Battery with an in-situ activation plated lithium anode

• US 6,168,884 B1
• Filed: 04/02/1999
• Issued: 01/02/2001
• Est. Priority Date: 04/02/1999
• Status: Expired due to Term

• Current Assignee: Lockheed Martin Energy Research Corporation (Martin Marietta Corporation)
• Original Assignee: Lockheed Martin Energy Research Corporation (Martin Marietta Corporation)
• Inventors: Dudney, Nancy J., Neudecker, Bernd J., Bates, John B.
• Primary Examiner(s): Nuzzolillo, Maria
• Assistant Examiner(s): Martin, Angela J.
• Application Number:
  US09/285,326
• Time in Patent Office: 641 Days
• Field of Search: 429/127, 429/162, 429/163, 429/231.95, 429/129, 429/130, 429/104, 429/246, 429/124
• US Class Current: 429/162
• CPC Class Codes: H01M 10/0436 Small-sized flat cells or batteries for portable equipment
• 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 2004/027 Negative electrodes
• CPC Class Codes: H01M 4/0447 of complete cells or cells stacks
• CPC Class Codes: H01M 4/661 Metal or alloys, e.g. alloy coatings H01M4/669 take precedence
• 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 6/40 Printed batteries , e.g. thin film batteries
• 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

Abstract

A thin-film rechargeable battery includes a cathode film; including a lithium transition metal oxide, an electrolyte film coupled to the cathode film, the electrolyte film being substantially nonreactive with oxidizing materials and with metallic lithium, an anode current collector coupled to the electrolyte film; and an overlying layer coupled to the anode current collector. The thin-film rechargeable battery is activated during an initial charge by electrochemical plating of a metallic lithium anode between the anode current collector and the electrolyte film. The plating of the anode during charging and the stripping of the anode layer during discharging are essentially reversible. Therefore, almost no diminishment of discharge capacity occurs, even after many discharge and charge cycles. Other advantages include no need for special packaging for shipping and handling. The battery eliminates the main drawbacks of the thin-film Li-ion battery (high capacity loss during the initial charge) and of the thin-film lithium battery (high air-sensitivity at all times, temperature limited to ˜100° C., expensive preparation of the lithium anode). The battery survives processing conditions that exceed those of a solder reflow process without any signs of degradation.

Claims

1. A thin-film rechargeable battery, comprising:

a cathode film including a lithium transition metal oxide;

an electrolyte film coupled to the cathode film, the electrolyte film being substantially non-reactive with oxidizing materials and with metallic lithium;

an anode current collector, which substantially avoids formation of inter-metallic compounds with lithium, is coupled to the electrolyte film; and

an overlying layer, which is substantially non-reactive with lithium, coupled to the anode current collector, wherein the thin-film rechargeable battery is activated during a charge by electrochemical plating of a metallic lithium anode between the anode current collector and the electrolyte film.

2. The thin-film rechargeable battery of claim 1, wherein the overlying layer, the anode current collector, and the electrolyte film provide:

substantially reversible stripping of the metallic lithium anode during a first discharge of the thin-film rechargeable battery;

electrochemical plating of a plurality of subsequently plated metallic lithium anodes during corresponding charges of the thin-film rechargeable battery, the plating of each of the subsequently plated metallic lithium anodes occurring after a corresponding discharge of the thin-film rechargeable battery; and

substantially reversible stripping of the subsequently plated metallic lithium anodes during subsequent discharges of the thin-film rechargeable battery.

3. The thin-film rechargeable battery of claim 1, wherein the overlying layer, the anode current collector and the electrolyte film are configured to confine the metallic lithium anode.

4. The thin-film rechargeable battery of claim 1, further comprising:

a cathode current collector coupled to the cathode film; and

a substrate coupled to the cathode current collector.

5. The thin-film rechargeable battery of claim 1, wherein the overlying layer acts as an insulator;

provides an impervious barrier to atomic lithium transport; and

is responsive to the electrochemical plating of a metallic lithium anode so as to maintain a substantially flat surface.

6. The thin-film rechargeable battery of claim 1, wherein the overlayer includes at least one material selected from the group consisting of lithium phosphorus oxynitride, aluminium nitride, BeO, MgO, CaO, SrO, BaO, BN, AlN, SiO₂, Si₃N₄, Si₂N₂O, Sc₂O₃, Y₂O₃, La₂O₃, ThO₂, Li₂Be₂O₃, Li₄BeO₃, Li₅AlO₄, Li₄SiO₄ Li₈SiO₆, LiScO₂, LiYO₂, Li₈ZrO₆, LiCeO₂, LiF, LiCI, LiBr, LiI, Be, Zr, Ta, W, polytetrafluoroethylene, polyethylene, and parylene.

7. The thin-film rechargeable battery of claim 1, wherein:

the electrolyte film comprises lithium phosphorus oxynitride having a thickness of from approximately 1 to approximately 2 microns; and

the overlying layer comprises lithium phosphorus oxynitride having a thickness of from approximately 0.1 to approximately 3.0 microns.

8. The thin-film rechargeable battery of claim 1, having less than five percent discharge capacity loss after:

heating at approximately 250°

C. for approximately ten minutes prior to the initial charge; and

at least fifty charge and discharge cycles in a voltage range of from approximately 4.5 to approximately 2.5 volts.

9. The thin-film rechargeable battery of claim 1, wherein:

the cathode film has a thickness in a range from approximately 0.01 to approximately 5.0 microns; and

the lithium transition metal oxide comprises lithium and oxygen, and at least one element selected from the groups consisting of columns IB-VIII B of the periodic table.

10. The thin-film rechargeable battery of claim 1, further comprising a protective coating coupled to the overlying layer, the protective coating being substantially impervious to moisture and substantially nonreactive with the overlying layer.

11. The thin-film rechargeable battery of claim 1, wherein:

the anode current collector has a thickness of from approximately 0.05 to approximately 2 microns; and

the anode current collector includes at least one member selected from the group consisting of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, lanthanum, hafnium, molybdenum, tantalum, tungsten, and titanium nitride.

12. The thin-film rechargeable battery of claim 2, wherein the overlying layer accommodates volume changes during the reversible stripping and the electrochemical plating.

13. The thin-film rechargeable battery of claim 4, wherein the cathode current collector:

includes a noble metal; and

has a thickness in the range of from approximately 0.02 to approximately 1 micron.