Electrodes Comprising Mixed Active Particles

Abstract

An electrode active material comprising two or more groups of particles having differing chemical compositions, wherein each group of particles comprises a material selected from: (a) materials of the formula A 2 e M 2 f O g ; and (b) materials of the formula A 3 h Mn i O 4 ; wherein (i) A 2 , and A 3 are independently selected from the group consisting of Li, Na, K, and mixtures thereof, 0<e≦6 and h≦2.0; (ii) M 2 is one or more metals, comprising at least one metal selected from the group consisting of Fe, Co, Ni, Mo, V, Zr, Ti, Mo, and Cr, and 1≦f≦6; (iii) 0<g≦15; (iv) M 2 , e, f, g, h, and i, are selected so as to maintain electroneutrality of said compound; and (v) said material of the formula A 3 h Mn i O 4 has an inner and an outer region, wherein the inner region comprises a cubic spinel manganese oxide, and the outer region comprises a manganese oxide that is enriched in Mn +4 relative to the inner region.

1 . An electrode active material comprising two or more groups of particles having differing chemical compositions, wherein each group of particles comprises a material selected from:
 (a) materials of the formula A 2   e M 2   f O g ; and   (b) materials of the formula A 3   h Mn i O 4 ;   
       wherein
 (i) A 2 , and A 3  are independently selected from the group consisting of Li, Na, K, and mixtures thereof, 0<e≦6; h≦2.0; and i≦2; 
 (ii) M 2  is one or more metals, comprising at least one metal selected from the group consisting of Fe, Co, Ni, Mo, V, Zr, Ti, Mo, and Cr, and 1≦f≦6; 
 (iii) 0<g≦15; 
 (iv) M 2 , e, f, g, h, and i, are selected so as to maintain electroneutrality of said compound; and 
 (v) said material of the formula A 3   h Mn i O 4  has an inner and an outer region, wherein the inner region comprises a cubic spinel manganese oxide, and the outer region comprises a manganese oxide that is enriched in Mn +4  relative to the inner region. 
 
     
     
         2 . An electrode active material according to  claim 1 , comprising a material of the formula A 2   e M 2   f O g . 
     
     
         3 . An electrode active material according to  claim 2 , wherein A 2  comprises Li. 
     
     
         4 . An electrode active material according to  claim 3 , wherein M 2  is M 4   k M 5   m M 6   n , wherein M 4  is a transition metal selected from the group consisting of Fe, Co, Ni, Mo, V, Zr, Ti, Cr, and mixtures thereof; M 5  is one or more transition metal from Groups 4 to 11 of the Periodic Table; M 6  is at least one metal selected from Group 2, 12, 13, or 14 of the Periodic Table; and k+m+n=f. 
     
     
         5 . An electrode active material according to  claim 4 , wherein M 6  is selected from the group consisting of Mg, Ca, Al, and mixtures thereof, and n>0. 
     
     
         6 . An electrode active material according to  claim 4 , comprising a material of the formula LiNi r Co s M 6   t O 2 , wherein 0<(r+s)≦1, and 0≦t<1. 
     
     
         7 . An electrode active material according to  claim 17 , comprising a material selected from the group consisting of LiNiO 2 , LiCoO 2 , γ-LiV 2 O 5  and mixtures thereof. 
     
     
         8 . An electrode active material comprising two or more groups of particles having differing chemical compositions, wherein
 (a) the first group of particles comprises a material of the formula A 1   a M 1   b (XY 4 ) c Z d ; and   (b) the second group of particles comprises a material of the formula A 1   a M 1   b (XY 4 ) c Z d  wherein said first and second group of particle have differing formulas; and   
       wherein
 (i) A 1  is independently selected from the group consisting of Li, Na, K, and mixtures thereof, and 0<a≦8; 
 (ii) M 1  is independently, one or more metals, comprising at least one metal which is capable of undergoing oxidation to a higher valence state, and 0.8≦b≦3; 
 (iii) XY 4  is selected from the group consisting of X′O 4−x Y′ x , X′O 4−y Y′ 2y , X″S 4 , and mixtures thereof, where X′ is selected from the group consisting of P, As, Sb, Si, Ge, V, S, and mixtures thereof; X″ is selected from the group consisting of P, As, Sb, Si, Ge, V, and mixtures thereof; Y′ is halogen; 0≦x<3; and 0<c≦3; 
 (iv) Z is OH, halogen, or mixtures thereof, and 0≦d≦6; 
 (v) wherein M 1 , X, Y, Z, a, b, c, d, and x are selected so as to maintain electroneutrality of said compound. 
 
