LITHIUM BATTERY AND METHOD OF PREPARING PROTECTED ANODE

• US 20170346099A1
• Filed: 12/23/2016
• Published: 11/30/2017
• Est. Priority Date: 05/27/2016
• Status: Abandoned Application

• Current Assignee: Samsung Electronics Co. Ltd., Samsung SDI Company Limited
• Original Assignee: Samsung Electronics Co. Ltd., Samsung SDI Company Limited
• Inventors: Choi, Hongsoo, Kim, Yongsu, Lee, Yonggun, Chang, Wonseok
• Application Number:
  US15/389,620
• Publication Number:
  US 20170346099A1
• Time in Patent Office: Days
• 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 2004/027 Negative electrodes
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/366 as layered products
• CPC Class Codes: H01M 4/382 Lithium H01M4/405 takes precedence
• CPC Class Codes: H01M 4/628 Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02T 10/70 Energy storage systems for electromobility, e.g. batteries

Abstract

A lithium battery includes: an anode including a lithium metal or a lithium alloy; an ion-conductive amorphous metal nitride layer disposed on a surface of the anode; a liquid electrolyte; and a cathode.

Claims

1. A lithium battery comprising:

an anode comprising a lithium metal or lithium alloy;

an ion-conductive amorphous metal nitride layer disposed on a surface of the anode;

a liquid electrolyte; and

a cathode.

2. The lithium battery of claim 1, wherein the ion-conductive amorphous metal nitride layer contacts the anode.

3. The lithium battery of claim 1, wherein the ion-conductive amorphous metal nitride layer covers an entire surface of the anode.

4. The lithium battery of claim 1, wherein the ion-conductive amorphous metal nitride layer has a thickness of about 1 nanometer to about 15 micrometers.

5. The lithium battery of claim 1, wherein the ion-conductive amorphous metal nitride layer comprises a metal nitride represented by Formula 1:

Li^xN 

 

Formula 1

wherein 0.01≦

x≦

3.

6. The lithium battery of claim 1, wherein the anode further comprises a compound represented by Formula 2 on at least a portion of the surface thereof:

Li_2-aCO_3-b 

 

Formula 2

wherein 0≦

a<

1 and 0≦

b<

1.

7. The lithium battery of claim 6, wherein an amount of the compound represented by Formula 2 is in a range of about 0.1 mole percent to about 5 mole percent, based on 100 mole percent of a total content of the surface of the lithium metal or the lithium alloy.

8. The lithium battery of claim 1, wherein the liquid electrolyte comprises a non-aqueous organic solvent and a lithium salt.

9. The lithium battery of claim 8, wherein the non-aqueous organic solvent comprises at least one organic solvent selected from a carbonate, an ester, an ether, a ketone, an amine, and a phosphine

10. The lithium battery of claim 8, wherein the non-aqueous organic solvent comprises at least one selected from a carbonate and an ester.

11. The lithium battery of claim 8, wherein the lithium salt comprises a lithium salt represented by Formula 3 below:

LiX₁ 

 

Formula 3

wherein X₁ comprises at least one anion selected from BF₄⁻

, PF₆⁻

, AsF₆⁻

, SbF₆⁻

, AlCl₄⁻

, HSO₄⁻

, CH₃SO₃⁻

, (CF₃SO₂)₂N⁻

, Cl⁻

, Br⁻

, I⁻

, SO₄⁻

, PF₆⁻

, ClO₄⁻

, F₃SO₃⁻

, CF₃CO₂⁻

, C₂F₅SO₂)₂N⁻

, (C₂F₅SO²)(CF₃SO₂)N⁻

, CF₃SO₂)₂N⁻

, NO₃⁻

, Al₂Cl₇⁻

, ASF₆⁻

, SbF₆⁻

, CH₃COO⁻

, (CF₃SO₂)₃C⁻

, (CF₃)₂PF₄⁻

, (CF₃)₃PF₃⁻

, (CF₃)₄PF₂⁻

, (CF₃)₅PF⁻

, (CF₃)₆P⁻

, SF₅CF₂SO₃⁻

, SF₅CHFCF₂SO₃⁻

, CF₃CF₂(CF₃)₂CO⁻

, (CF₃SO₂)₂CH⁻

, (SF₅)₃C⁻

, and (O(CF₃)₂C₂(CF₃)₂O)₂PO⁻

.

12. The lithium battery of claim 1, wherein a charge transfer resistance between the anode and the liquid electrolyte is at least about 10 percent less than a charge transfer resistance between the anode comprising the lithium metal or the lithium alloy and the liquid electrolyte when in a lithium battery not comprising the ion-conductive amorphous metal nitride layer, wherein the charge transfer resistance is determined by impedance measurement at 25°

C. and in a Nyquist plot.

13. The lithium battery of claim 1, wherein a bulk resistance between the anode and the cathode is at least about 10 percent less than a bulk resistance between the anode comprising the lithium metal or the lithium alloy and the cathode when in a lithium battery not comprising the ion-conductive amorphous metal nitride layer, wherein the charge transfer resistance is determined by impedance measurement at 25°

C. and in a Nyquist plot.

14. The lithium battery of claim 1, wherein the cathode comprises a cathode active material comprising a compound which intercalates and deintercalates lithium, inorganic sulfur, or a sulfur compound.

15. The lithium battery of claim 1, further comprising a separator disposed between the anode and the cathode.

16. The lithium battery of claim 1, wherein an operating voltage of the lithium battery is about 4 volts or greater.

17. A method of preparing a protected anode, the method comprising:

introducing an inert gas and an oxocarbon gas into a container in which an anode comprising a lithium metal or a lithium alloy is disposed to provide a compound represented by Formula 2 on at least a portion of a surface of the anode; and

exposing the anode, which comprises the lithium metal or the lithium alloy and the compound represented by Formula 2 on the at least a portion of the surface thereof, to a nitrogen gas to prepare the protected anode, wherein the protected anode comprises an ion-conductive amorphous metal nitride layer on a surface thereof;

Li_2-aCO_3-b 

 

Formula 2

wherein 0≦

a<

1 and 0≦

b<

1.

18. The method of claim 17, wherein the exposing is at a temperature of about 10°

C. to about 20°

C. for about 1 minute to about 120 minutes.

19. The method of claim 17, wherein the ion-conductive amorphous metal nitride layer comprises a metal nitride represented by Formula 1 below:

Li_xN 

 

Formula 1

wherein 0.01≦

x≦

3.

20. The method of claim 17, wherein the ion-conductive amorphous metal nitride layer has a thickness of about 1 nanometer to about 15 micrometers.

21. A protected anode comprising:

an anode comprising a lithium metal or a lithium alloy; and

an ion-conductive amorphous metal nitride layer disposed on a surface of the anode.

22. The protected anode of claim 21, wherein the ion-conductive amorphous metal nitride layer covers an entire surface of the anode.

23. The protected anode of claim 21, wherein the ion-conductive amorphous metal nitride layer has a thickness of about 1 nanometer to about 15 micrometers.

24. The protected anode of claim 21, wherein the ion-conductive amorphous metal nitride layer comprises a metal nitride represented by Formula 1:

Li_xN 

 

Formula 1

wherein 0.01≦

x≦

3.

25. The protected anode of claim 21, wherein the lithium metal or the lithium alloy comprises a compound represented by Formula 2 on at least a portion of a surface thereof:

Li_2-aCO_3-b 

 

Formula 2

wherein 0≦

a<

1 and 0≦

b<

1.