Substantially impervious lithium super ion conducting membranes

• US 8,652,686 B2
• Filed: 11/09/2012
• Issued: 02/18/2014
• Est. Priority Date: 12/19/2005
• Status: Active Grant

• Current Assignee: PolyPlus Battery Company
• Original Assignee: PolyPlus Battery Company
• Inventors: Visco, Steven J., De Jonghe, Lutgard C., Nimon, Yevgeniy S.
• Primary Examiner(s): Ryan, Patrick
• Assistant Examiner(s): Lewis, Ben
• Application Number:
  US13/673,789
• Publication Number:
  US 20130344397A1
• Time in Patent Office: 466 Days
• Field of Search: 429/465, 429475-479, 429/489, 429/492, 429529-532, 429/104, 429/126, 429/145, 429/300, 429/304, 429/306, 429321-323, 429/218.1, 429/231.95, 429/231.9, 429/236, 429/251, 429/249
• US Class Current: 429/231.95
• CPC Class Codes: H01B 1/122 Ionic conductors
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/056 characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
• CPC Class Codes: H01M 10/0561 the electrolyte being constituted of inorganic materials only
• CPC Class Codes: H01M 10/0566 Liquid materials
• CPC Class Codes: H01M 12/04 composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
• CPC Class Codes: H01M 12/06 with one metallic and one gaseous electrode
• CPC Class Codes: H01M 12/08 composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
• CPC Class Codes: H01M 2004/027 Negative electrodes
• CPC Class Codes: H01M 2300/0005 Acid electrolytes
• CPC Class Codes: H01M 2300/0017 Non-aqueous electrolytes
• CPC Class Codes: H01M 2300/0065 Solid electrolytes
• CPC Class Codes: H01M 2300/0068 inorganic
• CPC Class Codes: H01M 2300/0071 Oxides
• CPC Class Codes: H01M 2300/0082 Organic polymers
• CPC Class Codes: H01M 2300/0085 Immobilising or gelification of electrolyte
• CPC Class Codes: H01M 2300/0091 in the form of mixtures
• CPC Class Codes: H01M 4/04 Processes of manufacture in general
• CPC Class Codes: H01M 4/0416 involving impregnation with a solution, dispersion, paste or dry powder H01M4/0438 takes precedence
• CPC Class Codes: H01M 4/08 Processes of manufacture
• CPC Class Codes: H01M 4/13 : Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• CPC Class Codes: H01M 4/131 : Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/133 : Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/134 : Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/139 : Processes of manufacture
• CPC Class Codes: H01M 4/242 : Hydrogen storage electrodes
• CPC Class Codes: H01M 4/32 : Nickel oxide or hydroxide electrodes
• CPC Class Codes: H01M 4/38 : of elements or alloys
• CPC Class Codes: H01M 4/383 : Hydrogen absorbing alloys
• CPC Class Codes: H01M 4/385 : of the type LaNi5
• CPC Class Codes: H01M 4/387 : Tin or alloys based on tin
• CPC Class Codes: H01M 4/62 : Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• CPC Class Codes: H01M 4/86 : Inert electrodes with catalytic activity, e.g. for fuel cells
• CPC Class Codes: H01M 50/46 : Separators, membranes or diaphragms characterised by their combination with electrodes
• CPC Class Codes: H01M 6/04 : Cells with aqueous electrolyte
• CPC Class Codes: H01M 6/16 : with organic electrolyte H01M6/18 takes precedence
• CPC Class Codes: H01M 6/181 : with polymeric electrolytes
• CPC Class Codes: H01M 6/185 : with oxides, hydroxides or oxysalts as solid electrolytes
• CPC Class Codes: H01M 6/188 : Processes of manufacture
• CPC Class Codes: H01M 6/24 : Cells comprising two different electrolytes
• CPC Class Codes: H01M 6/34 : Immersion cells, e.g. sea-water cells
• CPC Class Codes: H01M 8/08 : Fuel cells with aqueous electrolytes
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02E 60/50 : Fuel cells

