Spherical Metal Carbonates and Lithium Metal Oxides for Lithium Rechargeable Batteries

Abstract

A number of materials with the composition Li 1+x Ni α Mn β Co γ M′ δ O 2−z F z (M′=Mg, Zn, Al, Ga, B, Zr, Ti) for use with rechargeable batteries, wherein x is between about 0 and 0.3, α is between about 0.2 and 0.6, β is between about 0.2 and 0.6, γ is between about 0 and 0.3, δ is between about 0 and 0.15, and z is between about 0 and 0.2. Adding the above metal and fluorine dopants affects capacity, impedance, and stability of the layered oxide structure during electrochemical cycling. Another aspect of the invention includes materials with the composition Li 1+x Ni α Co β Mn γ M′ δ O y F z (M′=Mg, Zn, Al, Ga, B, Zr, Ti), where the x is between 0 and 0.2, the α between 0 and 1, the β between 0 and 1, the γ between 0 and 2, the δ between about 0 and about 0.2, the y is between 2 and 4, and the z is between 0 and 0.5.

1 . A mixed nickel-cobalt-manganese carbonate comprising:
 (Ni a Co b Mn c )CO 3  having a spherical morphology, wherein a is between 0 and about 1, b is between 0 and about 1, and c is between 0 and about 1.   
   
   
       2 . The mixed nickel-cobalt-manganese carbonate of  claim 1 , further comprising a narrow size distribution of about 1 to about 50 microns of (Ni a Co b Mn c )CO 3 . 
   
   
       3 . A positive active composition comprising:
 a substituted lithium nickel-manganese oxide having a spherical morphology; and   the substituted lithium nickel-manganese oxide has the formula Li 1+x Ni α Co β Mn γ M′ δ O y F z  (M′=Mg, Zn, Al, Ga, B, Zr, Ti), wherein x is between about 0 and about 0.3, α is between about 0 and about 1, β is between about 0 and about 1, γ is between about 0 and about 2, 6 is between about 0 and about 0.2, y is between about 2 and about 4, and z is between about 0 and about 0.5.   
   
   
       4 . The positive active composition of  claim 3 , further comprising a narrow size distribution of about 1 to about 50 microns of substituted lithium nickel-manganese oxide. 
   
   
       5 . A positive electrode material having the positive active composition of  claim 3  further comprising a conducting agent and a binder. 
   
   
       6 . A non-aqueous lithium cell having the positive electrode material of  claim 5  further comprising a negative electrode and a non-aqueous electrolyte. 
   
   
       7 . The non-aqueous lithium cell of  claim 6 , wherein the negative electrode is chosen from the group consisting of lithium metal, graphite, silicon, silver, lithium titanium oxospinel (Li 4 Ti 5 O 12 ), tin oxide, and intermetallic compounds A-B (A, B: Ag, Al, Cu, Fe, Mg, Mo, Ni, Sb, Si, Sn, Ti). 
   
   
       8 . The non-aqueous lithium cell of  claim 6 , wherein the non-aqueous electrolyte is chosen from the group consisting of LiBF 4 , LiClO 4 , LiPF 6 , and LiB(C 2 O 4 ) 2  dissolved in a solvent chosen from the group consisting of ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), polyethylene carbonate (PC), ethyl nonafluorobutyl ether (EFE), vinylene carbonate (VC), methyl difluoroacetate (MFA), vinyl pyridine (VP), vinyl ethylene carbonate (VEC), siloxane, and combinations thereof. 
   
   
       9 . A positive active composition for use in a rechargeable battery comprising:
 a substituted lithium nickel-manganese oxide; and   the substituted lithium nickel-manganese oxide has the formula Li 1+x Ni α Mn β Co γ M′ δ O 2-z F z  (M′=Mg, Zn, Al, Ga, B, Zr, Ti), wherein x is between about 0 and about 0.3, α is between about 0.2 and about 0.6, β is between about 0.2 and about 0.6, γ is between about 0 and about 0.3, 6 is between about 0 and about 0.15, and z is between about 0 and about 0.2.   
   
   
       10 . The positive active composition of  claim 9 , further comprising a surface-coat on the substituted lithium nickel-manganese oxide 
   
   
       11 . The positive active composition of  claim 10 , wherein the surface-coat is chosen from the group consisting of A′-alkoxide, A′-salt, and A′-oxide, wherein A′ includes Al, Bi, Ga, Ge, In, Mg, Pb, Si, Sn, Ti, Tl, Zn, Zr or mixtures thereof. 
   
   
       12 . The positive active composition of  claim 11 , wherein the surface-coat comprises Al-isopropoxide between about 0.5 wt % and about 1.0 wt % of substituted lithium nickel-manganese oxide. 
   
   
       13 . A method of preparing a positive active composition comprising the steps of:
 mixing amounts of lithium hydroxide (or lithium carbonate or lithium nitrate), (Ni,Co,Mn)-carbonate of  claim 1 , M′-hydroxide (or M′-carbonate or M′-oxide; M′=Mg, Zn, Al, Ga, B, Zr, Ti), and LiF (or NH 4 F) for about 12 to 24 hours to form a mixed powder;   calcinating the mixed powder at about 450 to 700° C. for about 12 to 30 hours either in air or in oxygen atmospheres; and   calcinating the mixed powder at about 700 to 1000° C. for about 10 to 24 hours either in air or in oxygen atmospheres.