Production of nanoporous films

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.

We claim: 
     
         1 . A film produced by 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; forming a deposit on the substrate; removing the deposit from the substrate to form a freestanding layer; and anodizing the freestanding layer to produce a nanoporous film; wherein the composition of the electrochemical deposition bath comprises one of
 (a) 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 up to 2 g L −1 ; wherein the electrochemical bath has a temperature in the range of 15-45° C., and wherein the electrochemical deposition bath comprises a salt of Co in a concentration of at least 0.001 g/L; and
 (b) 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 up to 5 g L −1 ; wherein the electrochemical bath has a temperature in a range of 15-65° C., and wherein the electrochemical deposition bath comprises a salt of Ni and a salt of Fe each in a concentration of at least 0.001 g/L; and
 (c) 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 wherein the electrochemical deposition bath comprises a salt of Ni and a salt of Co in a concentration of at least 0.001 g/L; and
 (d) 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 wherein the electrochemical deposition bath comprises a salt of Fe and a salt of Co each in a concentration of at least 0.001 g/L; and
 (e) 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 the electrochemical deposition bath comprises a salt of Ni, a salt of Fe and a salt of Co each in a concentration of at least 0.001 g/L. 
     
     
         2 . A film of  claim 1  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. 
 
     
     
         3 . The film of  claim 2 , wherein the nanostructure is characterized by pores between 18 
     
     
         4 . The film of  claim 1 , 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. 
     
     
         5 . The film of  claim 1 , wherein the film is associated with an electronic device. 
     
     
         6 . The film of  claim 5 , wherein the electronic device is selected from the group consisting of lithium-ion batteries, storage devices, supercapacitors, electrodes, semiconductors, fuel cells, and combinations thereof. 
     
     
         7 . A lithium-ion battery containing a film prepared by the process of  claim 1 . 
     
     
         8 . A film produced by a process, the 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; forming a deposit on the substrate; removing the deposit from the substrate to form a freestanding layer; and anodizing the freestanding layer to produce a nanoporous film;
 wherein the composition of the electrochemical deposition bath comprises   Ni 2+  in a range of 0-350 g L −1 ,   Borate in a range of 0-45 g L −1 ,   Saccharin up to 2 g L −1 ; wherein the electrochemical bath has a temperature in a range of 15-45° C.; and   wherein the metal salt is a salt of Ni, and wherein the metal salt is present in the electrochemical deposition bath composition at a concentration of at least 0.001 g/L.