Method Of Making Active Materials For Use In Secondary Electrochemical Cells

Abstract

The present invention provides for the preparation of an “optimized” VPO 4 phase or V—P—O/C precursor. The VPO 4 precursor is an amorphous or nanocrystalline powder. The V—P—O/C precursor is amorphous in nature and contains finely divided and dispersed carbon. Throughout the specification it is understood that the VPO 4 precursor and the V—P—O/C precursor materials can be used interchangeably to produce the final vanadium phosphates, with the V—P—O/C precursor material being the preferred precursor. The precursors can subsequently be used to make vanadium based electroactive materials and use of such precursor materials offers significant advantages over other processes known for preparing vanadium phosphate compounds.

1 . A method for making a vanadium phosphate precursor comprising mixing V 2 O 5  with a phosphate compound and a carbon containing compound or a carbon precursor to form a mixture, and heating the mixture at a temperature and for a time sufficient to form a precursor selected from the group consisting of amorphous V—P—O/C precursor and nanocrystalline VPO 4  precursor.  
   
   
       2 . The method according to  claim 1  wherein the phosphate compound is (NH 4 ) 2 HPO 4  or (NH 4 )H 2 PO 4 .  
   
   
       3 . The method according to  claim 1  wherein the carbon is a conductive high surface area carbon with a surface area of from about 1 to about 1000 m 2 /g.  
   
   
       4 . The method according to  claim 3  wherein the carbon is selected from carbon black; Super P, Shawinaghan black and mixtures thereof.  
   
   
       5 . The method according to  claim 2  wherein the carbon is selected from a graphitic carbon and organic precursor materials.  
   
   
       6 . The method according to  claim 1  wherein the mixture is heated at a temperature in the range from about 650° C. to about 900° C.  
   
   
       7 . The method according to  claim 3  wherein the temperature is from about 700° C. to about 800° C.  
   
   
       8 . A method for making a vanadium phosphate compound of the formula: 
       A a V 1−x M x (PO 4 ) d Z f .  (I) wherein A is selected from the group consisting of Li, Na, K and mixtures thereof;    a is greater than 0.1 and less than or equal to 3;    x is greater than or equal to zero and less than 1;    d is greater than 0 and less than or equal to 3;    M is a metal selected from the group consisting of Al, Ti, Cr, Fe, Mn, Mo, and Nb;    Z is F, Cl, or OH:    and f is greater than or equal to zero but less than or equal to three;    comprising mixing the VPO 4  precursor or V—P—O/C precursor produced according to the method of  claim 1  with an alkali metal containing compound to form a mixture and heating the mixture at a temperature and for a time sufficient to form the vanadium phosphate compound.    
   
   
       9 . The method according to  claim 7  wherein the mixture further comprises a second metal containing compound.  
   
   
       10 . The method according to  claim 7  wherein the alkali metal compound is selected from the group consisting of LiF, NaF, NaOH, LiOH, Na 2 CO 3  and Li 3 PO 4 .  
   
   
       11 . The method according to  claim 8  wherein the metal containing compound comprises a metal ion of a metal selected from the group consisting of Al, Ti, Cr, Fe, Mn, Mo and Nb.  
   
   
       12 . The method according to  claim 7  wherein the vanadium phosphate compound produced is selected from LiVPO 4 , LiV 1−x Al x PO 4 F, Na x VPO 4 F x , Li 0.1 Na 0.9 VPO 4 F, NaVPO 4 F, NaVPO 4 OH, NaVPO 4 F, Li 3 V 2 (PO 4 ) 3 , LiV 0.75 Al 0.25 PO 4 F, LiV 0.5 Al 0.5 PO 4 F, Na 1.2 VPO 4 F 1.2  and Na 3 V 2 (PO 4 ) 2 F 3 .  
   
   
       13 . A method for making a vanadium phosphate compound of the formula: 
       A a V 1−x M x P 2 O 7   (I) wherein A is selected from the group consisting of Li, Na, K and mixtures thereof;    a is greater than 0.1 and less than or equal to 3;    x is greater than or equal to zero and less than 1; and    M is a metal selected from the group consisting of Al, Ti, Cr, Fe, Mn, Mo and Nb;    comprising mixing the VPO 4  precursor or V—P—O/C precursor produced according to the method of  claim 1  with an alkali metal containing compound to form a mixture and heating the mixture at a temperature and for a time sufficient to form the vanadium phosphate compound.    
   
   
       14 . The method according to  claim 7  wherein the mixture further comprises a second metal containing compound.  
   
   
       15 . The method according to  claim 7  wherein the alkali metal compound is selected from the group consisting of LiF, NaF, NaOH, LiOH, Na 2 CO 3  and Li 3 PO 4 .  
   
   
       16 . The method according to  claim 8  wherein the metal containing compound comprises a metal ion of a metal selected from the group consisting of Al, Ti, Cr, Fe, Mn, Mo and Nb.  
   
   
       17 . The method according to  claim 7  wherein the vanadium phosphate compound produced is LiVP 2 O 7 .  
   
   
       18 . A method for making a vanadium phosphate precursor comprising mixing V 2 O 5  with a phosphate compound and heating the mixture in a reducing atmosphere at a temperature and for a time sufficient to form a precursor selected from the group consisting of amorphous V—P—O/C precursor and nanocrystalline VPO 4  precursor.  
   
   
       19 . The method according to  claim 18  wherein the phosphate compound is (NH 4 ) 2 HPO 4  or (NH 4 )H 2 PO 4 .  
   
   
       20 . The method according to  claim 18  wherein the mixture additionally comprises a conductive high surface area carbon with a surface area of from about 1 to about 1000 m 2 /g.  
   
   
       21 . The method according to  claim 20  wherein the mixture additionally comprises carbon selected from carbon black; Super P, Shawinaghan black and mixtures thereof.  
   
   
       22 . The method according to  claim 18  wherein the mixture additionally comprises carbon selected from a graphitic carbon and organic precursor materials.  
   
   
       23 . The method according to  claim 18  wherein the mixture is heated at a temperature in the range from about 650° C. to about 900° C.  
   
   
       24 . The method according to  claim 18  wherein the temperature is from about 700° C. to about 800° C.