Alkali-ion battery with enhanced transition metal cyanometallate electrode structure

Patent metadata

Field	Value
Publication number	US-9660268-B2
Application number	US-201514928559-A
Country	US
Kind code	B2
Filing date	Oct 30, 2015
Priority date	Mar 28, 2012
Publication date	May 23, 2017
Grant date	May 23, 2017

Abstract

An alkali-ion battery is provided with a transition metal cyanometallate (TMCM) sheet cathode and a non-alkaline metal anode. The fabrication method mixes TMCM powders, conductive additives, and a polytetrafluoroethylene binder with a solution containing water, forming a wet paste. The wet paste is formed into a free-standing sheet of cathode active material, which is laminated to a cathode current collector, forming a cathode electrode. The free-standing sheet of cathode active material has a thickness typically in the range of 100 microns to 2 millimeters. The cathode electrode is assembled with a non-alkaline metal anode electrode and an ion-permeable membrane interposed between the cathode electrode and anode electrode, forming an assembly. The assembly is dried at a temperature of greater than 100 degrees C. The dried assembly is then inserted into a container (case) and electrolyte is added. Thick anodes made from free-standing sheets of active material can be similarly formed.

First claim

We claim:

1. An alkali-ion battery with a transition metal cyanometallate (TMCM) sheet cathode and non-alkaline metal anode, the battery comprising:
a cathode electrode comprising:
a cathode current collector;
a cathode active material sheet laminated to the cathode current collector formed from TMCM particles, conductive additives, and a polytetrafluoroethylene (PTFE) binder, the TMCM particles having a chemical formula A x M1 M M2 N (CN) Z .d[H 2 O] ZEO .e[H 2 O] BND ,
where A is a metal from Group 1A or Group 2 of the Periodic Table;
where M1 is a metal selected from the group consisting of 2+ and 3+ valance positions;
where M2 is a metal selected from the group consisting of 2+ and 3+ valance positions;
where [H 2 O] ZEO represents zeolitic water molecules;
where [H 2 O] BND represents bound water molecules;
where X is in a range of 0.5 to 2;
where M is in a range of 0.5 to 1.5;
where N is in a range of 0.5 to 1.5;
where Z is in a range of 5 to 6;
where d is 0;
where e is in a range of greater than 0 and less than 8;

a non-aqueous electrolyte capable of conducting A cations;
the non-alkaline metal anode electrode; and,
an ion-permeable membrane separating the non-alkaline metal anode electrode from the cathode electrode.

2. The battery of claim 1 wherein the cathode active material sheet has a thickness in a range of 100 microns to 2 millimeters (mm).

3. The battery of claim 1 wherein the non-alkaline metal anode electrode comprises an active material selected from the group consisting of hard carbon, tin (Sn), antimony (Sb), lead (Pb), NASICON-sodium titanium phosphate (NaTi 2 (PO 4 ) 3 ), SnSb alloys, and combinations thereof.

4. The battery of claim 1 wherein the cathode electrode comprises a ratio of cathode active material to non-active materials of greater than 35%.

5. The battery of claim 1 wherein the non-alkaline metal anode electrode comprises:
an anode current collector; and,
an anode active material sheet laminated to the anode current collector formed with a PTFE binder.

6. The battery of claim 5 wherein the anode active material sheet has a thickness in a range of 100 microns to 2 mm.

7. The battery of claim 1 wherein the ion-permeable membrane has a melting temperature of greater than 200 degrees C.

8. The battery of claim 7 wherein the ion-permeable membrane is a material selected from the group consisting of cellulose or nanofibrous polyimide, composites made from combinations of alumina, zirconia, or silicon, and polymers including polyethylene, polypropylene, and polyethylene terephthalate.

