Electrolyte for electrochemical cells having cathodes containing silver vanadium oxide

• US 6,017,656 A
• Filed: 10/03/1997
• Issued: 01/25/2000
• Est. Priority Date: 11/27/1996
• Status: Expired due to Term

• Current Assignee: Medtronic Incorporated (Medtronic Plc)
• Original Assignee: Medtronic Incorporated (Medtronic Plc)
• Inventors: Chen, Kevin, Crespi, Ann M.
• Primary Examiner(s): Nuzzolillo, Maria
• Assistant Examiner(s): WEINER, LAURA S
• Application Number:
  US08/943,637
• Time in Patent Office: 844 Days
• Field of Search: 429/330, 429/331, 429/332, 429/333, 429/335, 429/217, 429/219, 429/231.5, 429/231.7, 429/231.95, 429/307, 429/231.2
• US Class Current: 429/307
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0564 the electrolyte being constituted of organic materials only
• CPC Class Codes: H01M 10/0568 characterised by the solutes
• CPC Class Codes: H01M 10/0569 characterised by the solvents
• CPC Class Codes: H01M 2300/004 Three solvents
• CPC Class Codes: H01M 4/364 as mixtures
• CPC Class Codes: H01M 4/483 for non-aqueous cells H01M4/485 takes precedence
• CPC Class Codes: H01M 4/54 of silver
• CPC Class Codes: H01M 4/5825 Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: H01M 4/5835 Comprising fluorine or fluoride salts
• CPC Class Codes: H01M 50/103 prismatic or rectangular H01M50/109, H01M50/11 take precedence
• CPC Class Codes: H01M 6/10 with wound or folded electrodes
• CPC Class Codes: H01M 6/164 by the solvent
• CPC Class Codes: H01M 6/166 by the solute
• CPC Class Codes: H01M 6/5044 Cells or batteries structurally combined with cell condition indicating means
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

An electrochemical cell containing a cathode comprising silver vanadium oxide and an anode comprising lithium is disclosed that includes an improved electrolyte composition having the solvents propylene carbonate and 1,2-dimethoxyethane, and an additional third solvent that reduces the solubility of the composition of the silver vanadium cathode material. Preferably, the third solvent is a dialkyl carbonate such as dimethyl carbonate, diethyl carbonate or ethylmethyl carbonate. The improved electrolyte composition reduces the build up of resistance in the cell during cell discharge, and may affect the cell'"'"'s performance in implantable cardiac defibrillator applications. The cell of the present invention may include a hybrid cathode containing a mixture of silver vanadium oxide and carbon monofluoride (CF_x).

Claims

1. An electrochemical cell comprising:

(a) an anodc comprising lithium;

(b) a cathode comprising a silver vaniadium oxide material;

(c) an electrolyte comprising a solute and a solvent mixture of a first propylene carbonate solvent and a second 1,2-dimethoxyethane solvent, the solvent mixture further comprising a third solvent that reduces the solubility of the silver vanadium oxide material and that is miscible with the solvent mixture of propylene carbonate and 1,2-dimethoxyethane, the third solvent being different from the first and second solvents, the third solvent comprising at least one compound having a chemical formula represented by ArOC(O)OAr, ArOC(O)OAr'"'"', ArOC(O)OR, ROC(O)OR, ROC(O)OR'"'"', R-COC(O)OC-R, Ar-COC(O)OC-R, R-COC(O)OC-R'"'"', Ar-COC(O)OC-Ar, and Ar-COC(O)OC-Ar'"'"', Where R or R'"'"' are aliphatic groups or hydrogen, C is carbon, O is oxygen, Ar is an aryl group or a substituted aryl group, and Ar'"'"' is an aryl group or a substituted aryl group.

2. An electrochemical cell as in claim 1, wherein the solute is selected from the group consisting of lithium hexafluoroarsenate (LiAsF₆), lithium hexafluorophosphate (LiPF₆), lithium imide (Li(CF₃ SO₂)₂ N), lithium tris(trifluoromethane sulfonate) carbide ((Li(CF₃ SO₂)₃ C), lithium tetrafluoroborate (LiBF₄), lithium triflate (LiCF₃ SO₃), and lithium perchlorate (LiCIO₄).

3. An electrochemical cell as in claim 1, wherein the solvent mixture comprises about 20-30 percent by volume of propylene carbonate, 20-30 percent by volume of the third solvent and 40-60 percent by volume of 1,2-dimethoxyethane.

4. The electrochemical cell of claim 1, wherein the cathode comprises a mixture of the silver vanadium oxide material and carbon monofluoride.

5. An electrochemical cell, comprising:

(a) an anode comprising lithium;

(b) a cathode comprising a silver vanadium oxide material;

(c) an electrolyte comprising a solute and a solvent mixture of a first propylene carbonate solvent and a second 1,2-dimethoxyethane solvent, the solvent mixture further comprising a third solvent that reduces the solubility of the silver vanadium oxide material and that is miscible with the solvent mixture of propylene carbonate and 1,2-dimethoxyethane, the third solvent being different from the first and second solvents, the third solvent comprising at least one of dialkyl carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, dipropylcarboniate, diisopropylcarbonate, di-tert-butylcarbonate, dibutylcarbonate, diphenylcarbonate, dicyclopentylcarboate, ethylene carbonate, alkyl-substituted ethylene carbonate, and aryl-substituted ethylene carbonate.

