US2006083990A1PendingUtilityA1

Electrode active material and method of making the same

Individually held — no corporate assignee on recordPriority: Dec 19, 2002Filed: Dec 1, 2005Published: Apr 20, 2006
Est. expiryDec 19, 2022(expired)· nominal 20-yr term from priority
C04B 2235/3244H01M 4/582H01M 4/5825C04B 35/447C04B 2235/441C04B 2235/3272C04B 2235/3277C04B 2235/3262C04B 2235/3206H01M 4/58H01M 4/382C04B 2235/449C04B 2235/3251H01M 2300/0037C04B 2235/3239C04B 2235/3203C01P 2002/72H01M 10/052H01M 4/136Y02E60/10
51
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Claims

Abstract

The invention provides an electrochemical cell which includes a first electrode and a second electrode which is a counter electrode to said first electrode, and an electrolyte material interposed there between. The first electrode includes an alkali metal phosphorous compound doped with an element having a valence state greater than that of the alkali metal.

Claims

exact text as granted — not AI-modified
1 . A battery, comprising: 
 a first electrode comprising a compound represented by the general nominal formula:      [A a ,D d ]M m (XY 4 ) p Z e ,  wherein:    (i) A comprises at least one alkali metal, and 0<a≦9;    (ii) D is at least one element with a valence state of ≧2+, and 0<d≦1;    (iii) M comprises at least one redox active element, and 1≦m≦3;    (iv) XY 4  is selected from the group consisting of X′[O 4-x, Y′ x ], X′[O 4-y, Y′ 2y ], X″S 4 , [X z ′″,X′ 1-z ]O 4 , and mixtures thereof, wherein: 
 (a) X′ and X′″ are each independently selected from the group consisting of P, As, Sb, Si, Ge, V, S, and mixtures thereof;  
 (b) X″ is selected from the group consisting of P, As, Sb, Si, Ge, V, and mixtures thereof;  
 (c) Y′ is selected from the group consisting of a halogen, S, N, and mixtures thereof; and  
 (d) 0≦x≦3, 0≦y≦2, 0≦z≦1,and1≦p≦3; and  
   (v) Z is selected from the group consisting of OH, a halogen, and mixtures thereof, and 0≦e≦4; wherein A, D, M, X, Y, Z, a, d, m, p, e, x, y and z are selected so as to maintain electroneutrality of the compound;      the battery further comprising a second counter-electrode comprising an intercalation active material; and    an electrolyte.    
     
     
         2 . The battery of  claim 1 , wherein A is selected from the group consisting of Li, K, Na, and mixtures thereof.  
     
     
         3 . The battery of  claim 1 , wherein A is Li.  
     
     
         4 . The battery of  claim 1 , wherein D is a transition metal.  
     
     
         5 . The battery of  claim 4 , wherein D is selected from the group consisting of Nb, Zr, Ti, Ta, Mo, and W.  
     
     
         6 . The batter of  claim 1 , wherein D is selected from the group consisting of Mg, Zr and Nb.  
     
     
         7 . The battery of  claim 1 , wherein A is partially substituted by D by isocharge substitution.  
     
     
         8 . The battery of  claim 7 , wherein the compound is represented by the general nominal formula [A a-f ,D d ]M m (XY 4 ) p Z e , wherein f=d and 0<f≦1.  
     
     
         9 . The battery of  claim 7 , wherein the compound is represented by the general nominal formula [A a-f ,D d ]M m (XY 4 ) p Z e , wherein f≠d and 0<f≦9.  
     
     
         10 . The battery of  claim 1 , wherein A is partially substituted by D by aliovalent substitution.  
     
     
         11 . The battery of  claim 1   0 , wherein the compound is represented by the general nominal formula  
       
         
           
             
               
                 
                   [ 
                   
                     
                       A 
                       
                         a 
                         - 
                         
                           f 
                           
                             V 
                             A 
                           
                         
                       
                     
                     , 
                     
                       D 
                       
                         d 
                         
                           V 
                           D 
                         
                       
                     
                   
                   ] 
                 
                 ⁢ 
                 
                   
                     
                       M 
                       m 
                     
                     ⁡ 
                     
                       ( 
                       
                         XY 
                         4 
                       
                       ) 
                     
                   
                   p 
                 
                 ⁢ 
                 
                   Z 
                   e 
                 
               
               , 
             
           
         
       
       wherein f=d and 0<f≦1, V A  is the oxidation state of A and V D  is the oxidation state of D.  
     
