High energy/power density nickel oxide/hydroxide materials and nickel cobalt oxide/hydroxide materials and production thereof

Patent metadata

Field	Value
Publication number	US-10547046-B2
Application number	US-201615043226-A
Country	US
Kind code	B2
Filing date	Feb 12, 2016
Priority date	Nov 30, 2011
Publication date	Jan 28, 2020
Grant date	Jan 28, 2020

Abstract

According to one embodiment, a method includes forming a nickel oxide/hydroxide active film onto a substrate from a solution including a nickelous salt and an electrolyte, where the nickel oxide/hydroxide active film has a physical characteristic of maintaining greater than about 80% charge over greater than 500 charge/discharge cycles, and wherein the nickel oxide/hydroxide active film has a physical characteristic of storing electrons at greater than about 0.5 electron per nickel atom.

First claim

What is claimed is:

1. A method, comprising:
forming a nickel oxide/hydroxide active film via anodic electrodeposition onto a substrate from a solution including a nickelous salt and an electrolyte;
wherein the substrate comprises ordered, pyrolytic graphite;
wherein the electrolyte comprises at least one constituent selected from the group consisting of: an acetate, a nitrate, a sulfate; a hydroxide, and a fluoride;
wherein the nickelous salt and the electrolyte are each present in a concentration from about 0.45 molar to about 1.2 molar;
wherein the nickel oxide/hydroxide active film has a physical characteristic of exhibiting an increase in capacitance relative to an initial capacitance of the nickel oxide/hydroxide active film, over greater than 500 charge/discharge cycles; and
wherein the nickel oxide/hydroxide active film has a physical characteristic of storing electrons at about 1.33 electrons per nickel atom.

2. The method of claim 1 , wherein the nickelous salt comprises NiCl 2 .

3. The method of claim 1 , wherein the electrolyte is NaNO 3 .

4. The method of claim 1 , wherein the nickelous salt is present in an amount of about 1.2M;
wherein the nickelous salt comprises NiAc;
wherein the electrolyte is present in an amount of about 1.2M; and
wherein the electrolyte is selected from the group consisting of: LiAc, KAc, NaAc, KF, NaF, LiOH; and combinations thereof.

5. The method of claim 1 , wherein the electrolyte is selected from a group consisting of: LiAc, KAc NaF, and KF.

6. The method of claim 1 , wherein the electrolyte comprises one or more species selected from the group consisting of: LiAc, KAc, NaAc, KF, NaF, and LiOH.

7. A method, comprising:
forming a nickel oxide/hydroxide active film via anodic electrodeposition onto a substrate from an acidic solution including a nickelous salt and an electrolyte;
wherein the substrate comprises ordered, pyrolytic graphite;
wherein the electrolyte comprises at least one constituent selected from the group consisting of: an acetate, a nitrate, a sulfate; a hydroxide, and a fluoride;
wherein the nickel oxide/hydroxide active film has a physical characteristic of exhibiting an increase in capacitance relative to an initial capacitance of the nickel oxide/hydroxide active film, over greater than 500 charge/discharge cycles; and
wherein the nickel oxide/hydroxide active film has a physical characteristic of storing electrons at greater than about 1.0 electrons per nickel atom.

8. The method of claim 1 , wherein the nickel oxide/hydroxide active film formed on the substrate has a thickness in a range from about 20 to about 200 nm.

9. The method of claim 8 , wherein the thickness of the nickel oxide/hydroxide active film varies less than about ±1 nm along all codeposited portions thereof.

10. The method of claim 1 , wherein the nickel oxide/hydroxide active film includes cobalt.

11. The method of claim 10 , wherein the nickel oxide/hydroxide active film comprises a cobalt (Co) to nickel (Ni) ratio of about 2:1 to about 1:2.

12. The method of claim 1 , wherein the nickelous salt comprises NiAc.

13. The method of claim 1 , wherein each of the charge/discharge cycles is characterized by a charge rate of about 10 C and a depth of discharge of about 100%.

14. The method of claim 1 , comprising either charging or discharging the nickel oxide/hydroxide active film in a second solution of KOH, wherein the KOH is present in an amount from 3 M to about 6 M.

15. The method as recited in claim 7 , wherein
the nickelous salt comprises 0.45 M Ni(NO 3 ) 2 ; and
wherein the electrolyte comprises 0.3 M Ni(Ac) 2 .

16. The method of claim 7 , wherein the nickelous salt comprises a nickelous component and a pH-neutral anionic component;
wherein the electrolyte comprises at least one pH-neutral component;
wherein the nickelous component comprises NiAc; and
wherein the electrolyte comprises one or more species selected from the group consisting of: LiAc, KAc, NaAc, KF, NaF, and LiOH.

17. The method of claim 7 , wherein each of the charge/discharge cycles is characterized by a charge rate of about 10 C and a depth of discharge of about 100%.

18. The method of claim 1 , wherein the substrate is porous.

19. The method of claim 1 , further comprising charging and discharging the nickel oxide/hydroxide active film, wherein the charging and discharging is characterized by a charge/discharge rate in a range from about 100 C to about 1000 C.

20. The method of claim 13 , comprising either charging or discharging the nickel oxide/hydroxide active film in a second solution of KOH, wherein the KOH is present in an amount from 3 M to about 6 M;
wherein the nickelous salt comprises Ni present in an amount of about 1.2M; and
wherein the electrolyte comprises at least one material selected from a group consisting of: LiAc, KAc; NaAc, NaF, LiOH, and KF;
wherein the electrolyte is present in an amount of about 1.2M;
wherein the substrate is porous;
wherein some or all pores of the substrate are characterized by a pore size of 0.1 μm;
wherein the pores of the substrate are characterized by a substantially uniform distance therebetween; and
wherein the nickel oxide/hydroxide active film:
comprises cobalt;
exhibits a cobalt (Co) to nickel (Ni) ratio of about 2:1 to about 1:2;
has a thickness in a range from about 20 to about 200 nm, wherein the thickness of the nickel oxide/hydroxide active film varies less than about ±1 nm along all codeposited portions thereof; and
has physical characteristics of:
a charge/discharge rate of greater than about 100 C; and
about 97% charge efficiency.

Assignees

• L Livermore Nat Security Llc

Inventors

• Merrill Matthew
• Stadermann Michael

Classifications

• H01M10/30

  Nickel accumulators (H01M10/34 takes precedence) · CPC title

• H01M2220/30

  Batteries in portable systems, e.g. mobile phone, laptop · CPC title

• Y10S977/755

  Nanosheet or quantum barrier/well, i.e. layer structure having one dimension or thickness of 100 nm or less · CPC title

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• H01M4/38

  of elements or alloys · CPC title