Solvated electron lithium electrode for high energy density battery

• US 4,668,593 A
• Filed: 08/29/1986
• Issued: 05/26/1987
• Est. Priority Date: 08/29/1986
• Status: Expired due to Fees

• Current Assignee: Eltron Research & Development, LLC
• Original Assignee: Eltron Research & Development, LLC
• Inventors: Sammells, Anthony F.
• Primary Examiner(s): Skapars, Anthony
• Application Number:
  US06/902,304
• Time in Patent Office: 270 Days
• Field of Search: 429/191, 429/193, 429/194, 429/196, 429/197, 429/199, 429/201, 429/218, 429/101
• US Class Current: 429/323
• CPC Class Codes: H01M 10/36 Accumulators not provided for in groups H01M10/05-H01M10/34
• CPC Class Codes: H01M 6/18 with solid electrolyte
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A solvated electron lithium electrode comprising a solution of lithium dissolved in liquid ammonia is provided for use in rechargeable high energy density lithium-based cells utilizing a lithium ion conducting solid electrolyte to separate the liquid solvated negative electrode from liquid positive electroactive material or electrolyte. The rechargeable lithium-based cell according to the present invention reduces coulombic efficiency losses associated with surface morphological changes at a solid lithium electrode, and is suitable for electrical vehicle propulsion and load leveling applications.

Claims

1. A rechargeable high energy density lithium-based cell comprising:

a solvated electron lithium negative electrode comprising a solution of lithium dissolved in liquid ammonia;

a lithium ion conducting solid electrolyte contacting said negative electrode;

a liquid non-aqueous lithium ion conducting electrolyte comprising a lithium ion conducting supporting electrolyte dissolved in a non-aqueous solvent, said liquid electrolyte contacting said lithium ion conducting solid electrolyte; and

a solid lithium intercalation positive electrode contacting said liquid electrolyte.

2. A rechargeable high energy density lithium-based cell according to claim 1 wherein the concentration of said lithium in said liquid ammonia is about 0.l M to about 7.75M.

3. A rechargeable high energy density lithium-based cell according to claim 1 wherein said lithium in said liquid ammonia is about 1.0 M to about 3.5 M.

4. A rechargeable high energy density lithium-based cell according to claim 1 additionally comprising a current collector at said negative electrode.

5. A rechargeable high energy density lithium-based cell according to claim 1 wherein said lithium ion conducting solid electrolyte is selected from the group consisting of:

LiI-Li₂ S-SiS₂ ;

LiI-Li₂ S-P₂ S₅ ;

LiI-Li₂ S-B₂ S₃ ;

Li₂ O-SiO₂ -P₂ O₅ ;

LiI-Li₂ S-As₂ S₃ ;

LiBr-Li₂ S-SiS₂ ;

LiX-Li₂ O-B₂ O₃ where X=Cl or Br^- ;

Li₂ O-B₂ O₃ ;

LiAlSiO₄ ;

Li₇ BiO₄ ;

Li₈ SnO₆ ;

Li₈ HfO₆ ;

Li₈ CeO₆ ;

Li₈ ZrO₆ ;

Li₇ NbO₆ ;

Li₇ TaO₆ ;

Li₆ In₂ O₆ ;

LiI;

LiCl;

LiF; and

Li₄ SiO₄ (containing 9 and 50 m/o Li₃ PO₄); and

lithium ion conducting beta- and beta"-aluminas.

6. A rechargeable high energy density lithium-based cell according to claim 1 wherein said lithium ion conducting solid electrolyte comprises 0.3 m/o LiI-0.42 m/o Li₂ S-0.28 m/o SiS₂.

7. A rechargeable high energy density lithium-based cell according to claim 1 wherein said lithium ion conducting supporting electrolyte is selected from the group consisting of:

LiCF₃ SO₃ ;

LiAsF₆ ;

LiClO₄ ;

LiAlCl₄ ;

LiGaCl₄ ;

LiBF₄ ; and

LiCl; and

said non-aqueous solvent is selected from the group consisting of;

tetrahydrofuran and its derivatives;

propylene carbonate;

acetonitrile;

1,3-dioxalane;

N-methyl-2-pyrrolidone;

sulpholane;

methylformate;

dimethylsulfate;

γ

-butyrolactone; and

1,2 dimethoxyethane.

8. A rechargeable high energy density lithium-based cell according to claim 1 wherein said lithium intercalation positive electrode is selected from the group consisting of:

TiS₂ ;

ZrS₂ ;

ZrSe₂ ;

VSe₂ ;

V₂ S₅ ;

Fe₀.25 V₀.75 S₂ ;

Cr₀.75 V₀.25 S₂ ;

Cr₀.5 V₀.5 S₂ ;

NbS₃ ;

NiPS₃ ;

FeOCl;

UO₂ F₂ ;

NbSe3;

MoS₃ ;

CuS;

Cr₃ O₈ ;

V₆ O₁₃ (stoichiometric);

V₆ O₁₃ (non-stoichiometric);

TaS₂ ;

MoS₂ ;

MoSe₂ ;

WS₂ ; and

WSe₂.

