Method for manufacturing lithium metal phosphate
Disclosed is a method for manufacturing lithium metal phosphate (LMP) having, as a precursor, crystalline iron phosphate salt having a (meta)strengite structure or metal-doped crystalline iron phosphate salt having a (meta)strengite structure, the method comprising the steps of: mixing a lithium raw material with crystalline iron phosphate salt in a slurry phase or a cake phase; and heat-treating the mixture. The method, by mixing a lithium (Li) raw material and a carbon (C) coating material with crystalline iron phosphate salt in a slurry phase or a cake phase, allows elements such as Li, Fe, P and C to be homogeneously mixed, and then, by having the elements dried simultaneously, enables manufacturing of high-quality LMP. Therefore, the present invention is not only capable of providing convenience during the manufacturing process for lithium metal phosphate, but also capable of providing a lithium secondary battery positive electrode active material having excellent battery characteristics.
1. A method for manufacturing lithium metal phosphate having the following Formula I, the method comprising:
providing a crystalline iron phosphate salt in a slurry phase or a cake phase;
mixing a lithium raw material with the provided crystalline iron phosphate salt in the slurry phase or the cake phase to form a mixture, wherein the provided crystalline iron phosphate salt in the slurry phase or the cake phase is in a state of not having been subjected to a drying process; and
heat-treating the mixture:
LiM 1-n Fe n PO 4 , Formula I
where M is selected from Ni, Co, Mn, Cr, Zr, Nb, Cu, V, Ti, Zn, Al, Ga and Mg, and 0<n≦1.
2. The method of claim 1 , wherein heat-treating the mixture is performed in the range of 500 to 1,000° C.
3. The method of claim 1 , wherein the crystalline iron phosphate salt has a (meta)strengite structure.
4. The method of claim 1 , wherein the crystalline iron phosphate salt is a doped crystalline iron phosphate salt obtained by doping a metal (M) during a process of crystallizing an amorphous iron phosphate salt, the doped crystalline iron phosphate salt being expressed as the following Formula II:
M 1-x Fe x PO 4 , Formula II
where M is selected from Ni, Co, Mn, Cr, Zr, Nb, Cu, V, Ti, Zn, Al, Ga and Mg, and 0<x<1.
5. The method of claim 1 , further comprising drying the mixture after the mixing.
6. The method of claim 1 , wherein the crystalline iron phosphate is in the cake phase, and the crystalline iron phosphate salt in the cake phase is obtained by washing the crystalline iron phosphate salt after crystallization of an amorphous iron phosphate salt to form the crystalline iron phosphate salt is completed.
7. The method of claim 1 , wherein the lithium raw material is selected from LiOH, Li 2 CO 3 and LiCl.
8. The method of claim 1 , wherein in mixing the lithium raw material with the crystalline iron phosphate salt, the molar ratio between the crystalline iron phosphate salt and the lithium raw material is in the range from 1:0.5 to 1:1.5.
9. The method of claim 1 , wherein mixing the lithium raw material with the crystalline iron phosphate salt further includes mixing a carbon coating material with the lithium raw material and the crystalline iron phosphate salt.
10. The method of claim 9 , wherein the carbon coating material is selected from sucrose, glucose, fructose, xylose, sorbose, polyethylene, ethylene oxide, ascorbic acid, oleic acid, citric acid, PEG6000s, polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polysolvate 80 (Tween 80), Triton X-100, LupasolPN50, and hydroxypropyl methylcellulose (HPMC).
11. The method of claim 3 , wherein the (meta)strengite structure includes one or more selected from a crystal with a structure of strengite, a crystal with a structure of metastrengite 1 and a crystal with a structure of metastrengite 2.
12. A lithium metal phosphate (LMP) manufactured by the method of claim 1 .
13. A lithium secondary battery comprising the lithium metal phosphate (LMP) of claim 12 as a positive electrode active material.