3 F, LiB (C 6 H 5 ) 4 , LiCF 3 SO 3 , and mixtures thereof.
4. The electrolyte of claim 1 further comprising an additional additive selected from the group consisting of vinylene carbonate, fluorinated ethylene carbonate, biphenyl, cyclohexyl benzene, and combinations thereof.
5. The electrolyte of claim 1 not including a biphenyl compound.
6. An electrochemical cell comprising:
a) a negative electrode comprising an anode active material which intercalates with lithium;
b) a positive electrode comprising a cathode active material which intercalates with lithium;
c) a separator intermediate the negative and positive electrodes to thereby prevent the electrodes from direct physical contact with each other; and
d) an electrolyte activating the negative and positive electrodes, the electrolyte comprising:
i) a linear carbonate mixture of dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), and diethyl carbonate (DEC), wherein by volume percent, DMC is in the range of from about 5% to about 75%; EMC is in the range of from about 5% to about 50%; and DEC is in the range of from about 3% to about 45%;
ii) ethylene carbonate (EC) as a cyclic carbonate, wherein the EC is in the range of from about 10% to about 50% by volume percent;
iii) a lithium salt; and
iv) poly(2-vinylpyridine-co-styrene) at a concentration of from about 0.05 to less than 1.0 weight percent.
7. The electrochemical cell of claim 6 wherein the poly(2-vinylpyridine-co-styrene) comprises a molecular weight of 5,000.
8. The electrochemical cell of claim 6 wherein the electrolyte does not include a biphenyl compound.
9. The electrochemical cell of claim 6 wherein the anode active material comprises a carbonaceous material selected from coke, graphite, acetylene black, carbon black, glassy carbon, carbon nanotubes, and meso-carbon microbeads.
10. The electrochemical cell of claim 9 wherein the carbonaceous material is fibrous.
11. The electrochemical cell of claim 6 wherein the negative electrode comprises from about 90 to 97 weight percent graphite as the anode active material mixed with from about 3 to 10 weight percent of a fluoro-resin binder.
12. The electrochemical cell of claim 6 wherein the negative electrode comprises a current collector selected from the group consisting of copper, stainless steel, titanium, tantalum, platinum, gold, aluminum, nickel, cobalt nickel alloy, highly alloyed ferritic stainless steel containing molybdenum and chromium, and nickel-, chromium-, and molybdenum-containing alloys.
13. The electrochemical cell of claim 6 wherein the positive electrode comprises from about 90 to 97 weight percent LiCoO 2 as the cathode active material mixed with from about 1 to 10 weight percent of a conductive additive and from about 3 to 10 weight percent of a fluoro-resin binder.
14. The electrochemical cell of claim 6 wherein the cathode active material is selected from the group consisting of LiNiO 2 , LiMn 2 O 4 , LiCoO 2 , LiCo 0.92 Sn 0.08 O 2 , lithium cobalt nickel oxide, and LiMPO 4 (where M is one or metals from columns 4 through 13 of the Periodic Table of the Elements).
15. The electrochemical cell of claim 6 wherein the lithium salt is selected from the group consisting of LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 , LiClO 4 , LiAlCl 4 , LiGaCl 4 , LiC(SO 2 CF 3 ) 3 , LiNO 3 , LiN (SO 2 CF 3 ) 2 , LiSCN, LiO 3 SCF 2 CF 3 , LiC 6 F 5 SO 3 , LiO 2 CCF 3 , LiSO 3 F, LiB(C 6 H 5 ) 4 , LiCF 3 SO 3 , and mixtures thereof.
16. A method for making an electrochemical cell, comprising the steps of:
a) providing a negative electrode of an anode active material which intercalates with lithium;
b) providing a positive electrode comprising a cathode active material which intercalates with the lithium;
c) disposing a separator intermediate the negative and positive electrodes to thereby prevent the electrodes from direct physical contact with each other; and
d) activating the negative and positive electrodes with a nonaqueous electrolyte comprising:
i) a linear carbonate mixture of dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), and diethyl carbonate (DEC), wherein by volume percent, DMC is in the range of from about 5% to about 75%; EMC is in the range of from about 5% to about 50%; and DEC is in the range of from about 3% to about 45%;
ii) ethylene carbonate (EC) as a cyclic carbonate, wherein the EC is in the range of from about 10% to about 50% by volume percent;
iii) a lithium salt; and
iv) poly(2-vinylpyridine-co-styrene) at a concentration of from about 0.05 to less than 1.0 weight percent.
17. The method of claim 16 including mixing from about 90 to 97 weight percent graphite as the anode active material with from about 3 to 10 weight percent of a binder to thereby provide an anode active material mixture containing the anode active material for the negative electrode.
18. The method of claim 17 wherein the binder is selected from the group consisting of polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyethylenetetrafluoroethylene (ETFE), polyamides, polyimides, and mixtures thereof.
19. The method of claim 16 including contacting the anode active material to a current collector selected from the group consisting of copper, stainless steel, titanium, tantalum, platinum, gold, aluminum, nickel, cobalt nickel alloy, highly alloyed ferritic stainless steel containing molybdenum and chromium, and nickel-, chromium-, and molybdenum-containing alloys.
20. The method of claim 16 including mixing from about 90 to 97 weight percent LiCoO 2 as the cathode active material mixed with from about 1 to 10 weight percent of a conductive additive and from about 3 to 10 weight percent of a fluoro-resin binder to thereby provide a cathode active material mixture containing the cathode active material for the positive electrode.
21. The method of claim 16 including providing the poly(2-vinylpyridine-co-styrene) comprising a molecular weight of 5,000.
22. The method of claim 16 including selecting the lithium salt from the group consisting of LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 , LiClO 4 , LiAlCl 4 , LiGaCl 4 , LiC(SO 2 CF 3 ) 3 , LiNO 3 , LiN (SO 2 CF 3 ) 2 , LiSCN, LiO 3 SCF 2 CF 3 , LiC 6 F 5 SO 3 , LiO 2 CCF 3 ,LiSO 3 F, LiB (C 6 H 5 ) 4 , LiCF 3 SO 3 , and mixtures thereof.
23. The method of claim 16 wherein the electrolyte does not include a biphenyl compound.
24. The method of claim 16 including selecting the anode active material from the group consisting of coke, graphite, acetylene black, carbon black, glassy carbon, carbon nanotubes, and meso-carbon microbeads.
25. The method of claim 16 including providing the anode active material as a fibrous carbonaceous material.
26. The method of claim 16 including selecting the cathode active material from the group consisting of LiNiO 2 , LiMn 2 O 4 , LiCoO 2 , LiCo 0.92 Sn 0.08 O 2 , lithium cobalt nickel oxide, and LiMPO 4 (where M is one or metals from columns 4 through 13 of the Periodic Table of the Elements).