9. A rechargeable high energy density lithium-based cell according to claim 8 wherein said lithium ion conducting supporting electrolyte is selected from the group consisting of:

LiCF₃ SO₃ ;

LiAsF₆ ;

LiClO₄ ;

LiAlCl₄ ;

LiGaCl₄ ;

LiBF₄ ; and

LiCl; and

said non-aqueous solvent is selected from the group consisting of;

tetrahydrofuran and its derivatives;

propylene carbonate;

acetonitrile;

1,3-dioxalane;

N-methyl-2-pyrrolidone;

sulpholane;

methylformate;

dimethylsulfate;

γ

-butyrolactone; and

1,2 dimethoxyethane.

10. A rechargeable high energy density lithium-based cell according to claim 9 wherein said lithium ion conducting solid electrolyte is selected from the group consisting of:

LiI-Li₂ S-SiS₂ ;

LiI-Li₂ S-P₂ S₅ ;

LiI-Li₂ S-B₂ S₃ ;

Li₂ O-SiO₂ -P₂ O₅ ;

LiI-Li₂ S-As₂ S₃ ;

LiBr-Li₂ S-SiS₂ ;

LiX-Li₂ O-B₂ O₃ where X=Cl or Br^- ;

Li₂ O-B₂ O₃ ;

LiAlSiO₄ ;

Li₇ BiO₄ ;

Li₈ SnO₆ ;

Li₈ HfO₆ ;

Li₈ CeO₆ ;

Li₈ ZrO₆ ;

Li₇ NbO₆ ;

Li₇ TaO₆ ;

Li₆ In₂ O₆ ;

LiI, LiCl, LiF, and Li₄ SiO₄ (containing 9 and 50 m/o Li₃ PO₄); and

lithium ion conducting beta- and beta"-aluminas.

11. A rechargeable high energy density lithium-based cell according to claim 10 wherein said solution of lithium dissolved in liquid ammonia is provided in a sealed negative electrode compartment.

12. A rechargeable high energy density lithium-based cell according to claim 1 wherein said solution of lithium dissolved in liquid ammonia is provided in a sealed negative electrode compartment.

13. A rechargeable high energy density lithium-based cell comprising:

a solvated electron lithium negative electrode comprising a solution of lithium dissolved in liquid ammonia;

lithium ion conducting solid electrolyte contacting said negative electrode;

liquid non-aqueous lithium ion conducting positive electroactive material comprising a lithium ion conducting supporting electrolyte dissolved in a non-aqueous solvent and a liquid depolarizing agent contacting said lithium ion conducting solid electrolyte.

14. A rechargeable high energy density lithium-based cell according to claim 13 additionally comprising a current collector contacting said positive electroactive material.

15. A rechargeable high energy density lithium-based cell according to claim 13 wherein said lithium ion conducting solid electrolyte is selected from the group consisting of:

LiI-Li₂ S-SiS₂ ;

LiI-Li₂ S-P₂ S₅ ;

LiI-Li₂ S-B₂ S₃ ;

Li₂ O-SiO₂ -P₂ O₅ ;

LiI-Li₂ S-As₂ S₃ ;

LiBr-Li₂ S-SiS₂ ;

LiX-Li₂ O-B₂ O₃ where X=Cl or Br^-;

Li₂ O-B₂ O₃ ;

LiAlSiO₄ ;

Li₇ BiO₄ ;

Li₈ SnO₆ ;

Li₈ HfO₆ ;

Li₈ CeO₆ ;

Li₈ ZrO₆ ;

Li₇ NbO₆ ;

Li₇ TaO₆ ;

Li₆ In₂ O₆ ;

LiI, LiCl, LiF, and Li₄ SiO₄ (containing 9 and 50 m/o Li₃ PO₄); and

lithium ion conducting beta- and beta"-aluminas.

16. A rechargeable high energy density lithium-based cell according to claim 13 wherein said lithium ion conducting solid electrolyte comprises 0.3 m/o LiI-0.42 m/o Li₂ S-0.28 m/o SiS₂.

17. A rechargeable high energy density lithium-based cell according to claim 13 wherein said lithium ion conducting supporting electrolyte is selected from the group consisting of:

LiCF₃ SO₃ ;

LiAsF₆ ;

LiClO₄ ;

LiAlCl₄ ;

LiGaCl₄ ;

LiBF₄ ; and

LiCl; and

said non-aqueous solvent is selected from the group consisting of;

tetrahydrofuran and its derivatives;

propylene carbonate;

acetonitrile;

1,3-dioxalane;

N-methyl-2-pyrrolidone;

sulpholane;

methylformate;

dimethylsulfate;

γ

-butyrolactone; and

1,2 dimethoxyethane; and

said liquid depolarizing agent is selected from the group consisting of;

SO₂ ;

SO₂ Cl₂ ; and

SOCl₂.

