Alkali metal oxyanion electrode material having a carbon deposited by pyrolysis and process for making same

Abstract

An alkali metal oxyanion cathode material comprising particles, where the particles carry, on at least a portion of the particle surface, carbon deposit by pyrolysis is described. The particles have the general formula A: M:M′:X04 where the average valency of M is −2 or greater; A is at least one alkali metal selected from Li, Na and K; M is at least Fe and/or Mn; and M′ is a metal of valency of 2+ or more.

1 - 6 . (canceled) 
     
     
         7 . A process for making an alkali metal oxyanion cathode material comprising particles, where the particles carry, on at least a portion of the particle surface, a carbon coating deposited by pyrolysis and wherein the particles have the general formula A:M:M 1 :PO 4 :SiO 4 , wherein
 A is at least one alkali metal selected from Li, Na and K;   M is at least Fe and/or Mn, wherein the average valence of M is +2 or greater, and wherein M can be substituted by at most 15% at. of one or more metal at oxidation levels between +1 and +5;   M′ is a metal of valence of 2+ or more; and   wherein the elements of the general formula are present in the following general ratios 1:0.95-0.98:0.02 to <0.05:p:s, wherein the ratio “s” is equal to the ratio of M′ and wherein the ratio “p” is equal to (1−“s”);   
       said process comprising performing a thermal step on high-energy milled precursors of the cathode material, wherein at least a part of the thermal step is performed under a gaseous or vaporous atmosphere comprising a carbonaceous chemical and/or an organic chemical comprising carbon. 
     
     
         8 . The process according to  claim 7 , wherein M′ comprises Zr. 
     
     
         9 . The process according to  claim 7 , wherein the gaseous or vaporous atmosphere is humidified. 
     
     
         10 . The process according to  claim 7 , wherein the thermal step is performed in a chemical reactor that comprises a zone fed by an external flow of gas and/or vaporous atmosphere comprising a carbonaceous chemical and/or an organic chemical comprising carbon. 
     
     
         11 . A process according to  claim 7 , wherein the carbonaceous chemical comprises a decomposition product of an organic compound comprising carbon. 
     
     
         12 . The process according to  claim 7 , wherein the carbonaceous chemical is a compound having at least 40 wt. % of carbon. 
     
     
         13 . The process according to  claim 12 , wherein the carbonaceous compound is methanol, isopropanol and/or butanol. 
     
     
         14 . The process according to  claim 7 , wherein the precursors comprise:
 a) at least one source compound of an alkali metal;   b) at least one source compound of a metal M selected from Fe and/or Mn;   c) at least one source compound of a metal M′, where M′ in the final product is a 2+ or more metal;   d) at least one source compound of P, if the element P is not present in another source compound;   e) at least one source compound of Si, if the element Si is not present in another source compound; and   f) at least one source compound of carbon.   
     
     
         15 . The process according to  claim 14 , wherein the source compound b) is partially replaced by at most 15% of one or more other metals selected from Ni and Co, and/or by one or more aliovalent or isovalent metals selected from the group consisting of Mg, Mo, Mn, V, Pb, Sn, Nb, Ti, Ai, Ta, Ge, La, Y, Yb, Cu, Ag, Sm, Ce, Hf, Cr, Zr, Bi, Zn, Ca, B and W, and/or atoms of Fe(111). 
     
     
         16 . The process according to  claim 7 , further comprising performing a flash pyrolysis to obtain the carbon coating. 
     
     
         17 . The process according to  claim 7 , wherein an organic source of carbon is present in the precursors to obtain the carbon coating and pyrolysis is performed during the thermal step. 
     
     
         18 . The process according to  claim 7 , wherein the process further comprises, prior to the thermal step, performing a high-energy milling step of the alkali metal oxyanion cathode material precursors. 
     
     
         19 . The process according to  claim 18 , wherein an organic source of carbon is also present during the high-energy milling step. 
     
     
         20 . The process according to  claim 18 , wherein the high-energy milling is a high-energy ball milling or a dry high-energy milling. 
     
     
         21 . The process according to  claim 7 , wherein the thermal step is operated at a temperature selected from the range of temperatures between about 400° C. and about 800° C., about 450° C. and about 800° C., about 500° C. and about 800° C., about 525° C. and about 800° C., about 550° C. and about 800° C., or about 575° C. and about 800° C., about 600° C. and about 800° C., about 400° C. and about 700° C., about 450° C. and about 650° C., or about 500° C. and about 600° C. 
     
     
         22 . The process according to  claim 19 , wherein the high-energy milling is a high-energy ball milling or a dry high-energy milling.