Electrochemical cells

• US 3,998,657 A
• Filed: 07/25/1975
• Issued: 12/21/1976
• Est. Priority Date: 07/25/1975
• Status: Expired due to Term

• Current Assignee: Yardney Technical Products, Inc. (Vectra Corp.)
• Original Assignee: GTE Laboratories Incorporated (Lumen Technologies, Inc.)
• Inventors: Auborn, James J., Bezman, Richard D.
• Primary Examiner(s): Skapars, Anthony
• Application Number:
  US05/599,273
• Time in Patent Office: 515 Days
• Field of Search: 136/6 LN, 136/20, 136/83 R, 136/100 R, 136/137, 136/155, 136/121, 136/122
• US Class Current: 429/345
• CPC Class Codes: H01M 10/36 Accumulators not provided for in groups H01M10/05-H01M10/34
• CPC Class Codes: H01M 4/58 of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Electrochemical cells having an oxidizable anode material, such as lithium, a cathode material, such as carbon or (C₄ F)_n, upon the surface of which the solvent material is electrochemically reduced during operation of the cell, and an electrolytic solution comprising an inorganic solvent and a solute dissolved therein. The electrolytic solution further contains an additive such as sulfur monochloride (S₂ Cl₂), which is capable of dissolving any sulfur generated during operation of the cell and which is unreactive with the other components of the cell.

Claims

1. An electrochemical cell comprising an oxidizable active anode material;

a cathode material; and

an electrolytic solution between and in contact with said anode and said cathode, said electrolytic solution comprising an inorganic solvent material and a solute dissolved therein;

said solvent material being electrochemically reduced upon the surface of said cathode material during discharge of said cell whereby elemental sulfur is formed as one of the reaction products;

said electrolytic solution further including an additive in sufficient amount to dissolve all of said elemental sulfur which is formed during operation of said cell.

2. The electrochemical cell of claim 1 wherein said active anode material is lithium.

3. The electrochemical cell of claim 1 wherein said cathode material comprises carbon black or graphite.

4. The electrochemical cell of claim 1 wherein said cathode material comprises (C₄ F)_n, wherein n refers to the presence of a large, but indefinite, number of recurring (C₄ F) groups in said cathode material.

5. The electrochemical cell of claim 1 wherein said active cathode material is a mixture of (C₄ F)_n and (CF)_n to give a material represented by the general formula (C_x F)_n, where x is greater than 1 and less than 4, and n refers to the presence of a large, but indefinite, number of recurring (C_x F) groups in said cathode material.

6. The electrochemical cell of claim 1 wherein said electrolytic solution includes a solvent material selected from the group consisting of thionyl chloride, thionyl bromide, sulfuryl chloride, mixtures thereof, and mixtures thereof with phosphorus oxychloride.

7. The electrochemical cell of claim 1 wherein said solvent material includes thionyl chloride.

8. The electrochemical cell of claim 1 wherein said solute provides at least one anion having the formula X^-, MX₄ ^-, M'"'"'X₆ ^-, or M"Cl₆ ⁼, where M is an element selected from the group consisting of aluminum and boron;

M'"'"' is an element selected from the group consisting of phosphorus, arsenic and antimony;

M" is an element selected from the group consisting of tin, zirconium and titanium; and

X is a halogen;

said solute further providing at least one cation selected from the group consisting of alkali metals, the alkaline earth metals, the lanthanides, SOCl⁺, and SO₂ Cl⁺.

9. The electrochemical cell of claim 1 wherein said solute includes at least one compound selected from the group consisting of lithium tetrachloroaluminate, lithium tetrachloroborate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium hexafluoroantimonate, lithium hexachloroantimonate, lithium hexachlorostannate, lithium hexachlorozirconate, lithium hexachlorotitanate and lithium chlorosulfate.

10. The electrochemical cell of claim 1 wherein said active anode material, said cathode material, and at least one separator are bonded together to form a spiral electrode assembly.

11. An electrochemical cell comprising a lithium anode;

a carbon cathode;

an electrolytic solution between and in contact with said anode and said cathode, said electrolytic solution including a solvent material selected from the group consisting of thionyl chloride, sulfuryl chloride, mixtures thereof, and mixtures thereof with phosphorus oxychloride, and a solute dissolved therein;

said solvent material being electrochemically reduced upon the surface of said cathode during discharge of said cell whereby elemental sulfur is formed as one of the reaction products of said discharge;

said electrolytic solution further including an additive in sufficient amount to dissolve all of said elemental sulfur which is formed during operation of said cell.

12. The electrochemical cell of claim 11 wherein said active anode material, said cathode material, and at least one separator are bonded together to form a spiral electrode assembly.

13. The electrochemical cell of claim 13 wherein said carbon cathode material is present in said electrolytic solution which is in paste form, said cell further including an inert cathode current collector.

14. An electrochemical cell comprising a lithium anode;

a (C₄ F)_n cathode, wherein n refers to the presence of a large, but indefinite, number of recurring (C₄ F) groups in said cathode material; and

an electrolytic solution between and in contact with said anode and said cathode, said electrolytic solution including a solvent material selected from the group consisting of thionyl chloride, sulfuryl chloride, mixtures thereof and mixtures thereof with phosphorus oxychloride, and a solute dissolved therein;

said solvent material being electrochemically reduced upon the surface of said cathode during discharge of said cell whereby elemental sulfur is formed as one of the reaction products of said discharge;

said electrolytic solution further including an additive in sufficient amount to dissolve all of said elemental sulfur which is formed during operation of said cell.

15. The electrochemical cell of claim 14 wherein said active anode material, said cathode material, and at least one separator are bonded together to form a spiral electrode assembly.

16. An electrochemical cell comprising an oxidizable active anode material;

a cathode material; and

an electrolytic solution between and in contact with said anode material and said cathode material, said electrolytic solution comprising an inorganic solvent material and a solute dissolved therein;

said solvent material being electrochemically reduced upon the surface of said cathode material during discharge of said cell whereby elemental sulfur is formed as one of the reaction products;

said electrolytic solution further including sulfur monochloride in sufficient amount to dissolve all of said elemental sulfur formed during operation of said cell.

17. The electrochemical cell of claim 16 wherein said inorganic solvent material includes a solvent material selected from the group consisting of thionyl chloride, thionyl bromide, sulfuryl chloride, mixtures thereof, and mixtures thereof with phosphorus oxychloride.

18. The electrochemical cell of claim 16 wherein said anode material is lithium, said cathode material is carbon, and said solvent includes thionyl chloride, sulfuryl chloride, mixtures thereof, and mixtures thereof with phosphorus oxychloride.

19. The electrochemical cell of claim 18 wherein said solvent includes thionyl chloride.

20. The electrochemical cell of claim 16 wherein said anode material is lithium, said cathode material is (C₄ F)_n where n refers to the presence of a large, but indefinite, number of recurring (C₄ F) groups in said cathode material, and said solvent includes thionyl chloride, sulfuryl chloride, mixtures thereof, and mixtures thereof with phosphorus oxychloride.

21. The electrochemical cell of claim 20 wherein said solvent includes thionyl chloride.

22. The electrochemical cell of claim 16 wherein said anode material is lithium.

23. The electrochemical cell of claim 16 wherein said cathode material comprises carbon black or graphite.

24. The electrochemical cell of claim 16 wherein said cathode material includes (C₄ F)_n where n refers to the presence of a large, but indefinite, number of recurring (C₄ F) groups in said cathode material.