Solid, glyme-containing electrolytes including ion salt derivatives and electrolytic cells produced therefrom

• US 5,411,820 A
• Filed: 06/08/1993
• Issued: 05/02/1995
• Est. Priority Date: 06/08/1993
• Status: Expired due to Term

• 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): Maples, John S.
• Application Number:
  US08/073,910
• Time in Patent Office: 693 Days
• Field of Search: 429/192, 429/197
• US Class Current: 429/307
• 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 6/166 by the solute
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

This invention is directed to solid electrolytes containing a solvent and, in particular, a solvent comprising a mixture of an organic carbonate and an ion salt derivative (e.g., lithium) which functions as a source of ions for producing conductivity. The invention is also directed to electrolytic cells prepared from such solid electrolytes.

Claims

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

a solid polymeric matrix; and

a solvent comprising about a 10;

1 to 1;

4 (w/w) mixture of an organic carbonate and a glyme, and an ionically conducting amount of an ion salt derivative selected from the group consisting of;

(a) an alkylene glycol(ether) derivative represented by Formula I;

space="preserve" listing-type="equation">RO(R.sub.1 O).sub.p.sup.M I

or represented by Formula II;

space="preserve" listing-type="equation">MO(R.sub.1 O).sub.p M II

where R is selected from the group consisting of alkyl of from 1 to 6 carbon atoms, phenyl, alkphenyl of from 7 to 12 carbon atoms, and phenyl substituted with 1 to 3 substituents selected from the group consisting of alkyl of from 1 to 4 carbon atoms, alkoxy of from 1 to 4 carbon atoms, chloro and bromo;

R₁ is (CR₃ R₄)_q where R₃ and R₄ are independently selected from the group consisting of hydrogen and alkyl of from 1 to 4 carbon atoms, q is an integer from 1 to 6, and wherein when q is greater than 1, the R₃ and on each carbon atom may be the same or different;

M is a metal ion selected from the group consisting of Li, Na, K and Mg; and

p is an integer of from 2 to 6; and

(b) an ion sulfonate salt represented by Formula III;

space="preserve" listing-type="equation">RO(R.sub.1 O).sub.p (CH.sub.2).sub.1 SO.sub.3 M III

or represented by Formula IV;

space="preserve" listing-type="equation">MSO.sub.3 (CH.sub.2).sub.s O(R.sub.1 O).sub.p (CH.sub.2).sub.r SO.sub.3 M IV

where M, R and R₁ are as defined above and r and s are independently integers from 1 to 6; and

(c) mixtures thereof.

2. The solid, single-phase, solvent-containing electrolyte of claim 1, wherein the organic carbonate is a cyclic aliphatic carbonate represented by the formula:

##STR4## where R₈, R₉, R₁₀, R₁₁, R₁₂, and R₁₃ are independently selected from the group consisting of hydrogen and alkyl of 1 or 2 carbon atoms, and m is an integer equal to 0 or 1.

3. The solid, single-phase, solvent-containing electrolyte of claim 1, wherein the organic carbonate is a linear aliphatic carbonate represented by the formula:

space="preserve" listing-type="equation">R.sub.14 [OC(O)].sub.n OR.sub.15 or R.sub.14 [OC(O)R.sub.16 ].sub.t OC(O)R.sub.15

where each R₁₄ and R₁₅ are independently selected from the group consisting of alkyl of from 1 to 4 carbon atoms;

R₁₆ is an alkylene group of from 2 to 4 carbon atoms;

n is an integer of from 1 to 2, and t is an integer from 1 to 4.

4. The solid, single-phase, solvent-containing electrolyte of claim 1, wherein the glyme is triglyme, and wherein the weight ratio of organic carbonate to triglyme is about 4:

1.

5. The solid, single-phase, solvent-containing electrolyte of claim 1, wherein said ion salt derivative is an alkylene glycol(ether) derivative represented by Formula I and wherein M is lithium and p is 3.

6. The solid, single-phase, solvent-containing electrolyte of claim 1, wherein said ion salt derivative is an alkylene glycol(ether) derivative represented by Formula II and wherein each M is lithium and p is 3.

7. The solid, single-phase, solvent-containing electrolyte of claim 1, wherein said ion salt derivative is an ion sulfonate salt represented by Formula III and wherein M is lithium, p is 3 and r and s are independently 3 or 4.

8. The solid, single-phase, solvent-containing electrolyte of claim 1, wherein said ion salt derivative is an ion sulfonate salt represented by Formula IV and wherein each M is lithium, p is 3 and r and s are independently 3 or 4.