     
         12 . The battery of  claim 10 , wherein the compound is represented by the general nominal formula  
       
         
           
             
               
                 
                   [ 
                   
                     
                       A 
                       
                         a 
                         - 
                         
                           f 
                           
                             V 
                             A 
                           
                         
                       
                     
                     , 
                     
                       D 
                       
                         d 
                         
                           V 
                           D 
                         
                       
                     
                   
                   ] 
                 
                 ⁢ 
                 
                   
                     
                       M 
                       m 
                     
                     ⁡ 
                     
                       ( 
                       
                         XY 
                         4 
                       
                       ) 
                     
                   
                   p 
                 
                 ⁢ 
                 
                   Z 
                   e 
                 
               
               , 
             
           
         
       
       wherein f≠d and 0<f≦9, V A  is the oxidation state of A and V D  is the oxidation state of D.  
     
     
         13 . The battery of  claim 1 , wherein M is selected from the group consisting of Ti 2+ , V 2+ , Cr 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Mo 2+ , Si 2+ , Sn 2+ , and Pb 2+ .  
     
     
         14 . The battery of  claim 1 , wherein M is selected from the group consisting of Ti 3+ , V 3+ , Cr 3+ , Mn 3+ , Fe 3+ , Co 3+ , Ni 3+ , Mo 3+ , and Nb 3+ .  
     
     
         15 . The battery of  claim 1 , wherein M=MI n MII o , 0<o+n≦3 and 0<o,n, wherein MI and MII are each independently selected from the group consisting of redox active elements and non-redox active elements, wherein at least one of MI and MII is redox active.  
     
     
         16 . The battery of  claim 15 , wherein MI and MII are both redox active.  
     
     
         17 . The battery of  claim 15 , wherein MI is substituted by MII by isocharge substitution.  
     
     
         18 . The battery of  claim 17 , wherein M=MI n-p MII o , and o=p.  
     
     
         19 . The battery of  claim 17 , wherein M=MI n-p MII o , and o≠p.  
     
     
         20 . The battery of  claim 17 , wherein MI is selected from the group consisting of Ti 2+ , V 2+ , Cr 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Mo 2+ , Si 2+ , Sn 2+ , Pb 2+ , and mixtures thereof, and MII is selected from the group consisting of Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Zn 2+ , Cd 2+ , Ge 2+ , and mixtures thereof.  
     
     
         21 . The battery of  claim 17 , wherein MI is selected from the group consisting of Ti 2+ , V 2+ , Cr 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Mo 2+ , Si 2+ , Sn 2+ , Pb 2+ , and mixtures thereof, and MII is selected from the group consisting of Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , and mixtures thereof.  
     
     
         22 . The battery of  claim 17 , wherein MI is selected from the group consisting of Ti 2+ , V 2+ , Cr 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Mo 2+ , Si 2+ , Sn 2+ , Pb 2+ , and mixtures thereof, and MII is selected from the group consisting of Zn 2+ , Cd 2+ , and mixtures thereof.  
     
     
         23 . The battery of  claim 17 , wherein MI is selected from the group consisting of Ti 3+ , V 3+ , Cr 3+ , Mn 3+ , Fe 3+ , Co 3+ , Ni 3+ , Mo 3+ , Nb 3+ , and mixtures thereof, and MII is selected from the group consisting of Sc 3+ , Y 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , and mixtures thereof.  
     
     
         24 . The battery of  claim 15 , wherein MI is substituted by MII by aliovalent substitution.  
     
     
         25 . The battery of  claim 24 , wherein M=MI n-o MII o .  
     