Abstract

A composite solid electrolyte includes a monolithic solid electrolyte base component that is a continuous matrix of an inorganic active metal ion conductor and a filler component used to eliminate through porosity in the solid electrolyte. In this way a solid electrolyte produced by any process that yields residual through porosity can be modified by the incorporation of a filler to form a substantially impervious composite solid electrolyte and eliminate through porosity in the base component. Methods of making the composites are also disclosed. The composites are generally useful in electrochemical cell structures such as battery cells and in particular protected active metal anodes, particularly lithium anodes, that are protected with a protective membrane architecture incorporating the composite solid electrolyte. The protective architecture prevents the active metal of the anode from deleterious reaction with the environment on the other (cathode) side of the architecture, which may include aqueous, air and organic liquid electrolytes and/or electrochemically active materials.

Claims

1. A composite active metal ion conducting solid electrolyte membrane, comprising:

an inorganic monolithic active metal ion conducting base component comprising a continuous inorganic solid electrolyte matrix having through pores that extend from one major surface of the base component to the opposing major surface, and a filler component contained in the through pores of the base component;

wherein the active metal ion conductivity of the composite is within the same order of magnitude as the active metal ion conductivity of the base component matrix.

2. The composite active metal ion conducting solid electrolyte membrane of claim 1, wherein the active metal ion conductivity of the composite is not less than half the active metal ion conductivity of the base component.

3. The composite active metal ion conducting solid electrolyte membrane of claim 1, wherein the density of the active metal ion conducting base component is greater than 75% and less than 95% of the theoretical density of the base component material.

4. The composite active metal ion conducting solid electrolyte membrane of claim 1, wherein the density of the active metal ion conducting base component is greater than 95% of the theoretical density of the base component material.

5. The composite active metal ion conducting solid electrolyte membrane of claim 1, wherein the filler component is a conductor of the active metal ion.

6. The composite active metal ion conducting solid electrolyte membrane of claim 5, wherein the conductive filler component is a polymer electrolyte.

7. The composite active metal ion conducting solid electrolyte membrane of claim 6, wherein the polymer electrolyte comprising a polymer and an active metal salt.

8. The composite active metal ion conducting solid electrolyte membrane of claim 7, wherein the polymer comprises polyethylene oxide (PEO).

9. The composite active metal ion conducting solid electrolyte membrane of claim 7, wherein the polymer comprises crosslinked PEO.

10. The composite active metal ion conducting solid electrolyte membrane of claim 7, wherein the polymer comprises amorphous PEO.

11. The composite active metal ion conducting solid electrolyte membrane of claim 1, wherein the active metal ion conducting filler component is an active metal ion conducting glass-ceramic.

12. The composite active metal ion conducting solid electrolyte membrane of claim 1, wherein the active metal ion conducting filler component is an active metal ion conducting glass.

13. The composite active metal ion conducting solid electrolyte membrane of claim 1, wherein the inorganic base component is a ceramic and the active metal ion conductive filler component is a glass.

14. The composite active metal ion conducting solid electrolyte membrane of claim 1, wherein the inorganic base component is a ceramic and the active metal ion conductive filler component is a glass-ceramic.

15. The composite active metal ion conducting solid electrolyte membrane of claim 14, wherein the density of the active metal ion conducting base component is greater than 95% of the theoretical density of the base component material.

16. The composite active metal ion conducting solid electrolyte membrane of claim 1, wherein the inorganic base component is a glass-ceramic and the active metal ion conductive filler component is a polymer electrolyte.

17. The composite active metal ion conducting solid electrolyte membrane of claim 1, wherein the inorganic base component is a ceramic and the active metal ion conductive filler component is a polymer electrolyte.

18. The composite active metal ion conducting solid electrolyte membrane of claim 1, wherein the active metal ion is lithium.

19. A protected anode, comprising:

an active metal anode having a first and second surface;

a protective membrane architecture on at least the first surface of the anode, the architecture having ionic conductivity of the active metal of at least 10<sup>−

6</sup> S/cm; and

wherein the protective membrane architecture comprises a substantially impervious composite solid electrolyte membrane according to claim 1.

20. A battery cell, comprising:

a protected anode in accordance with claim 19; and

a cathode structure.