Mixed material cathode for secondary alkaline batteries

Patent metadata

Field	Value
Publication number	US-10276860-B2
Application number	US-201715467240-A
Country	US
Kind code	B2
Filing date	Mar 23, 2017
Priority date	Oct 13, 2014
Publication date	Apr 30, 2019
Grant date	Apr 30, 2019

Abstract

A secondary alkaline battery using manganese dioxide is described. The battery includes a mixed cathode material with birnessite-phase manganese dioxide or electrolytic manganese dioxide (EMD), a bismuth compound and a copper compound selected from the group consisting of elemental copper and a copper salt. In some embodiments, a conductive carbon and/or a binder may also be included.

First claim

What is claimed is:

1. A method of producing a battery, the method comprising:
mixing manganese chloride, a bismuth salt, and an acid in a reactor to form a reaction mixture;
adding an alkaline hydroxide to the reaction mixture;
oxidizing the reaction mixture; and
forming, based on the oxidizing, a manganese oxide compound comprising a birnessite phase manganese dioxide;
producing a cathode, the cathode comprising a cathode material comprising:
the manganese oxide compound;
a bismuth compound selected from the group consisting of elemental bismuth and a bismuth salt; and
copper,

disposing the cathode into a housing;
disposing an anode into the housing;
disposing a polymeric separator between the anode and the cathode such that the anode and the cathode are separated; and
adding an electrolyte to the housing.

2. The method of claim 1 , wherein the bismuth salt comprises bismuth chloride.

3. The method of claim 1 , further comprising:
mixing a copper salt with the reaction mixture prior to oxidizing the reaction mixture.

4. The method of claim 1 , wherein the birnessite phase manganese dioxide has a layered nanostructure, and wherein the birnessite phase manganese dioxide comprises the bismuth and the copper ion exchanged within the layered nanostructure.

5. A method of producing a cathode, the method comprising steps of:
mixing multiple ingredients to form a cathode paste, the multiple ingredients comprising:
a manganese oxide compound comprising electrolytic manganese dioxide (EMD), wherein the manganese oxide compound comprises a non-birnessite-phase of manganese dioxide;
a bismuth compound selected from the group consisting of: elemental bismuth, a bismuth salt, and combinations thereof; and
a copper compound comprising elemental copper,

pressing the cathode paste onto a cathode current collector at a pressure between 6.9×106 and 1.4×108 Pascals to form a pressed assembly;
drying the pressed assembly to produce a cathode;
performing one or more conditioning cycles on the cathode, wherein each conditioning cycle of the one or more conditioning cycles comprises:
discharging the cathode to an end of the manganese dioxide compound second electron stage;
recharging at least a portion of the manganese oxide compound back to a Mn 4+ state; and
converting at least a portion of the non-birnessite phase of manganese dioxide into birnessite phase manganese dioxide as a result of the discharging and recharging.

6. The method as recited in claim 5 , wherein the multiple ingredients further comprises a conductive carbon.

7. The method as recited in claim 5 , wherein the multiple ingredients further comprises a binder.

8. The method as recited in claim 5 , further comprising:
simultaneously pressing the cathode paste onto the cathode current collector and onto a substrate of elemental copper to form the pressed assembly.

9. The method of claim 5 , wherein the elemental copper is in a powder form or a metallic support form, wherein the metallic support form comprises at least one of a mesh, a foil, an ingot, a sheet, or a wire.

10. The method of claim 5 , wherein the cathode material further comprises a conductive carbon, and wherein the cathode material consists essentially of greater than 0 wt. % and less than or equal to 30 wt. % of the conductive carbon; between 1-20 wt. % of the bismuth compound; between 1-70 wt. % of the copper compound; greater than 0 wt. % and less than or equal to 10 wt. % of a binder; and the balance being the manganese oxide compound.

11. The method of claim 5 , wherein the elemental copper is a solid copper support.

12. The method of claim 5 , wherein the cathode material further comprises a cellulose-based hydrogel binder.

13. The method of claim 5 , wherein the bismuth compound is bismuth oxide.

14. A method of producing a battery, the method comprising:
forming a birnessite-phase manganese dioxide by mixing manganese chloride with bismuth chloride and nitric acid in a chilled 1-10 M solution of alkaline hydroxide, wherein the chilled 1-10 M solution is between 0-10 C for 0.5-24 hours;
producing a cathode, the cathode comprising a cathode material comprising:
a manganese oxide compound comprising the birnessite-phase manganese dioxide;
a bismuth compound selected from the group consisting of elemental bismuth and a bismuth salt; and
copper,

disposing the cathode into a housing;
disposing an anode into the housing;
disposing a polymeric separator between the anode and the cathode such that the anode and the cathode are separated; and
adding an electrolyte to the housing.

15. The method of claim 14 , wherein the step of mixing manganese chloride further comprises mixing copper chloride.

16. The method of claim 14 , wherein the step of mixing manganese chloride with the bismuth chloride, the copper chloride and the nitric acid occurs simultaneously.

Assignees

• Univ City New York Res Found

Inventors

• Yadav Gautam G
• Gallaway Joshua
• Nyce Michael
• Banerjee Sanjoy

Classifications

• H01M10/24

  Alkaline accumulators · CPC title

• H01M4/626

  Metals · CPC title

• H01M4/50 Primary

  of manganese · CPC title

• H01M4/24

  Electrodes for alkaline accumulators · CPC title

• C01P2006/40

  Electric properties · CPC title