9. The solid, single phase, solvent-containing electrolyte of claim 1, wherein said ion salt derivative is Li(OCH₂ CH₂)₃ OCH₃.

10. The solid, single phase, solvent-containing electrolyte of claim 1, wherein said ion salt derivative is Li(OCH₂ CH₂)₃ OLi.

11. The solid, single phase, solvent-containing electrolyte of claim 1, wherein said ion salt derivative is CH₃ (OCH₂ CH₂)₃ O(CH₂)₃ SO₃ Li.

12. The solid, single phase, solvent-containing electrolyte of claim 1, wherein said ion salt derivative is CH₃ (OCH₂ CH₂)₃ O(CH₂)₄ SO₃ Li.

13. The solid, single phase, solvent-containing electrolyte of claim 1, wherein said ion salt derivative is LiO₃ S(CH₂)₃ (OCH₂ CH₂)₃ O(CH₂)₃ SO₃ Li.

14. The solid, single phase, solvent-containing electrolyte of claim 1, wherein said ion salt derivative is LiO₃ S(CH₂)₄ (OCH₂ CH₂)₃ O(CH₂)₄ SO₃ Li.

15. The solid, single phase, solvent-containing electrolyte of claim 1, further including an inorganic ion salt.

16. An electrolytic cell which comprises:

an anode containing a compatible anodic material;

cathode containing a compatible cathodic material; and

interposed therebetween a solid, solvent-containing electrolyte which comprises;

a solid polymeric matrix; and

a solvent comprising about a 10;

1 to 1;

4 mixture of an organic carbonate and a glyme, and an ion conducting amount of an ion salt derivative selected from the group consisting of;

(a) an alkylene glycol(ether) derivative represented by Formula I;

space="preserve" listing-type="equation">RO(R.sub.1 O).sub.p.sup.M I

or represented by Formula II;

space="preserve" listing-type="equation">MO(R.sub.1 O).sub.p M II

where R is selected from the group consisting of alkyl of from 1 to 6 carbon atoms, phenyl, alkphenyl of from 7 to 12 carbon atoms, and phenyl substituted with 1 to 3 substituents selected from the group consisting of alkyl of from 1 to 4 carbon atoms, alkoxy of from 1 to 4 carbon atoms, chloro and bromo;

R₁ is (CR₃ R₄)_q where R₃ and R₄ are independently selected from the group consisting of hydrogen and alkyl of from 1 to 4 carbon atoms, q being an integer from 1 to 6 and wherein when q is greater than 1, the R₃ and R₄ on each carbon atom may be the same or different;

M is a metal ion selected from the group consisting of Li, Na, K and Mg; and

p is an integer of from 2 to 6; and

(b) an ion sulfonate salt represented by Formula III;

space="preserve" listing-type="equation">RO(R.sub.1 O).sub.p (CH.sub.2).sub.1 SO.sub.3 M III

or represented by Formula IV;

space="preserve" listing-type="equation">MSO.sub.3 (CH.sub.2).sub.s O(R.sub.1 O).sub.p (CH.sub.2).sub.r SO.sub.3 M IV

where M, R and R₁ are as defined above and r and s are independently integers from 1 to 6; and

(c) mixtures thereof.

17. The electrolytic cell of claim 16, wherein the organic carbonate is a cyclic aliphatic carbonate represented by the formula:

##STR5## where R₈, R₉, R₁₀, R₁₁, R₁₂, and R₁₃ are independently selected from the group consisting of hydrogen and alkyl of from 1 to 2 carbon atoms, and m is an integer equal to 0 or 1.

18. The electrolytic cell of claim 16, wherein the organic carbonate is a linear aliphatic carbonate represented by the formula:

space="preserve" listing-type="equation">R.sub.14 [OC(O)].sub.n OR.sub.15 and R.sub.14 [OC(O)R.sub.16 ].sub.t OC(O)R.sub.15

where each R₁₄ and R₁₅ are independently selected from the group consisting of alkyl of from 1 to 4 carbon atoms;

R₁₆ is an alkylene group of from 2 to 4 carbon atoms;

n is an integer of from 1 to 2, and t is an integer from 1 to 4.

19. The electrolytic cell of claim 16, wherein the glyme is triglyme, and wherein the molar ratio of organic carbonate to triglyme is about 4:

1.

20. The electrolytic cell of claim 16, wherein said ion salt derivative is an alkylene glycol(ether) derivative represented by Formula I and wherein M is lithium and p is 3.

