Solid electrolyte utilizing a polymeric matrix obtained by the polymerization of a substituted allylic chloroformate

• US 5,482,795 A
• Filed: 05/25/1994
• Issued: 01/09/1996
• Est. Priority Date: 05/25/1994
• Status: Expired due to Fees

• Current Assignee: Valence Technology Incorporated (Lithium Werks B.V.)
• Original Assignee: Valence Technology Incorporated (Lithium Werks B.V.)
• Inventors: Chaloner-Gill, Benjamin
• Primary Examiner(s): Kalafut, Stephen
• Assistant Examiner(s): Chaney, Carol
• Application Number:
  US08/249,002
• Time in Patent Office: 594 Days
• Field of Search: 429/192
• US Class Current: 429/316
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0565 Polymeric materials, e.g. gel-type or solid-type
• CPC Class Codes: H01M 6/18 with solid electrolyte
• CPC Class Codes: H01M 6/181 with polymeric electrolytes
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

This invention is directed to a single phase solid solvent-containing electrolyte having recurring units derived from a substituted allylic chloroformate incorporated within the solid polymeric matrix of the solid electrolyte. A novel electrolytic cell that incorporates the subject electrolyte also is provided. The specific molecular structure exhibited by such solid polymeric matrix is believed to advantageously facilitate the positioning of an inorganic ion salt and solvent between adjacent polymeric molecules during service within the solid electrolyte.

Claims

1. A single phase, solid, solvent-containing electrolyte comprising:

a solid polymeric matrix,

an inorganic ion salt, and

a solvent,

wherein said solid polymeric matrix was obtained by polymerizing a substituted allylic chloroformate formed by the reaction of an allylic chloroformate of formula (I);

##STR8## and an aliphatic reactant selected from the group consisting of monohydroxy alcohols having 1 to 11 carbon atoms or the sodium salts thereof, dihydroxy alcohols having 2 to 50 carbon atoms or the sodium salts thereof, primary monoamines having 1 to 7 carbon atoms or the sodium salts thereof, and secondary diamines having 2 to 12 carbon atoms or the sodium salts thereof, and mixtures of two or more of the foregoing.

2. A single phase, solid, solvent-containing electrolyte according to claim 1 wherein said inorganic ion salt is a sodium, lithium, or ammonium salt of a less mobile anion.

3. A single phase, solid, solvent-containing electrolyte according to claim 2 wherein said inorganic ion salt is selected from the group consisting of LiPF₆, LiClO₄, NaClO₄, LiCF₃ SO₃, Li[N(CF₃ SO₂)₂ ], and LiBF₄.

4. A single phase, solid, solvent-containing electrolyte according to claim 1 wherein said solvent is a mixture of propylene carbonate and triglyme.

5. A single phase, solid, solvent-containing electrolyte according to claim 1 wherein said aliphatic reactant utilized in the formation of said substituted allylic chloroformate is provided as a sodium salt during said formation reaction.

6. A single phase, solid, solvent-containing electrolyte according to claim 1 wherein said aliphatic reactant utilized in the formation of said substituted allylic chloroformate is a monohydroxy alcohol of the formula:

##STR9## or the sodium salt thereof where R₁ is H or CH₃, and n=0 to 10.

7. A single phase, solid, solvent-containing electrolyte according to claim 6 wherein said aliphatic reactant utilized in the formation of said substituted allylic chloroformate is a monohydroxy alcohol of the specified formula or the sodium salt thereof wherein n is 1 to 4.

8. A single phase, solid, solvent-containing electrolyte according to claim 7 wherein said aliphatic reactant utilized in the formation of said substituted allylic chloroformate is a monohydroxy alcohol of the specified formula or the sodium salt thereof wherein R₁ is H, and n is 3.

9. A single phase, solid, solvent-containing electrolyte according to claim 1 wherein said aliphatic reactant utilized in the formation of said substituted allylic chloroformate is a dihydroxy alcohol of the formula:

##STR10## or the sodium salt thereof wherein n is 2 to 10, and m is 1 to 5.

10. A single phase, solid, solvent-containing electrolyte according to claim 9 wherein said aliphatic reactant utilized in the formation of said substituted allylic chloroformate is a dihydroxy alcohol of the specified formula or the sodium salt thereof wherein n is 2 to 6, and m is 1.

11. A single phase, solid, solvent-containing electrolyte according to claim 9 wherein said aliphatic reactant utilized in the formation of said substituted allylic chloroformate is a dihydroxy alcohol of the specified formula or the sodium salt thereof wherein n is 6, and m is 1.

12. A single phase, solid, solvent-containing electrolyte according to claim 1 wherein said aliphatic reactant utilized in the formation of said substituted allylic chloroformate is a primary monamine of the formula:

##STR11## or the sodium salt thereof wherein n is 0 to 6.

13. A single phase, solid, solvent-containing electrolyte according to claim 12 wherein said aliphatic reactant utilized in the formation of said substituted allylic chloroformate is a primary diamine of the specified formula or the sodium salt thereof wherein n is 2 to 4.

14. A single phase, solid, solvent-containing electrolyte according to claim 12 wherein said aliphatic reactant utilized in the formation of said substituted allylic chloroformate is a primary diamine of the specified formula or a sodium salt thereof wherein n is 4.

15. A single phase, solid, solvent-containing electrolyte according to claim 1 wherein said aliphatic reactant utilized in the formation of said substituted allylic chloroformate is a secondary diamine of the formula:

##STR12## wherein n is 2 to 10.

16. A single phase, solid, solvent-containing electrolyte according to claim 15 wherein said aliphatic reactant utilized in the formation of said substituted allylic chloroformate is a secondary diamine of the specified formula or the sodium salt thereof wherein n is 6.

