IONICALLY CONDUCTIVE MEMBRANES FOR PROTECTION OF ACTIVE METAL ANODES AND BATTERY CELLS

• US 20090297935A1
• Filed: 05/29/2009
• Published: 12/03/2009
• Est. Priority Date: 10/15/2002
• Status: Active Grant

• Current Assignee: PolyPlus Battery Company
• Original Assignee: PolyPlus Battery Company
• Inventors: Visco, Steven J., Katz, Bruce D., Nimon, Yevgeniy S.
• Granted Patent: US 7,838,144 B2
• Time in Patent Office: Days
• US Class Current: 429/144
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 10/056 characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
• CPC Class Codes: H01M 10/0562 Solid materials
• CPC Class Codes: H01M 10/0565 Polymeric materials, e.g. gel-type or solid-type
• CPC Class Codes: H01M 2300/0065 Solid electrolytes
• CPC Class Codes: H01M 2300/0071 Oxides
• CPC Class Codes: H01M 2300/008 Halides
• CPC Class Codes: H01M 2300/0094 in the form of layered products, e.g. coatings
• CPC Class Codes: H01M 50/46 Separators, membranes or diaphragms characterised by their combination with electrodes
• CPC Class Codes: H01M 50/497 Ionic conductivity
• CPC Class Codes: H01M 6/18 with solid electrolyte
• CPC Class Codes: H01M 6/181 with polymeric electrolytes
• CPC Class Codes: H01M 6/182 with halogenide as solid electrolyte
• CPC Class Codes: H01M 6/185 with oxides, hydroxides or oxysalts as solid electrolytes
• CPC Class Codes: H01M 6/187 Solid electrolyte characterised by the form
• CPC Class Codes: H01M 6/188 Processes of manufacture
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y10T 29/49108 Electric battery cell making
• CPC Class Codes: Y10T 29/49115 including coating or impregnating

Abstract

Disclosed are ionically conductive membranes for protection of active metal anodes and methods for their fabrication. The membranes may be incorporated in active metal negative electrode (anode) structures and battery cells. In accordance with the invention, the membrane has the desired properties of high overall ionic conductivity and chemical stability towards the anode, the cathode and ambient conditions encountered in battery manufacturing. The membrane is capable of protecting an active metal anode from deleterious reaction with other battery components or ambient conditions while providing a high level of ionic conductivity to facilitate manufacture and/or enhance performance of a battery cell in which the membrane is incorporated.

Claims

1. A protective composite battery separator, consisting essentially of:

an ionically conductive first material layer precursor selected from the group consisting of red phosphorus, a metal phosphide, a metal nitride, silicon nitride, a metal halide, and LiPON coated with a wetting layer; and

a second material layer in contact with the first layer, the second material selected from the group consisting of ceramic metal ion conductors and glass ceramic active metal ion conductors;

wherein the ionic conductivity of the composite separator is at least 10<sup>−

4</sup> S/cm.

44. The separator of claim 1, wherein the ionic conductivity of the second material layer is about 10⁻

3 S/cm.

45. The separator of claim 1, wherein the thickness of the first material layer is about 0.1 to 5 microns.

46. The separator of claim 1, wherein the thickness of the second material layer is about 0.1 to 1000 microns.

47. The separator of claim 1, wherein the ionic conductivity of the second material layer is between 10⁻

4 and 10<sup>−

3</sup> S/cm and the thickness of the second material layer is about 10 to 500 microns.

48. The separator of claim 47, wherein the thickness of the second material layer is 10 to 100 microns

49. The separator of claim 1, wherein the first layer comprises LiPON coated with a wetting layer.

50. The separator of claim 1, wherein the second layer comprises a material selected from the group consisting of glass-ceramic active metal ion conductors, lithium beta-alumina, LISICON, sodium beta-alumina and NASICON.

51. The separator of claim 1, wherein the second layer is an ion conductive glass-ceramic having the following composition:

Composition mol % P₂O₅ 26-55% SiO₂ 0-15% GeO₂ + TiO₂ 25-50% in which GeO₂ 0-50% TiO₂ 0-50% ZrO₂ 0-10% M₂O₃ 0 <

10% Al₂O₃ 0-15% Ga₂O₃ 0-15% Li₂O 3-25%

and containing a predominant crystalline phase composed of Li_1+x(M, Al, Ga)_x(Ge<sub>1−

y</sub>Ti_y)<sub>2−

x</sub>(PO₄)₃ where X≦

0.8 and 0≦

Y≦

1.0, and where M is an element selected from the group consisting of Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb and/or and Li_1+x+yQ_xTi<sub>2−

x</sub>Si_yP<sub>3−

y</sub>O₁₂ where 0<

X≦

0.4 and 0<

Y≦

0.6, and where Q is Al or Ga.

