Production of nanoporous films

Patent metadata

Field	Value
Publication number	US-2020208287-A1
Application number	US-201716334558-A
Country	US
Kind code	A1
Filing date	Sep 19, 2017
Priority date	Sep 19, 2016
Publication date	Jul 2, 2020
Grant date	—

Abstract

A process is provided comprising submerging a substrate in an electrochemical deposit bath having at least a metal salt and saccharin. In embodiments, the film is further treated with anodization, and in other cases chemical vapor deposition. Films are also provided formed by the disclosed processes. The films are nanoporous on at least a portion of a surface of the films. Also disclosed are electronic devices having the films disclosed, including lithium-ion batteries, storage devices, supercapacitors, electrodes, semiconductors, fuel cells, and/or combinations thereof.

First claim

We claim:

1 . A process comprising at least partially submerging a substrate into an electrochemical deposition bath wherein a composition of the electrochemical deposition bath comprises at least a metal salt and saccharin.

2 . A process of claim 1 for forming an electrochemical deposit on the substrate, wherein the metal salt is a salt of Ni, Co, Fe, or a combination thereof.

3 . The process of claim 2 , wherein the concentration of Ni, Co, Fe, or a combination thereof are each between 0-300 g/L; provided the concentration of at least one of the metal salts is present in a concentration of at least 0.001 g/L.

4 . The process of claim 2 wherein the composition of the electrochemical deposition bath further comprises is one of
(a) Ni 2+ in a range of 0-350 g L −1 ,
Borate in a range of 0-45 g L −1 ,
Saccharin in a range of 0-2 g L −1 ; wherein the electrochemical bath has a temperature in a range of 15-45° C.; and

(b) Co 2+ in a range of 0-250 g L −1 ,
Borate in a range of 0-45 g L −1 ,
a citrate salt in a range of 0-30 g L −1 ,
Saccharin in a range of 0-2 g L −1 ; wherein the electrochemical bath has a temperature in the range of 15-45° C.; and

(c) Ni 2+ in a range of 0-230 g L −1 ,
Fe 2+ in a range of 0-40 g L −1 ,
Borate in a range of 0-50 g L −1 ,
the citrate salt in a range of 0-30 g L −1 ,
Saccharin in a range of 0-5 g L −1 ; wherein the electrochemical bath has a temperature in a range of 15-65° C.; and

(d) Ni 2+ in a range of 0-220 g L −1 ,
Co 2+ in a range of 0-155 g L −1 ,
Borate in a range of 0-40 g L −1 ,
Cl − in a range of 0-13 g L −1 , wherein the electrochemical bath has a temperature in a range of 10-60° C.; and

(e) The electrodeposition bath in a range of:
Fe 2+ in a range of 0-100 g L −1 ,
Co 2+ in a range of 0-200 g L −1 ,
H 3 BO 3 in a range of 0-60 g L −1 ,
NaCl in a range of 0.001-50 g L −1 ,
Saccharin in a range of 0.001-5 g L −1 ; wherein the electrochemical bath has a temperature in a range of 10-50° C.; and

(f) Ni 2+ in a range of 0-100 g L −1 ,
Fe 2+ in a range of 0-100 g L −1 ,
Co 2+ in a range of 0-200 g L −1 ,
Borate in a range of 0-60 g L −1 ,
Cl − in a range of 0-50 g L −1 ,
Saccharin in a range of 0-5 g L −1 ; wherein the electrochemical bath has a temperature in a range of 10-55° C.; and
wherein in either of the electrochemical bath compositions, at least one metal salt is present in a concentration of at least 0.001 g/L.

5 . A process according to claim 1 , wherein the substrate comprises copper foil, nickel foil, stainless steel, indium tin oxide glass, indium tin oxide coated polyethylene or other conductive substrates.

6 . A process according to claim 1 , which further comprises conducting an electrochemical deposition process on the substrate, wherein a current is applied having a current density is 0.001-1000 mA cm −2 .

7 . A process according to claim 2 , wherein the Fe is an Fe 2+ salt and the Fe 2+ is presented in the bath in an amount of at most 20% by weight based on the total weight of discharge ion salts.