21. The electrolytic cell of claim 16, wherein said ion salt derivative is an alkylene glycol(ether) derivative represented by Formula II and wherein each M is lithium and p is 3.

22. The electrolytic cell of claim 16, wherein said lithium salt derivative is a lithium sulfonate salt represented by Formula III and wherein M is lithium, p is 3 and r and s are independently 3 or 4.

23. The electrolytic cell of claim 16, wherein said ion salt derivative is an ion sulfonate salt represented by Formula IV and wherein M is lithium, p is 3 and r and s are independently 3 or 4.

24. The electrolytic cell of claim 16, wherein said ion salt derivative is Li(OCH₂ CH₂)₃ OCH₃.

25. The electrolytic cell of claim 16, wherein said ion salt derivative is Li(OCH₂ CH₂)₃ OLi.

26. The electrolytic cell of claim 16, wherein said ion salt derivative is CH₃ (OCH₂ CH₂)₃ O(CH₂)₃ SO₃ Li.

27. The electrolytic cell of claim 16, wherein said ion salt derivative is CH₃ (OCH₂ CH₂)₃ O(CH₂)₄ SO₃ Li.

28. The electrolytic cell of claim 16, wherein said ion salt derivative is LiO₃ S(CH₂)₃ (OCH₂ CH₂)₃ O(CH₂)₃ SO₃ Li.

29. The electrolytic cell of claim 16, wherein said ion salt derivative is LiO₃ S(CH₂)₄ (OCH₂ CH₂)₃ O(CH₂)₄ SO₃ Li.

37. The electrolytic cell of claim 16, wherein the anode is an intercalation based anode comprising carbon.

30. A method for enhancing the cumulative capacity of an electrolytic cell which comprises an anode containing a compatible anodic material, a cathode containing a compatible cathodic material, and interposed therebetween a solid, solvent-containing electrolyte containing a solid polymeric matrix and a solvent comprising about a 10:

1 to 1;

4 (w/w) mixture of an organic carbonate and a glyme, which method comprises including in said electrolyte an ion salt derivative comprising;

(a) an alkylene glycol(ether) derivative represented by Formula I;

space="preserve" listing-type="equation">RO(R.sub.1 O).sub.p M I

or represented by Formula II;

space="preserve" listing-type="equation">MO(R.sub.1 O).sub.p M II

where R is selected from the group consisting of alkyl of from 1 to 6 carbon atoms, phenyl, alkphenyl of from 7 to 12 carbon atoms, and phenyl substituted with 1 to 3 substituents selected from the group consisting of alkyl of from 1 to 4 carbon atoms, alkoxy of from 1 to 4 carbon atoms, chloro and bromo;

R₁ is (CR₃ R₄)_q where R₃ and R₄ are independently selected from the group consisting of hydrogen and alkyl of from 1 to 4 carbon atoms, q being an integer from 1 to 6 and wherein when q is greater than 1, the R₃ and R₄ on each carbon atom may be the same or different;

M is a metal ion selected from the group consisting of Li, Na, K and Mg; and

p is an integer of from 2 to 6;

or

(b) an ion sulfonate salt represented by Formula III;

space="preserve" listing-type="equation">RO(R.sub.1 O).sub.p (CH.sub.2).sub.r SO.sub.3 M III

or represented by Formula IV;

space="preserve" listing-type="equation">MSO.sub.3 (CH.sub.2).sub.s O(R.sub.1 O).sub.p (CH.sub.2).sub.r SO.sub.3 M IV

where M, R₁ and R₂ are as defined above and r and s are independently integers from 1 to 6;

or

(c) mixtures thereof.

31. The method of claim 30, wherein said ion salt derivative is Li(OCH₂ CH₂)₃ OCH₃.

32. The method of claim 30, wherein said ion salt derivative is Li(OCH₂ CH₂)₃ OLi.

33. The method of claim 30, wherein said ion salt derivative is CH₃ (OCH₂ CH₂)₃ O(CH₂)₃ SO₃ Li.

34. The method of claim 30, wherein said ion salt derivative is CH₃ (OCH₂ CH₂)₃ O(CH₂)₄ SO₃ Li.

35. The method of claim 30, wherein said ion salt derivative is LiO₃ S(CH₂)₃ (OCH₂ CH₂)₃ O(CH₂)₃ SO₃ Li.

36. The method of claim 30, wherein said ion salt derivative is LiO₃ S(CH₂)₄ (OCH₂ CH₂)₃ O(CH₂)₄ SO₃ Li.