     
         26 . The battery of  claim 24 , wherein  
       
         
           
             
               
                 M 
                 = 
                 
                   
                     MI 
                     
                       n 
                       - 
                       
                         o 
                         
                           V 
                           MI 
                         
                       
                     
                   
                   ⁢ 
                   
                     MII 
                     
                       o 
                       
                         V 
                         MII 
                       
                     
                   
                 
               
               , 
             
           
         
       
       wherein V MI  is the oxidation state of MI, and V MII  is the oxidation state of MII.  
     
     
         27 . The battery of  claim 26 , wherein MI is selected from the group consisting of Ti 2+ , V 2+ , Cr 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Mo 2+ , Si 2+ ,Sn 2+ , Pb 2+ , and mixtures thereof, and MII is selected from the group consisting of Sc 3+ , Y 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , and mixtures thereof.  
     
     
         28 . The battery of  claim 26 , wherein MI is selected from the group consisting of Ti 2+ , V 2+ , Cr 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Mo 2+ , Si 2+ , Sn 2+ , Pb 2+ , and mixtures thereof, and MII is selected from the group consisting of alkali metals, Cu 1+ , Ag 1+ , and mixtures thereof.  
     
     
         29 . The battery of  claim 26 , wherein MI is selected from the group consisting of Ti 3+ , V 3+ , Cr 3+ , Mn 3+ , Fe 3+ , Co 3+ , Ni 3+ , Mo 3+ , Nb 3+ , and mixtures thereof, and MII is selected from the group consisting of Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Zn 2+ , Cd 2+ , Ge 2+ , and mixtures thereof.  
     
     
         30 . The battery of  claim 26 , wherein MI is selected from the group consisting of Ti 3+ , V 3+ , Cr 3+ , Mn 3+ , Fe 3+ , Co 3+ , Ni 3+ , Mo 3+ , Nb 3+ , and mixtures thereof MII is selected from the group consisting of alkali metals, Cu 1+ , Ag 1+ , and mixtures thereof.  
     
     
         31 . The battery of  claim 1 , wherein M=M1 q M2 r M3 s , wherein: 
 (a) M1 is a redox active element with a 2+ oxidation state;    (b) M2 is selected from the group consisting of redox and non-redox active elements with a 1 + oxidation state;    (c) M3 is selected from the group consisting of redox and non-redox active elements with a 3+ oxidation state; and    (d) at least one of p, q and r is greater than 0, and at least one of M1, M2, and M3 is redox active.    
     
     
         32 . The battery of  claim 31 , wherein q=q−(r+s).  
     
     
         33 . The battery of  claim 31 , wherein  
       
         
           
             
               
                 M 
                 = 
                 
                   M 
                   ⁢ 
                   
                       
                   
                   ⁢ 
                   
                     1 
                     
                       q 
                       - 
                       
                         r 
                         
                           V 
                           M1 
                         
                       
                       - 
                       
                         s 
                         
                           V 
                           M1 
                         
                       
                     
                   
                   ⁢ 
                   M 
                   ⁢ 
                   
                       
                   
                   ⁢ 
                   
                     2 
                     
                       r 
                       
                         V 
                         M2 
                       
                     
                   
                   ⁢ 
                   M 
                   ⁢ 
                   
                       
                   
                   ⁢ 
                   
                     3 
                     
                       s 
                       
                         V 
                         M3 
                       
                     
                   
                 
               
               , 
             
           
         
       
       wherein V MI  is the oxidation state of M1, V M2  is the oxidation state of M2, and V M3  is the oxidation state of M3.  
     
     
         34 . The battery of  claim 33 , wherein M1 is selected from the group consisting of Ti 2+ , V 2+ , Cr 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Mo 2+ , Si 2+ , Sn 2+ , Pb 2+ , and mixtures thereof; M2 is selected from the group consisting of Cu 1+ , Ag 1+  and mixtures thereof; and M3 is selected from the group consisting of Ti 3+ , V 3+ , Cr 3+ , Mn 3+ , Fe 3+ , Co 3 , Ni 3+ , Mo 3+ , Nb 3+ , and mixtures thereof.  
     
