Surface modifications for electrode compositions and their methods of making

Abstract

Compositions and methods of making are provided for surface modified electrodes and batteries comprising the same. The compositions may comprise a base composition having an active material capable of intercalating the metal ions during a discharge cycle and deintercalating the metal ions during a charge cycle, wherein the active material is selected from the group consisting of LiCoO 2 , LiMn 2 O 4 , Li 2 MnO 3 , LiNiO 2 , LiMn 1.5 Ni 0.5 O 4 , LiFePO 4 , Li 2 FePO 4 F, Li 3 CoNiMnO 6 , Li(Li a Ni x Mn y Co z )O 2 , Li a Mn 1.5-b Ni 0.5-c M d O 4-x , and mixtures thereof. The compositions may also comprise an annealed composition covering a portion of the base composition, formed by a reaction of the base composition in a reducing atmosphere. The methods of making comprise providing the base composition and annealing the base electrode in a reducing atmosphere.

What is claimed is: 
     
         1 . An electrode for a battery comprising:
 a base composition having an active material capable of intercalating the metal ions during a discharge cycle and deintercalating the metal ions during a charge cycle, wherein the active material is selected from the group consisting of LiCoO 2 , LiMn 2 O 4 , Li 2 MnO 3 , LiNiO 2 , LiMn 1.5 Ni 0.5 O 4 , LiFePO 4 , Li 2 FePO 4 F, Li 3 CoNiMnO 6 , Li(Li a Ni x Mn y Co z )O 2 , Li a Mn 1.5-b Ni 0.5-c M d O 4-x , and mixtures thereof; and   an annealed composition covering a portion of the base composition, formed by a reaction of the base composition in a reducing atmosphere.   
     
     
         2 . The electrode of  claim 1 , wherein the active material in the base composition of the cathode comprises LiMn 1.5 Ni 0.5 O 4 . 
     
     
         3 . The electrode of  claim 1 , wherein the active material in the base composition of the cathode comprises Li a Mn 1.5-b Ni 0.5-c M d O 4 . 
     
     
         4 . The electrode of  claim 3 , wherein M is a metal selected from the group consisting of: Li, Na, K, Mg, Be, Ca, Sr, Ba, Si, Al, Ga, In, Tl, Sc, Ti, V, Cr, Fe, Pt, Os, Cu, or Zn. 
     
     
         5 . The electrode of  claim 1 , wherein the capacity is at least 125% greater at 3 C, 5 C, or 10 C when compared with an electrode having the same base composition without the annealed composition. 
     
     
         6 . The electrode of  claim 1 , having a capacity of at least 120 mAh/g at a rate of C/10, 1 C, 3 C, 5 C, or 10 C. 
     
     
         7 . A battery comprising:
 an anode;   a cathode having a base composition with an active material capable of intercalating the metal ions during a discharge cycle and deintercalating the metal ions during a charge cycle, wherein the active material is selected from the group consisting of LiCoO 2 , LiMn 2 O 4 , Li 2 MnO 3 , LiNiO 2 , LiMn 1.5 Ni 0.5 O 4 , LiFePO 4 , Li 2 FePO 4 F, Li 3 CoNiMnO 6 , Li(Li a Ni x Mn y Co z )O 2 , Li a Mn 1.5-b Ni 0.5-c M d O 4-x , and mixtures thereof;   an annealed composition covering a portion of the base composition of the cathode, formed by a reaction the base composition in a reducing atmosphere; and   an electrolyte capable of supporting reversible deposition and stripping of metal at the anode, and reversible intercalation and deintercalation of the metal at the cathode.   
     
     
         8 . The battery of  claim 7 , wherein the active material in the base composition of the cathode comprises LiMn 1.5 Ni 0.5 O 4 . 
     
     
         9 . The battery of  claim 7 , wherein the active material in the base composition of the cathode comprises Li a Mn 1.5-b Ni 0.5-c M d O 4-x . 
     
     
         10 . The battery of  claim 9 , wherein M is a metal selected from the group consisting of: Li, Na, K, Mg, Be, Ca, Sr, Ba, Si, Al, Ga, In, Tl, Sc, Ti, V, Cr, Fe, Pt, Os, Cu, or Zn. 
     
     
         11 . The battery of  claim 7 , wherein the capacity is at least 125% greater at 3 C, 5 C, or 10 C when compared with an battery having the same anode, electrolyte, and base composition of the cathode without the annealed composition. 
     
     
         12 . The battery of  claim 7 , having a capacity of at least 120 mAh/g at a rate of C/10, 1 C, 3 C, 5 C, or 10 C. 
     
     
         13 . The battery of  claim 7 , wherein the base composition of the anode comprises at least 90 wt. % lithium as the primary electrochemically active material of the anode. 
     
     
         14 . The battery of  claim 7 , wherein the anode comprises mesoporous metal oxide microspheres, having (a) microspheres with an average diameter between 200 nm and 10 μm, and (b) mesopores on the surface and interior of the microspheres, wherein the mesopores have an average diameter between 1 nm and 50 nm and the microspheres have a surface area between 50 m 2 /g and 500 m 2 /g. 
     
     
         15 . The battery of  claim 7 , wherein the battery is selected from the group consisting of the following battery types: lithium-ion, aluminum-ion, magnesium-ion, sodium-ion, metal-air, and metal-sulfur, wherein the metal is lithium, aluminum, magnesium, zinc, or sodium. 
     
     
         16 . The battery of  claim 7 , wherein the battery is a lithium-ion battery. 
     
     
         17 . The battery of  claim 7  having an ability to charge from 0% to 50% of the full range capacity in 6 minutes, or an ability to charge from 0% to 33% of the full range capacity in 1 minute. 
     
     
         18 . The battery of  claim 7  having a functional discharge capacity of at least 90% of the initial discharge capacity after 100 cycles. 
     
     
         19 . The battery of  claim 7 , wherein the battery is used in a grid storage application, vehicle battery application, military application, portable electronic device application, medical device application, or standard cell size battery application. 
     
     
         20 . A method of forming an electrode comprising:
 providing a base electrode composition having an active material comprising LiMn 1.5 Ni 0.5 O 4 ; and   annealing the base electrode composition in a reducing atmosphere.   
     
     
         21 . The method of  claim 20 , wherein the reducing atmosphere contains a flowing reducing gas selected from the group consisting of: hydrogen, argon, nitrogen, fluorine, sulfur, carbon monoxide, methane, ammonia, carbon dioxide, and mixtures thereof. 
     
     
         22 . The method of  claim 21 , wherein the flowing reducing gas is ammonia. 
     
     
         23 . The method of  claim 20 , further comprising doping the base electrode composition with a metal oxide prior to the annealing step, therein forming a doped electrode composition comprising Li a Mn 1.5-b Ni 0.5-c M d O 4 . 
     
     
         24 . The method of  claim 23 , wherein M is a metal selected from the group consisting of: Li, Na, K, Mg, Be, Ca, Sr, Ba, Si, Al, Ga, In, Tl, Sc, Ti, V, Cr, Fe, Pt, Os, Cu, or Zn.