     
     
         9 . An electrode active material of  claim 8 , comprising a material of the formula A a M b (XY 4 ) c Z d  having an olivine structure. 
     
     
         10 . An electrode active material of  claim 8 , comprising a material of the formula A a M b (XY 4 ) c Z d  having a NASICON structure. 
     
     
         11 . An electrode active material according to  claim 8 , wherein M l  comprises at least one element from Groups 4 to 11 of the Periodic Table, and at least one element from Groups 2, 3, and 12-16 of the Periodic Table. 
     
     
         12 . An electrode active material according to  claim 11 , wherein M 1  comprises a transition metal selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr, and mixtures thereof. 
     
     
         13 . An electrode active material according to  claim 12 , wherein M 1  comprises a transition metal selected from the group consisting of Fe, Co, Mn, Ti, and mixtures thereof. 
     
     
         14 . An electrode active material according to  claim 11 , wherein M 1  comprises a metal selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al, and mixtures thereof. 
     
     
         15 . An electrode active material according to  claim 11 , wherein XY 4  is PO 4 . 
     
     
         16 . An electrode active material of  claim 11 , comprising a material of the formula:
   LiFe 1−q M 12   q PO 4      
       wherein M 12  is selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, and mixtures thereof; and 0<q<1. 
     
     
         17 . An electrode active material of  claim 16 , wherein 0<q≦0.2. 
     
     
         18 . An electrode active material of claim  64 , wherein M 12  is selected from the group consisting of Mg, Ca, Zn, Ba, and mixtures thereof. 
     
     
         19 . An electrode active material of  claim 18 , wherein M 12  is Mg. 
     
     
         20 . An electrode active material of  claim 19 , comprising a material of the formula LiFe 1−q Mg q PO 4 , wherein 0<q≦0.5. 
     
     
         21 . An electrode active material according to  claim 20  wherein said active material is selected from the group consisting of LiFe 0.9 Mg 0.1 PO 4  and LiFe 0.8 Mg 0.2 PO 4 , and mixtures thereof. 
     
     
         22 . An electrode active material comprising a first group of particles comprising an active material according to  claim 21 , and a second group of particles comprising an active material selected from the group consisting of γ-LiV 2 O 5 , LiNi 0.8 Co 0.15 Al 0.05 O 2 , LiCoO 2 , LiNi r Co s O 2 , Li 1+p Mn 2−p O 4 , LiNiO 2 , Li 2 CuO 2  and mixtures thereof, wherein 0<(r+s)≦1, and 0≦p<0.2. 
     
     
         23 . An electrode active material comprising a first group of particles comprising an active material according to  claim 21 , and a second group of particles comprising an active material having an inner and an outer region, wherein the inner region comprises a cubic spinel manganese oxide, and the outer region comprises a manganese oxide that is enriched in Mn +4  relative to the inner region. 
     
     
         24 . An electrode active material comprising a first group of particles comprising an active material selected from the group consisting of LiFe 0.9 Mg 0.1 PO 4 , LiFe 0.8 Mg 0.2 PO 4 , LiFe 0.95 Mg 0.05 PO 4 , LiCo 0.9 Mg 0.1 PO 4 , and mixtures thereof; and a second group of particles comprising an active material selected from the group consisting of LiCoO 2 , LiNi r Co s O 2 , Li i+p Mn 2−p O 4 , Li 2 CuO 2 , and mixtures thereof, wherein 0<(r+s)≦1, and 0≦p<0.2. 
     
     
         25 . A lithium battery comprising:
 (a) a first electrode comprising a powder mixture according to  claim 1 ,   (b) a second electrode which is a counter-electrode to said first electrode; and   (c) an electrolyte between said electrodes.   
     
     
         26 . A lithium battery comprising:
 (a) a first electrode comprising a powder mixture according to  claim 11 ,   (b) a second electrode which is a counter-electrode to said first electrode; and   (c) an electrolyte between said electrodes.