Ni-, Co-, and Mn- multi-element doped positive electrode material for lithium battery and its preparation method
A Ni—, Co—, and Mn— multi-element doped positive electrode material for lithium ion batteries and its preparation method are provided. The method for preparing said material consists of: first forming a Ni—, Co—, and Mn— multi-element doped intermediate compound by coprecipitation or chemical synthesis; mixing said multi-element intermediate compound with lithium salt and pre-processing the resulting mixture; adding polyvinyl alcohol into the mixture and mixing uniformly, then pressing the resulting mixture into blocks, and calcining these at 800˜930° C.; cooling outside the furnace, crushing and passing through a 400-mesh sieve; calcining the resulting powder at 700˜800° C., cooling outside the furnace and crushing to obtain the product. The positive electrode material obtained by the method described is in the form of non-agglomerated monocrystal particles, with a particle diameter of 0 5˜30 μm, the chemical formula LiNi x Co y Mn z M (1-x-y-z) O 2 , a compacted density of up to 3.4 g/cm 3 , and an initial discharge capacity of 145˜152 mAh/g. This positive electrode material shows excellent cycle performance and a high degree of safety.
1. A method for preparing a multi-element cathode material comprising the following steps:
a) preparing a Ni, Co and Mn multi-element intermediate wherein step (a) comprises the steps of:
dissolving one or more sulfate or nitrate of Ni, Co and Mn in water to form a first solution;
adding a salt of Mo, Cr, Ge, In, Sr, Ta, Mg or a salt of one or more of rare earth elements to the first solution to make a second solution, wherein the second solution has a molar concentration of all metal elements in the range of 0.8-1.3 mol/L, in which a molar ratio of Ni, Co and Mn is Ni:Co:Mn=(0.9-1.2):1:(0.9-1.2), and a total amount of Mo, Cr, Ge, In, Sr, Ta, Mg and/or rare earth elements is 0.13-0.3% of the total weight of Ni, Co and Mn;
adding the second solution into a basic solution of NaOH and NH 3 that contains polyethylene glycol or an oxalate solution that contains polyethylene glycol at a rate of 5-30 mL/min in a temperature range of 40-70° C. to obtain a third solution;
stirring the third solution for 1-2 hours before settling for 1-4 hours and filtering to obtain a solid;
washing the solid with de-ionized water until a weight percentage of element Na is less than 0.01%;
drying the solid at 105-120° C. for 3-5 hours to obtain the Ni, Co and Mn multi-element intermediate;
b) mixing the Ni, Co and Mn multi-element intermediate with a Lithium salt to obtain a first mixture, wherein the molar ratio of the mixture is Li:(Ni+Co+Mn)=1.05-1.1:1, grounding the first mixture for 2-8 hours before preheating at 500-520° C. for 2 hours; mixing polyvinyl alcohol (PVA) with the pretreated material to form lumps, where an amount of PVA used is 0.98-2% of the total weight of Ni, Co and Mn;
c) calcining the lumps obtained above at 800-930° C. for 16-22 hours before cooling to 45-55° C., and crashing the calcining lumps and sieving through a 400 mesh sieve to obtain a filtrate;
d) placing the filtrate in a porcelain dish and calcining at 700-800° C. for 5-8 hours before cooling to 45-55° C., and crashing the calcined filtrate through a 400 mesh sieve to obtain the multi-element cathode material.
2. The preparation method of claim 1 , wherein the amount of polyethylene glycol used is about 0.4-1.5% of the total weight of Ni, Co and Mn.
3. The preparation method of claim 1 , wherein the concentration of NaOH and NH 3 in the basic NaOH and NH3 solution is 0.02-0.9 mol/L and 0.01-0.9 mol/L, respectively.
4. The preparation method of claim 1 , wherein the amount of the basic NaOH and NH 3 solution is 1.04-1.07 times of an stoichiometric amount.
5. The preparation method of claim 1 , wherein the oxalate solution contains 0.8-1.2 mol/L ammonium oxalate or sodium oxalate solution.
6. The preparation method of claim 1 , wherein the amount of the oxalate solution used is 1.05-1.1 times of an stoichiometric amount.
7. The preparation method of claim 3 , wherein the amount of the basic NaOH and NH 3 solution is 1.04-1.07 times of an stoichiometric amount.
8. The preparation method of claim 5 , wherein the amount of the oxalate solution used is 1.05-1.1 times of an stoichiometric amount.