Method for manufacturing of three-dimensional freestanding porous thin-graphite with hierarchical porosity

Abstract

The present invention includes an apparatus and a method of making a three dimensional graphite structure with a controlled porosity comprising: plating a metal layer on at least one of a nickel, an iron or a cobalt foam substrate; annealing the metal and the nickel, iron or cobalt foam into a porous metal-nickel, iron or cobalt catalyst, wherein the catalyst has a smooth and a porous surface; etching the smooth surface of the annealed porous metal-nickel, iron or cobalt catalyst; growing a carbonaceous layer on the porous surface of the annealed porous metal-nickel, iron or cobalt catalyst; and completely etching the porous metal-nickel, iron or cobalt catalyst to obtain the graphite layer.

1 . A method of making a three dimensional graphite structure with a controlled porosity comprising:
 plating a metal layer on at least one or a nickel, an iron or a cobalt foam substrate;   annealing the metal and the nickel, iron or cobalt foam into a porous metal-nickel, iron or cobalt catalyst, wherein the catalyst has a smooth and a porous surface;   etching the smooth surface of the annealed porous metal-nickel, iron or cobalt catalyst;   growing a carbonaceous layer on the porous surface of the annealed porous metal-nickel, iron or cobalt catalyst; and   etching the porous metal-nickel, iron or cobalt catalyst to obtain the graphite layer.   
     
     
         2 . The method of  claim 1 , wherein the carbonaceous layer is graphene or graphite that is deposited on the annealed porous copper-nickel catalyst by at least one of chemical vapor deposition, plasma enhanced chemical vapor deposition or sputtering. 
     
     
         3 - 4 . (canceled) 
     
     
         5 . The method of  claim 1 , wherein the metal is selected from at least one of copper, nickel, iron, cobalt, gold, platinum, or rhodium, but different from the foam material. 
     
     
         6 . The method of  claim 1 , wherein the carbonaceous layer is deposited on the annealed porous copper-nickel catalyst by chemical vapor deposition in ethylene at between 600-700° C. 
     
     
         7 . The method of  claim 1 , wherein the carbonaceous layer is graphite. 
     
     
         8 . The method of  claim 1 , wherein the carbonaceous layer is freestanding and flexible. 
     
     
         9 . (canceled) 
     
     
         10 . The method of  claim 1 , further comprising the step of growing a metal hydroxide layer on the graphite layer. 
     
     
         11 . The method of  claim 1 , further comprising the step of growing at least one of a metal hydroxide, an oxide or a sulfide layer on the graphite layer, wherein the metal hydroxide/oxide/sulfide is selected from at least one of Ruthenium(IV) oxide; Aluminum hydroxide; Beryllium hydroxide; Cobalt(II) hydroxide; Cobalt oxide; Copper(II) hydroxide; Copper oxide; Curium hydroxide; Gold(III) hydroxide; Iron(II) hydroxide; Iron oxide; Mercury(II) hydroxide; Nickel(II) hydroxide; Nickel oxide; Nickel sulfide; Manganese oxide (MnO 2  or Mn 3 O 4 ); Manganese sulfide; Tin(II) hydroxide; Tin(IV) Oxide; Uranyl hydroxide; Zinc hydroxide; Zirconium(IV) hydroxide; Gallium(III) hydroxide; Lead(II) hydroxide; or Thallium hydroxide. 
     
     
         12 . The method of  claim 1 , wherein the carbonaceous layer is formed into an electrode support for metal hydroxide supercapacitors. 
     
     
         13 - 16 . (canceled) 
     
     
         17 . The method of  claim 1 , wherein the step of etching the porous metal-nickel, iron or cobalt catalyst is defined further as selecting an etching agent that etches the annealed porous metal-nickel, iron or cobalt. 
     
     
         18 . The method of  claim 1 , wherein the step of etching the porous metal-nickel, iron or cobalt catalyst is defined further as etching the copper-nickel catalyst in 1 M iron chloride (FeCl 3 ) and 2 M hydrochloride (HCl) at 50-80° C. overnight. 
     
     
         19 - 50 . (canceled) 
     
     
         51 . A three-dimensional graphite structure comprising:
 a first level of pores and a second level of pores, wherein the second level of pores are smaller than the first level of pores and are disposed on the walls of said first level of pores. having different porosities   
     
     
         52 . The graphite structure of  claim 51 , wherein the graphite layer is freestanding and flexible. 
     
     
         53 . The graphite structure of  claim 51 , comprising a metal hydroxide, an oxide or a sulfide layer on the graphite. 
     
     
         54 . The graphite structure of  claim 53 , wherein the metal hydroxide, oxide, or sulfide is selected from at least one of ruthenium(IV) oxide; aluminum hydroxide; beryllium hydroxide; cobalt(II) hydroxide; cobalt oxide; copper(II) hydroxide; copper oxide; curium hydroxide; gold(II) hydroxide; iron(II) hydroxide; iron oxide; mercury(II) hydroxide; nickel(II) hydroxide; nickel oxide; nickel sulfide; manganese oxide (MnO 2  or Mn 3 O 4 ); manganese sulfide; tin(II) hydroxide; tin(IV) Oxide; uranyl hydroxide; zinc hydroxide; zirconium(IV) hydroxide; gallium(III) hydroxide; lead(II) hydroxide; or thallium hydroxide. 
     
     
         55 . The graphite structure of  claim 53 , having a specific capacitance of at least 1149 F/g at a current density of 1.5 A/g. 
     
     
         56 . The graphite structure of  claim 53 , having at least 97.5% capacitance retention after 4,000 cycles. 
     
     
         57 . The graphite structure of  claim 53 , having at least 90% capacitance after 10,000 cycles.