9. A method decreasing the size of an alkali-ion transition metal cyanometallate (TMCM) cathode battery, the method comprising:
providing a battery having a first capacity and first volumetric energy density, formed from a first plurality of cells, each cell comprising a cathode including a current collector coated with TMCM active material having a thickness of x microns, a non-alkali metal anode, an ion permeable membrane between the anode and cathode, and an electrolyte;
replacing the first plurality of cells with a single cell comprising a current collector with a laminated TMCM film having a thickness of y microns, where y is greater than x, a non-alkali metal anode, an ion permeable membrane between the anode and cathode, and an electrolyte; and;
in response to replacing the first plurality of cells with the single cell, maintaining the battery first capacity; wherein the TMCM active material comprises: TMCM particles having a chemical formula A X M1 M M2 N (CN)z.d[H 2 O] ZEO . e[H 2 O] BND ,
where A is a metal from Group 1A or Group 2 of the Periodic Table;
where M1is a metal selected from the group consisting of 2+ and 3+ valance positions;
where M2 is a metal selected from the group consisting of 2+ and 3+ valance positions;
where [H 2 O] ZEO represents zeolitic water molecules;
where [H 2 O] BND represents bound water molecules;
where x is in a range of 0.5 to 2;
where M is in a range of 0.5 to 1.5;
where N is in a range of 0.5 to 1.5;
where z is in a range of 5 to 6;
where d is 0; and,
where e is in a range of greater than 0 and less than 8.

10. The method of claim 9 wherein the single cell TMCM film includes a polytetrafluoroethylene (PTFE) binder.

11. The method of claim 9 wherein the single cell non-alkali metal anode includes a film laminated to an anode current collector, has a thickness of greater than 100 microns, and comprises a PTFE binder.

12. The method of claim 9 further comprising:
increasing the battery volumetric energy density in response to replacing the first plurality of cells with the single cell.

13. The method of claim 9 wherein the single cell TMCM active material thickness of y is greater than 100 microns and less than 2 millimeters.

14. The method of claim 9 wherein the single cell electrolyte is a non-aqueous electrolyte.

15. A method for fabricating an alkali-ion battery with a transition metal cyanometallate (TMCM) sheet cathode and a non-alkaline metal anode, the method comprising:
assembling a TMCM cathode electrode with a non-alkaline metal anode electrode and an ion-permeable membrane interposed between the cathode electrode and anode electrode, forming an assembly;
drying the assembly at a temperature of greater than 100 degrees C.;
inserting the dried assembly into a container; and,
adding a non-aqueous electrolyte to the container wherein the TMCM cathode material comprises: TMCM particles having a chemical formula A x M1 M M2 N (CN)z. d[H 2 O]z ZEO .e[H 2 O] BND ,
where A is a metal from Group 1A or Group 2 of the Periodic Table;
where M1is a metal selected from the group consisting of 2+ and 3+ valance positions;
where M2 is a metal selected from the group consisting of 2+ and 3+ valance positions;
where [H 2 O] ZEO represents zeolitic water molecules;
where [H 2 O] BND represents bound water molecules;
where x is in a range of 0.5 to 2;
where M is in a range of 0.5 to 1.5;
where N is in a range of 0.5 to 1.5;
where z is in a range of 5 to 6;
where d is 0; and,
where e is in a range of greater than 0 and less than 8.

16. The method of claim 15 wherein the non-alkaline metal anode electrode comprises an active material selected from the group consisting of hard carbon, tin (Sn), antimony (Sb), lead (Pb), NASICON-sodium titanium phosphate (NaTi 2 (PO 4 ) 3 ), SnSb alloys, and combinations thereof.

17. The method of claim 15 wherein the ion-permeable membrane has a melting temperature of greater than 200 degrees C.

18. The method of claim 17 wherein the ion-permeable membrane is a material selected from the group consisting of cellulose or nanofibrous polyimide, composites made from combinations of alumina, zirconia, or silicon, and polymers including polyethylene, polypropylene, and polyethylene terephthalate.

Assignees

• Sharp Laboratories America Inc

Inventors

• Song Jie
• Lu Yuhao
• Zhao Xin

Classifications

• H01M50/417

  Polyolefins · CPC title

• H01M50/429

  Natural polymers · CPC title

• H01M2/1646

  Electricity · mapped topic

• H01M4/1397

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

• H01M4/136

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