Transition metal cyanometallate cathode battery with metal plating anode

Patent metadata

Field	Value
Publication number	US-9531002-B2
Application number	US-201514668788-A
Country	US
Kind code	B2
Filing date	Mar 25, 2015
Priority date	Mar 28, 2012
Publication date	Dec 27, 2016
Grant date	Dec 27, 2016

Abstract

A method is provided for cycling power in a transition metal cyanometallate (TMCM) cathode battery. The method provides a battery with a TMCM cathode, an anode, and an electrolyte, where TMCM corresponds to the chemical formula of A X M1 N M2 M (CN) Y -d(H 2 O), where “A” is an alkali or alkaline earth metal, and where M1 and M2 are transition metals. The method charges the battery using a first charging current, or greater. In response to the charging current, a plating of “A” metal is formed overlying a plating surface of the anode. In response to discharging the battery, the “A” metal plating is removed from the anode plating surface. In one aspect, in an initial charging of the battery, a permanent solid electrolyte interphase (SEI) layer is formed overlying the anode plating surface. In subsequent charging and discharging cycles, the permanent SEI layer is maintained overlying the anode plating surface.

First claim

We claim:

1. A transition metal cyanometallate (TMCM) cathode battery with a metal plating anode, the battery comprising:
a TMCM cathode comprising A X M1 N M2 M N(CN) Y .d(H 2 O),
where “A” is selected from a group of alkali or alkaline earth metals;
where M1 and M2 are transition metals;
where X is in a range of 0 to 4;
where N is in a range of 0 to 2;
where M is in a range of 0 to 2;
where Y is in a range of 1 to 6;
where d is in a range of 0 to 14;

a non-aqueous electrolyte; and,
an anode comprising a plating surface, configured such that no “A” metal overlying the plating surface when the battery is in the discharged state.

2. The battery of claim 1 wherein the anode plating surface includes an overlying layer of “A” metal plating, when the battery is in the charged state.

3. The battery of claim 2 wherein the “A” ions fail to intercalate into the plating surface of the anode when the battery is in the charged state.

4. The battery of claim 2 further comprising:
subsequent to an initial charge, a permanent solid electrolyte interphase (SEI) layer, existing in both the battery charged and battery discharged states, overlying the anode plating surface.

5. The battery of claim 4 wherein the permanent SEI layer is formed over an anode plating surface having an architecture selected from the group consisting of pillars and pores.

6. The battery of claim 5 wherein the pore size is in a range of 0.1 nanometers (nm) to 100 microns.

7. The battery of claim 5 where the pillar diameter is in a range of 0.1 nm to 100 microns, with a distance between pillars in a range of 0.1 nm to 100 microns.

8. The battery of claim 1 wherein the anode plating surface is a material selected from the group consisting of metals, carbonaceous materials, semiconductors, and conductive polymers.

9. The battery of claim 8 wherein the anode further comprises a current collector made from a first electrically conductive material; and,
wherein the anode plating surface is a substrate overlying the current collector, made from a second electrically conductive material.

10. The battery of claim 1 wherein the anode further comprises an ion-permeable barrier with an SEI-free surface, permeable to “A”-ions, coating the anode plating surface.

11. The battery of claim 10 wherein the ion-permeable barrier is selected from the group consisting of beta-alumina, phosphate, thiophosphate, and combinations thereof.

12. The battery of claim 1 further comprising:
an “A”-ion permeable membrane in the electrolyte separating the anode from the cathode; and,
wherein the electrolyte is a liquid electrolyte.

13. The method for cycling power in a transition metal cyanometallate (TMCM) cathode battery, the method comprising:
providing a battery with a TMCM cathode, an anode, and a non-aqueous electrolyte, where TMCM corresponds to the chemical formula of A X M1 N M2 M (CN) Y .d(H 2 O):
where “A” is selected from a group of alkali or alkaline earth metals;
where M1 and M2 are transition metals;
where X is in a range of 0 to 4;
where N is in a range of 0 to 2;
where M is in a range of 0 to 2;
where Y is in a range of 1 to 6;
where d is in a range of 0 to 14;

charging the battery using a charging current;
in response to the charging current, forming a plating of “A” metal overlying a plating surface of the anode;
discharging the battery; and,
in response to discharging the battery, removing the “A” metal plating from the anode plating surface.

14. The method of claim 13 wherein charging the battery includes charging the battery with a charging current greater than a first current level.

15. The method of claim 14 further comprising:
subsequent to discharging the battery, charging the battery with a charging current less than the first current level; and,
“A”-ions intercalating into the anode plating surface.

16. The method of claim 13 further comprising:
in an initial charging of the battery, forming a permanent solid electrolyte interphase (SEI) layer overlying the anode plating surface; and,
in subsequent charging and discharging cycles, maintaining the permanent SEI layer overlying the anode plating surface.

17. The method of claim 16 wherein charging the battery includes the permanent SEI layer passing “A”-ions to the anode plating surface.

18. The method of claim 13 wherein providing the anode includes the anode plating surface being a material selected from the group consisting of metals, carbonaceous materials, semiconductors, and conductive polymers.

19. The method of claim 13 wherein providing the anode includes providing an anode with an ion-permeable barrier, permeable to “A”-ions, coating the anode plating surface; and,
wherein charging the battery includes failing to form an SEI layer overlying the anode plating surface when the battery is being charged.

20. The method of claim 19 wherein the ion-permeable barrier is selected from the group consisting of beta-alumina, phosphate, thiophosphate, and combinations thereof.

21. A transition metal cyanometallate (TMCM) cathode battery with a metal plating anode, the battery comprising:
a TMACM cathode comprising A X M1 N M2 M (CN) Y .d(H 2 O),
where “A” is selected from a group of alkali or alkaline earth metals;
where M1 and M2 are transition metals;
where X is in a range of 0 to 4;
where N is in a range of 0 to 2;
where M is in a range of 0 to 2;
where Y is in a range of 1 to 6;
where d is in a range of 0 to 14;

a non-aqueous electrolyte; and,
an anode comprising a plating surface, configured such that no “A” metal overlying the plating surface when the battery is in the discharged state, and with an overlaying layer of “A” metal plating when the battery is in the charged state, and wherein the “A” ions fail to intercalate into the plating surface of the anode when the battery is in the charged state.

Assignees

• Sharp Laboratories America Inc

Inventors

• Lu Yuhao
• Wang Long
• Lee Jong-Jan

Classifications

• H01M4/661

  Metal or alloys, e.g. alloy coatings (H01M4/669 take precedence) · CPC title

• H01M4/1397

  of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy · CPC title

• H01M4/667

  in the form of layers, e.g. coatings · CPC title

• H01M4/663

  containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres · CPC title

• H01M4/0452

  from solutions · CPC title