8 . A process according to claim 2 , wherein the Fe is an Fe 2+ salt and the Fe 2+ is presented in the bath in an amount of at most 35% by weight based on the total weight of discharge ion salts.

9 . A process according to claim 2 , wherein the Fe is an Fe 2+ salt and the Fe 2+ is presented in the bath in an amount of at most 25% by weight based on the total weight of discharge ion salts.

10 . A process according to claim 2 , wherein a source of the Fe comprises FeSO 4 , FeCl 2 , Fe(NO 3 ) 2 or other inorganic chemicals containing Fe.

11 . The process according to claim 1 for forming a deposit on the substrate, wherein the deposit is removed from the substrate to form a film.

12 . The process according to claim 11 , wherein the film is further anodized.

13 . The process of claim 12 , wherein the anodization is performed using an anodic electrolyte comprising
F − in a range of 0.01-11 g L −1 , and water in a range of 0-54 g L −1 .

14 . A process according to claim 13 , wherein a solvent for the anodic electrolyte comprises ethylene glycol, glycerol, dimethyl sulphoxide, N,N-dimethylformamide, or isopropyl alcohol, or a combination thereof.

15 . A process according to claim 13 , wherein the F − source comprises NH 4 F, HF, NaF, or a combination thereof.

16 . A process according to claim 2 , wherein the pH of the electrochemical deposition bath is 1-6.

17 . A process according to claim 16 , wherein a voltage is applied to the electrochemical deposition bath having a constant potential of 5-300 V.

18 . A film produced by the process of claim 11 .

19 . A film of claim 18 which is nanoporous on at least a portion of a surface of the film.

20 . A film of claim 18 comprising at least 90% of Ni, Co, NiFe, NiCo, FeCo, NiFeCo or a combination thereof, wherein
a) the film comprises a nanostructure characterized by pores greater than 15 nm in size on at least a portion of the film,
b) and wherein the thickness of the film is about 0.05-50 μm on at least a cross sectional area of the film.

21 . The film of claim 20 , wherein the nanostructure is characterized by pores between 18-22 nm in size.

22 . The film of claim 20 , wherein the nanostructure is characterized by pores between 20.0-21.0 nm in size and wherein the pores are substantially uniformly distributed throughout the film.

23 . A film produced by the process of claim 12 .

24 . The film of claim 23 , wherein the film is comprised of one of Ni, Co, NiFe, NiCo, FeCo, NiFeCo, or one of the oxides of Ni, Co, NiFe, NiCo, FeCo, or NiFeCo, or a combination thereof.

25 . The film of claim 23 which is nanoporous on at least a portion of a surface of the film.

26 . The film of claim 23 , wherein the film is associated with an electronic device.

27 . The film of claim 26 , wherein the electronic device is selected from the group consisting of lithium-ion batteries, storage devices, supercapacitors, electrodes, semiconductors, fuel cells, and combinations thereof.

28 . The film of claim 18 , wherein the film is associated with an electronic device.

29 . The film of claim 28 , wherein the electronic device is selected from the group consisting of lithium-ion batteries, storage devices, supercapacitors, electrodes, semiconductors, fuel cells, and combinations thereof.

30 . The film of claim 18 comprising a photocatalyst, electrochemical catalyst, or photoelectrochemical catalyst, hydrogen storage material, CO 2 storage material, uranium separation and sensing material, writing head, compact disk material, or shielding-foil material.

31 . A lithium-ion battery comprising a NiS 2 /FeS film which is nanoporous on at least a portion of a surface of the NiS 2 /FeS film.

32 . The process of claim 12 , further comprising treating the film with a chemical vapor deposition (CVD) treatment.

33 . A lithium-ion battery containing a film prepared by the process of claim 32 .

Assignees

• Univ Central Florida Res Found Inc

Inventors

• Yang Yang
• Marcus Kyle
• Liang Kun

Classifications

• C25D3/18

  Heterocyclic compounds · CPC title

• C25D1/04

  Wires; Strips; Foils · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title

• Y02E60/13

  Energy storage using capacitors · CPC title

• H01G11/86

  specially adapted for electrodes (carbonisation or activation of carbon for the manufacture of electrodes H01G11/34) · CPC title