52. An electrochemical device component, comprising:

an active metal negative electrode having a first surface and a second surface; and

a protective composite separator as claimed in claim 1 on the first surface of the electrode and having a smooth gap-free interface therewith.

53. The component of claim 52, wherein the active metal of the electrode is an alkali metal.

54. The component of claim 52, wherein the active metal of the electrode is lithium or a lithium alloy.

55. The component of claim 52, wherein the second layer is an ion conductive glass-ceramic having the following composition:

Composition mol % P₂O₅ 26-55% SiO₂ 0-15% GeO₂ + TiO₂ 25-50% in which GeO₂ 0-50% TiO₂ 0-50% ZrO₂ 0-10% M₂O₃ 0 <

10% Al₂O₃ 0-15% Ga₂O₃ 0-15% Li₂O 3-25%

and containing a predominant crystalline phase composed of Li_1+x(M, Al, Ga)_x(Ge<sub>1−

y</sub>Ti_y)<sub>2−

x</sub>(PO₄)₃ where X≦

0.8 and 0≦

Y≦

1.0, and where M is an element selected from the group consisting of Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb and/or and Li_1+x+yQ_xTi<sub>2−

x</sub>Si_yP<sub>3−

y</sub>O₁₂ where 0<

X≦

0.4 and 0<

Y≦

0.6, and where Q is Al or Ga.

56. The component of claim 55, further comprising a positive electrode chosen from a sulfur-based positive electrode, a metal oxide based positive electrode, and a metal sulfide based positive electrode in contact with said second layer material.

2-43. -43. (canceled)

57. A method of fabricating an electrochemical device component, the method comprising:

providing a substrate of a second layer material selected from the group consisting of substantially impervious ceramic metal ion conductors and glass ceramic active metal ion conductors;

forming on the substrate a layer of a first material layer precursor selected from the group consisting of red phosphorus, a metal phosphide, a metal nitride, silicon nitride, a metal halide, and LiPON coated with a wetting layer; and

applying an active metal negative electrode to the layer of the first material precursor on the substrate, thereby reacting the precursor with active metal of the negative electrode to form the first layer material;

wherein an anode protected by a composite of the first and second layers having ionic conductivity of at least 10<sup>−

4</sup> S/cm and having a smooth gap-free interface therewith results.

58. The method of claim 57, wherein the active metal of the electrode is an alkali metal.

59. The method of claim 57, wherein the active metal of the electrode is lithium or a lithium alloy.

60. The method of claim 57, wherein the second layer comprises a material selected from the group consisting of glass-ceramic active metal ion conductors, lithium beta-alumina, LISICON, sodium beta-alumina and NASICON.

61. The method of claim 59, wherein the second layer is an ion conductive glass-ceramic having the following composition:

Composition mol % P₂O₅ 26-55% SiO₂ 0-15% GeO₂ + TiO₂ 25-50% in which GeO₂ 0-50% TiO₂ 0-50% ZrO₂ 0-10% M₂O₃ 0 <

10% Al₂O₃ 0-15% Ga₂O₃ 0-15% Li₂O 3-25%

and containing a predominant crystalline phase composed of Li_1+x(M, Al, Ga)_x(Ge<sub>1−

y</sub>Ti_y)<sub>2−

x</sub>(PO₄)₃ where X≦

0.8 and 0≦

Y≦

1.0, and where M is an element selected from the group consisting of Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb and/or and Li_1+x+yQ_xTi<sub>2−

x</sub>Si_yP<sub>3−

y</sub>O₁₂ where 0<

X≦

0.4 and 0<

Y≦

0.6, and where Q is Al or Ga.

62. The method of claim 57, further comprising applying a positive electrode selected from the group consisting of a sulfur-based positive electrode, a metal oxide based positive electrode, and a metal sulfide based positive electrode in contact with said second material layer.