17. A single phase, solid, solvent-containing electrolyte according to claim 1 wherein said solid polymeric matrix is obtained by copolymerizing said substituted allylic chloroformate with an acrylate.

18. A single phase, solid, solvent-containing electrolyte according to claim 17 wherein said solid polymeric matrix comprises less than approximately 22 percent by weight of recurring units derived from said substituted allylic chloroformate.

19. A single phase, solid, solvent-containing electrolyte according to claim 17 wherein said solid polymeric matrix comprises approximately 10 to 18 percent by weight of recurring units derived from said substituted allylic chloroformate.

20. An electrolytic cell which comprises:

(i) an anode comprising a compatible anodic material,

(ii) a cathode comprising a compatible cathodic material, and

(iii) interposed therebetween a single phase, solid, solvent-containing electrolyte which comprises a solid polymeric matrix, an inorganic ion salt, and a solvent,

wherein said solid polymeric matrix was obtained by polymerizing a substituted allylie chloroformate formed by the reaction of an allylie chloroformate of formula (I);

##STR13## and an aliphatic reactant selected from the group consisting of monohydroxy alcohols having 1 to 11 carbon atoms or the sodium salts thereof, dihydroxy alcohols having 2 to 50 carbon atoms or the sodium salts thereof, primary monoamines having 1 to 7 carbon atoms or the sodium salts thereof, and secondary diamines having 2 to 12 carbon atoms or the sodium salts thereof, and mixtures of two or more of the foregoing.

21. An electrolytic cell according to claim 20 wherein said inorganic ion salt is a sodium, lithium, or ammonium salt.

22. An electrolytic cell according to claim 21 wherein said inorganic ion salt is selected from the group consisting of LiPF₆, LiClO₄, NaClO₄, LiCF₃ CSO₃, Li[N(CF₃ SO₂)₂ ], and LiBF₄.

23. An electrolytic cell according to claim 20 wherein said solvent is a mixture of propylene carbonate and triglyme.

24. An electrolytic cell according to claim 20 wherein said aliphatic reactant utilized in the formation of said substituted allylic chloroformate is provided as a sodium salt during said formation reaction.

25. An electrolytic cell according to claim 20 wherein said aliphatic reactant utilized in the formation of said substituted allylic chloroformate is a monohydroxy alcohol of the formula:

##STR14## or the sodium salt thereof where R₁ is H or CH₃, and n=0 to 10.

26. An electrolytic cell according to claim 25 wherein said aliphatic reactant utilized in the formation of said substituted allylic chloroformate is a monohydroxy alcohol of the specified formula or the sodium salt thereof wherein n is 1 to 4.

27. An electrolytic cell according to claim 26 wherein said aliphatic reactant utilized in the formation of said substituted allylic chloroformate is a monohydroxy alcohol of the specified formula or the sodium salt thereof wherein R₁ is H, and n is 3.

28. An electrolytic cell according to claim 20 wherein said aliphatic reactant utilized in the formation of said substituted allylic chloroformate is a dihydroxy alcohol of the formula:

##STR15## or the sodium salt thereof where n is 2 to 10, and m is 1 to 5.

29. An electrolytic cell according to claim 28 wherein said aliphatic reactant utilized in the formation of said substituted allylic chloroformate is a dihydroxy alcohol of the specified formula or the sodium salt thereof wherein n is 2 to 6, and m is 1.

30. An electrolytic cell according to claim 28 wherein said aliphatic reactant utilized in the formation of said substituted allylic chloroformate is a dihydroxy alcohol of the specified formula or the sodium salt thereof wherein n is 6, and m is 1.

31. An electrolytic cell according to claim 20 wherein said aliphatic reactant utilized in the formation of said substituted allylic chloroformate is a primary monamine of the formula:

##STR16## or the sodium salt thereof wherein n is 0 to 6.

32. An electrolytic cell according to claim 31 wherein said aliphatic reactant utilized in the formation of said substituted allylic chloroformate is a primary diamine of the specified formula or the sodium salt thereof wherein n is 2 to 4.

33. An electrolytic cell according to claim 31 wherein said aliphatic reactant utilized in the formation of said substituted allylic chloroformate is a primary diamine of the specified formula or a sodium salt thereof wherein n is 4.

34. An electrolytic cell according to claim 20 wherein said aliphatic reactant utilized in the formation of said substituted allylic chloroformate is a secondary diamine of the formula:

##STR17## or the sodium salt thereof wherein n is 2 to 10.

35. A single phase, solid, solvent-containing electrolyte according to claim 34 wherein said aliphatic reactant used in the formation of said substituted allylic chloroformate is a secondary diamine of the specified formula or the sodium salt thereof wherein n is 6.

36. An electrolytic cell according to claim 20 wherein said solid polymeric matrix is obtained by copolymerizing said substituted allylic chloroformate with an acrylate.

37. An electrolytic cell according to claim 20 wherein said solid polymeric matrix comprises less than approximately 22 percent by weight of recurring units derived from said substituted allylic chloroformate.

38. An electrolytic cell according to claim 20 wherein said solid polymeric matrix comprises approximately 10 to 18 percent by weight of recurring units derived from said substituted allylic chloroformate.

39. The electrolytic cell according to claim 20 wherein the anode is an intercalation based anode comprising carbon.

40. The electrolytic cell according to claim 39 wherein the cathode comprises cathodic material selected from the group consisting of vanadium oxides, lithiated cobalt oxides, lithiated manganese oxides, and mixtures thereof.

41. The electrolytic cell according to claim 20 wherein the cathode comprises cathodic material selected from the group consisting of vanadium oxides, lithiated cobalt oxides, lithiated manganese oxides, and mixtures thereof.