18. A rechargeable high energy density lithium-based cell according to claim 13 wherein said lithium intercalation positive electrode is selected from the group consisting of:

TiS₂ ;

ZrS₂ ;

ZrSe₂ ;

VSe₂ ;

V₂ S₅ ;

Fe₀.25 V₀.75 S₂ ;

Cr₀.75 V₀.25 S₂ ;

Cr₀.5 V₀.5 S₂ ;

NbS₃ ;

NiPS₃ ;

FeOCl;

UO₂ F₂ ;

NbSe₃ ;

MoS₃ ;

CuS;

Cr₃ O₈ ;

V₆ O₁₃ (stoichiometric);

V₆ O₁₃ (non-stoichiometric);

TaS₂ ;

MoS₂ ;

MoSe₂ ;

WS₂ ; and

WSe₂.

20. A rechargeable high energy density lithium-based cell according to claim 13 wherein said lithium in said liquid ammonia is about 1.0 M to about 3.5 M.

21. A rechargeable high energy density lithium-based cell according to claim 13 wherein said positive electroactive material additionally comprises a dissolved transition metal halide.

22. A rechargeable high energy density lithium-based cell according to claim 21 wherein said dissolved transition metal halide comprises CuCl₂.

23. A rechargeable high energy density lithium-based cell according to claim 22 additionally comprising a current collector at said negative electrode.

24. A rechargeable high energy density lithium-based cell according to claim 23 wherein said lithium ion conducting solid electrolyte is selected from the group consisting of:

LiI-Li₂ S-SiS₂ ;

LiI-Li₂ S-P₂ S₅ ;

LiI-Li₂ S-B₂ S₃ ;

Li₂ O-SiO₂ -P₂ O₅ ;

LiI-Li₂ S-As₂ S₃ ;

LiBr-Li₂ S-SiS₂ ;

LiX-Li₂ O-B₂ O₃ where X=Cl or Br^-;

Li₂ O-B₂ O₃ ;

LiAlSiO₄ ;

Li₇ BiO₄ ;

Li₈ SnO₆ ;

Li₈ HfO₆ ;

Li₈ CeO₆ ;

Li₈ ZrO₆ ;

Li₇ NbO₆ ;

Li₇ TaO₆ ;

Li₆ In₂ O₆ ;

LiI, LiCl, LiF, and Li₄ SiO₄ (containing 9 and 50 m/o Li₃ PO₄ ; and

lithium ion conductinb beta- and beta"-aluminas.

25. A rechargeable high energy density lithium-based cell according to claim 24 wherein said lithium ion conducting solid electrolyte comprises 0.3 m/o LiI-0.42 m/o Li₂ S-0.28 m/o SiS₂.

26. A rechargeable high energy density lithium-based cell according to claim 25 wherein said lithium ion conducting supporting electrolyte is selected from the group consisting of:

LiCF₃ SO₃ ;

LiAsF₆ ;

LiClO₄ ;

LiAlCl₄ ;

LiGaCl₄ ;

LiBF₄ ; and

LiCl; and

said non-aqueous solvent is selected from the group consisting of;

tetrahydrofuran and its derivatives;

propylene carbonate;

acetonitrile;

1,3-dioxalane;

N-methyl-2-pyrrolidone;

sulpholane;

methylformate;

dimethylsulfate;

γ

-butyrolactone; and

1,2 dimethoxyethane; and

said liquid depolarizing agent is selected from the froup consisting of;

SO₂ ;

SO₂ Cl₂ ; and

SOCl₂.

27. A rechargeable high energy density lithium-based cell according to claim 26 wherein said lithium intercalation positive electrode is selected from the group consisting of:

TiS₂ ;

ZrS₂ ;

ZrSe₂ ;

VSe₂ ;

V₂ S₅ ;

Fe₀.25 V₀.75 S₂ ;

Cr₀.75 V₀.25 S₂ ;

Cr₀.5 V₀.5 S₂ ;

NbS₃ ;

NiPS₃ ;

FeOCl;

U0₂ F₂ ;

NbSe₃ ;

MoS₃ ;

CuS;

Cr₃ O₈ ;

V₆ O₁₃ (stoichiometric);

V₆ O₁₃ (non-stoichiometric);

TaS₂ ;

MoS₂ ;

MoSe₂ ;

WS₂ ; and

WSe₂.

28. A rechargeable high energy density lithium-based cell according to claim 27 wherein the concentration of said lithium in said liquid ammonia is about 0.1 M to about 7.75 M.

29. A rechargeable high energy density lithium-based cell according to claim 28 wherein said solution of lithium dissolved in liquid ammonia is provided in a sealed negative electrode compartment.

30. A rechargeable high energy density lithium-based cell according to claim 13 wherein said solution of lithium dissolved in liquid ammonia is provided in a sealed negative electrode compartment.

19. A rechargeable high energy density lithium-based cell according to claim3 1 wherein the concentration of said lithium in said liquid ammonia is about 0.1 M to about 7.75 M.