Methods for preparing particle precursor and cathode active particles, and particle precursor prepared thereby
The invention relates to a method for preparing transitional-metal particles (cathode particle precursor) under a co-precipitation reaction. In this method, by feeding different types of anion compositions and/or cation compositions, and adjusting the pH to match with the species, precipitated particles are deposited to form a slurry, colleting the slurry, treating with water, and drying to get a cathode particle precursor. Mixing the cathode particle precursor with a lithium source and calcining to yield core-shell structured cathode active particles. Such cathode active particle can be used to prepare cathode of lithium-ion battery.
1. A method for preparing a particle precursor, comprising the following steps:
feeding stream (b) into a reactor for providing precipitating anions, feeding stream (a) for providing transitional-metal cations, whereby the precipitating anions and the transitional-metal cations reacting to form a precipitated particle slurry; wherein the stream (b) is fed by the following steps: feeding the stream (b) with only a first anion composition B 1 ; and stopping the first anion composition B 1 and feeding the stream (b) with only a second anion composition B 2 which is different from the first anion composition B 1 at a first switching time between the time when precipitation starts and the time when the reaction ends, wherein the stream (a) comprises at least one cation composition; and
filtering, and drying the precipitated particle slurry to yield the particle precursor comprising a core-shell structure;
wherein the first anion composition B 1 is in a core layer and the second anion composition B 2 is in a shell layer to form the core-shell structure, and the second anion composition B 2 in the shell layer initiates a concentration gradient when the first anion composition B 1 stops feeding and the second anion composition B 2 starts feeding.
2. The method of claim 1 , wherein, for indicating whole compositions of the particle precursor, the particle precursor has a formula of (Ni x Mn y Co z Me 1-x-y-z ) (CO 3 ) a (OH) 2-2a , where x+y+z≥0.9, z≤0.2, 0≤a≤1, “Me” is at least one additional metal element selected from the group consisting of Mg, Ca, Zr, Ti, V, Cr, Fe, Cu and Al.
3. The method of claim 1 , wherein the stream (b) comprises anions whose concentration is 0.001-14 mol anion/L; and/or the stream (a) comprises cations whose concentration is 0.001-6 mol cation/L.
4. The method of claim 1 , wherein the stream (b) comprises at least one species selected from the group consisting of NaOH, Na 2 CO 3 , NaHCO 3 , Na 2 C 2 O 4 , LiOH, Li 2 CO 3 , LiHCO 3 , Li 2 C 2 O 4 , KOH, K 2 CO 3 , KHCO 3 , K 2 C 2 O 4 , or combination of the species.
5. The method of claim 1 , wherein the first anion composition B 1 is hydroxide salts, the second anion composition B 2 is at least one selected from the group consisting of carbonate, oxalate, or combination thereof.
6. The method of claim 1 , wherein the first switching time when switching the first anion composition B 1 to the second anion composition B 2 is greater than 50% of the reaction time.
7. The method of claim 1 , wherein the stream (a) comprises a first cation composition A 1 and a second cation composition A 2 , the first cation composition A 1 is gradually or abruptly switched to the second cation composition A 2 at a second switching time between the time the co-precipitation starts and the time the reaction ends.
8. The method of claim 7 , wherein the second switching time coincides with the first switching time, or the second switching time is different from the first switching time.
9. The method of claim 7 , wherein the first cation composition A 1 is the same as the second cation composition A 2 .
10. The method of claim 7 , wherein the first cation composition A 1 and the second cation composition A 2 has a cation ratio of Ni x Mn y Co z Me 1-x-y-z , where x+y+z≥0.9, z≤0.2, “Me” is at least one additional metal elements selected from the group consisting of Mg, Ca, Zr, Ti, V, Cr, Fe, Cu and Al.
11. The method of claim 10 , wherein the first cation composition A 1 has a cation ratio of Ni x Mn y Co z Me 1-x-y-z , where x+y+z≥0.9, 0.75≤x≤1; 0≤z≤0.1; the second cation composition A 2 has a cation ratio of Ni x Mn y Co z Me 1-x-y-z , where x+y+z≥0.9, 0.3≤x≤0.7; 0.25≤y≤0.5, Me is at least one additional metal elements selected from the group consisting of Mg, Ca, Zr, Ti, V, Cr, Fe, Cu and Al.
12. The method of claim 1 , wherein a pH during the reaction is 7-13 and a temperature during the reaction is 30-800° C.
13. The method of claim 1 , further comprising a step of feeding stream (c) into the reactor for providing ammonia.
14. A method for preparing cathode active particles, comprising the following steps:
preparing the particle precursor by the method of claim 1 ;
mixing the particle precursor with a lithium source to form a mixture; and
calcining the mixture to yield the cathode active particles;
the lithium source is at least one selected from the group consisting of lithium hydroxide, LiOH·H 2 O, lithium carbonate, LiNO 3 , lithium acetate, lithium metal and Li 2 O; and/or a mole ratio between Li from the lithium source and the metal cation from the stream (a) is in a range of 0.5-1.5.
15. The method of claim 14 , wherein the calcination is under a temperature of 300-9500° C.; and/or under atmosphere selected from N 2 , air, dried air, oxygen, or combination thereof.
16. The method of claim 1 , wherein the stream (a) provides at least one cation selected from the group consisting of Mg, Ca, Zr, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Al, or combination thereof, the anion provided by stream (a) is in a form of sulfate, carbonate, chloride, nitrate, fluoride, oxide, hydroxide, oxyhydroxide, oxalate, carboxylate, acetate, phosphate or borate.