     
         35 . The battery of  claim 33 , wherein MI is selected from the group consisting of Ti 2+ , V 2+ , Cr 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Mo 2+ , Si 2+ , Sn 2+ , Pb 2+ , and mixtures thereof; M2 is selected from the group consisting of Li 1+ , K 1+ , Na 1+ , Ru 1+ , Cs 1+ , and mixtures thereof; and M3 is selected from the group consisting of Ti 3+ , V 3+ , Cr 3+ , Mn 3+ , Fe 3+ , Co 3+ , Ni 3+ , Mo 3+ , Nb 3+ , and mixtures thereof.  
     
     
         36 . The battery of  claim 33 , wherein MI is selected from the group consisting of Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Zn 2+ , Cd 2+ , Ge 2+ , and mixtures thereof; M2 is selected from the group consisting of Cu 1+ , Ag 1+  and mixtures thereof; and M3 is selected from the group consisting of Ti 3+ , V 3+ , Cr 3+ , Mn 3+ , Fe 3+ , Co 3+ , Ni 3+ , Mo 3+ , Nb 3+ , and mixtures thereof.  
     
     
         37 . The battery of  claim 33 , wherein Ml is selected from the group consisting of Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Zn 2+ , Cd 2+ , Ge 2+ , and mixtures thereof; M2 is selected from the group consisting of Li 1+ , K 1+ , Na 1+ , Ru 1+ , Cs 1+ , and mixtures thereof; and M3 is selected from the group consisting of Ti 3+ , V 3+ , Cr 3+ , Mn 3+ , Fe 3+ , Co 3+ , Ni 3+ , Mo 3+ , Nb 3+ , and mixtures thereof.  
     
     
         38 . The battery of  claim 33 , wherein M1 is selected from the group consisting of Ti 2+ , V 2+ , Cr 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Mo 2+ , Si 2+ , Sn 2+ , Pb 2+ , and mixtures thereof; M2 is selected from the group consisting of Cu 1+ , Ag 1+  and mixtures thereof; and M3 is selected from the group consisting of Sc 3+ , Y 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , and mixtures thereof.  
     
     
         39 . The battery of  claim 33 , wherein M1 is selected from the group consisting of Ti 2+ , V 2+ , Cr 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Mo 2+ , Si 2+ , Pb 2+ , and mixtures thereof; M2 is selected from the group consisting of Li 1+ , K 1+ , Na 1+ , Ru 1+ , Cs 1+, and mixtures thereof; and M3 is selected from the group consisting of Sc 3+ , Y 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , and mixtures thereof.  
     
     
         40 . The battery of  claim 1 , wherein the counter-electrode comprises an intercalation active material selected from the group consisting of a transition metal oxide, a metal chalcogenide, carbon, and mixtures thereof.  
     
     
         41 . The battery of  claim 40 , wherein the counter-electrode comprises graphite.  
     
     
         42 . A compound made by a process comprising the step of reacting at least one A-containing compound, at least one D-containing compound, one or more M-containing compounds, at least one XY 4 -supplying or containing compound, and (optionally) one or more Z-containing compounds, at a temperature and for a time sufficient to form the compound; 
 Wherein the compound is represented by the general nominal formula:      [A a ,D d ]M m (XY 4 ) p Z e ,    wherein:    (i) A comprises at least one alkali metal, and 0<a≦9;    (ii) D is at least one element with a valence state of ≧2+, and 0<d≦1;    (iii) M comprises at least one redox active element, and 1≦m≦3;    (iv) XY 4  is selected from the group consisting of X′[O 4-x, Y′ x ], X′[O 4-y, Y′ 2y ], X″S 4 , [X z ′″,X′ 1-z ]O 4 , and mixtures thereof, wherein: 
 (a) X′ and X′″ are each independently selected from the group consisting of P, As, Sb, Si, Ge, V, S, and mixtures thereof;  
 (b) X″ is selected from the group consisting of P, As, Sb, Si, Ge, V, and mixtures thereof;  
 (c) Y′ is selected from the group consisting of a halogen, S, N, and mixtures thereof; and  
 (d) 0≦x≦3, 0≦y≦2, 0≦z≦1, and 1≦p≦3; and  
   (v) Z is selected from the group consisting of OH, a halogen, and mixtures thereof, and 0≦e≦4;    wherein A, D, M, X, Y, Z, a, d, m, p, e, x, y and z are selected so as to maintain electroneutrality of the compound.

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