6. An electrochemical cell as in claim 5, wherein the solute is selected from the group consisting of lithium hexafluoroarsenate (LiAsF₆), lithium hexafluorophosphate (LiPF₆), lithium imide (Li(CF₃ SO₂)₂ N), lithium tris(trifluoromethane sulfonate) carbide ((Li(CF₃ SO₂)₃ C), lithium tetrafluoroborate (LiBF₄), lithium triflate (LiCF₃ SO₃), and lithium perchlorate (LiCIO₄).

7. An electrochemical cell as in claim 5, wherein the solvent mixture comprises about 20-30 percent by volume of propylene carbonate, 20-30 percent by volume of the third solvent and 40-60 percent by volume of 1,2-dimethoxyethane.

8. The electrochemical cell of claim 5, wherein the cathode comprises a mixture of the silver vanadium oxide material and carbon moinofluoride.

9. In an electrochemical cell having a first quantity of lithium anode material and a second quantity of silver vanadium oxide cathode material, the cell producing a voltage discharge curve having a second voltage plateau at about 2.6 volts and having an electrolyte composition in contact with at least a portion of the first quantity of lithium anode material and in contact with at least a portion of the second quantity of silver vanadium oxide cathode material, the electrolyte composition including a solute and a solvent mixture of a first propylene carbonate solvent and a second 1,2-dimethoxyethane solvent, the solvent mixture further comprising a third solvent that reduces the solubility of the silver vanadium oxide material and that is miscible with the solvent mixture of propylene carbonate and 1,2-dimethoxyethane, the third solvent being different from the first and second solvents, the third solvent comprising at least one compound having a chemical formula represented by ArOC(O)OAr, ArOC(O)OAr'"'"', ArOC(O)OR, ROC(O)OR, ROC(O)OR'"'"', R-COC(O)OC-R, Ar-COC(O)OC-R, R-COC(O)OC-R'"'"', Ar-COC(O)OC-Ar, and Ar-COC(O)OC-Ar'"'"', where R or R'"'"' are aliphatic groups or hydrogen, C is carbon, O is oxygen, Ar is an aryl group or a substituted aryl group, and Ar'"'"' is an aryl group or a substituted aryl group.

10. An electrochemical cell as in claim 9, wherein the solute is selected from the group consisting of lithium hexafluoroarsenate (LiAsF₆), lithium hexafluorophosphate (LiPF₆), lithium imide (Li(CF₃ SO₂)₂ N), lithium tris(trifluoromethane sulfonate) carbide ((Li(CF₃ SO₂)₃ C), lithium tetrafluoroborate (LiBF₄), lithium triflate (LiCF₃ SO₃), and lithium perchlorate (LiCIO₄).

11. An electrochemical cell as in claim 9, wherein the solvent mixture comprises about 20-30 percent by volume of propylene carbonate, 20-30 percent by volume of the third solvent and 40-60 percent by volume of 1,2-dimethoxyethane.

12. The electrochemical cell of claim 9, wherein the cathode comprises a mixture of the silver vanadium oxide material and carbon monofluoride.

13. In an electrochemical cell having a first quantity of lithium anode material and a second quantity of silver vanadium oxide cathode material, the cell producing a voltage discharge curve having a second voltage plateau at about 2.6 volts and having an electrolyte composition in contact with at least a portion of the first quantity of lithium anode material and in contact with at least a portion of the second quantity of silver vanadium oxide cathode material, the electrolyte composition including a solute and a solvent mixture of a first propylene carbonate solvent and a second, 1,2-dimethoxyethane solvent, the solvent mixture further comprising a third solvent that reduces the solubility of the silver vanadium oxide material and that is miscible with the solvent mixture of propylene carbonate and 1,2-diethoxyethane, the third solvent being different from the first and second solvents, the third solvent comprising at least one of dialkyl carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, dipropylcarbonate, di-isopropylcarbonate, di-tert-butylcarbonate, dibutylcarbonate, diphenylcarbonate, dicyclopentylcarboate, ethylene carbonate, alkyl-substituted ethylene carbonate, and aryl-substituted ethylene carbonate.

14. An electrochemical cell as in claim 13, wherein the solute is selected from the group consisting of lithium hexafluoroarsenate (LiAsF₆), lithium hexafluorophosphate (LiPF₆), lithium imide (Li(CF₃ SO₂)₂ N), lithium tris(trifluoromethane sulfonate) carbide ((Li(CF₃ SO₂)₃ C), lithium tetrafluoroborate (LiBF₄), lithium triflate (LiCF₃ SO₃), and lithium perchlorate (LiCIO₄).

15. An electrochemical cell as in claim 13, wherein the solvent mixture comprises about 20-30 percent by volume of propylene carbonate, 20-30 percent by volume of the third solvent and 40-60 percent by volume of 1,2-dimethoxyethane.

16. The electrochemical cell of claim 13, wherein the cathode comprises a mixture of the silver vanadium oxide material and carbon monofluoride.